CN1115348C - Polyolefin catalyst containing azabenzene in ligand and its preparing process and application - Google Patents
Polyolefin catalyst containing azabenzene in ligand and its preparing process and application Download PDFInfo
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- CN1115348C CN1115348C CN 00109743 CN00109743A CN1115348C CN 1115348 C CN1115348 C CN 1115348C CN 00109743 CN00109743 CN 00109743 CN 00109743 A CN00109743 A CN 00109743A CN 1115348 C CN1115348 C CN 1115348C
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Abstract
The present invention relates to a catalyst for olefin polymerization. The catalyst for olefin polymerization has a general formula expression of [N, N]MXn, wherein [N, N] in the expression has a structural formula of pyridinium-2-acylimine derivative; R1 and R2 in the expression are respectively selected from hydrogen, an alkyl group of C1 to C6, and a perfluoroalkyl group of C1 to C6 or an aralkyl group of C7 to C14; R3 is selected from the hydrogen, the alkyl group of C1 to C6, and the perfluoroalkyl group of C1 to C6 or the aralkyl group of C7 to C14; one or many substituent groups are arranged on pyridine and a benzene ring. M in the general formula expression is selected from the transitional metal of an IVB group or a VB group, n is an integer of 2 to 5, X is selected from halogen, oxygen, an alkyl group of C1 to C24, an alkoxyl group, a silica group or the aralkyl group, and X can be selected from the same components or different components. The catalyst is matched with cocatalyst alkyl aluminum oxygen alkane, and a polyolefin product with high molecular weight can be prepared.
Description
Technical field
The present invention is a kind of olefin polymerization catalysis and preparation method thereof and application, specifically, be the transition metal compound catalizer and preparation method thereof that contains pyridine in a kind of part with olefinic polymerization in application.
Background technology
After metallocene catalyst successfully was used for polyolefin industry production, a kind of was the transition metal complex of part with the heteroatomic compound, and promptly Nonmetallocene polyolefine catalyst is developed rapidly.As USP5,539,124 disclose a kind of transition metal compound catalizer that contains pyrrole ring, this catalyzer uses pyrroles, indoles, carbazole or their alkyl substituent as part, with central atom titanium or zirconium coordination, under promotor methylaluminoxane (MAO) effect, make alpha-olefin, carry out homopolymerization or copolymerization as ethene.
CN1,181,089 disclose the catalyst system of a class transistion metal compound and other promotor composition, and this system is used to prepare the homopolymerization or the multipolymer of alpha-olefin.Wherein, the nickel compound by selected alpha-diimine part can be used for ethylene oligomerization with the selected Lewis or the mixture of Bronsted acid as catalyst system, or the synthetic line style alpha-olefinic polymer of the alpha-nickel diimine compound in the selecting catalyst system.The C that obtains by this catalyst system
4～C
20Ethylene low polymer in, contain the alpha-olefin more than 90%, its product wider distribution.In addition, this class catalyst system also can be used for producing the polyethylene of higher molecular weight.
USP5; 932; 670 disclose a kind of pyridine-2-acyl group imines dihalide nickel (2-pyridinecarboxaldimime nickel dihalide) title complex; contain two six-rings in this complex ligand; one is the phenyl ring that links to each other with the imido grpup nitrogen-atoms, and another is the azepine phenyl ring (pyridine ring) that links to each other with the imido grpup carbon atom, in addition; also can be connected with substituent R on the imido grpup carbon atom, R is the alkyl or aryl of 1～70 carbon atom.This title complex can be used as the Primary Catalysts of olefinic polymerization, need use organoaluminum to be promotor during polymerization.When this title complex is used for polymerization,,, be promotor with MAO, then can only prepare the low oligopolymer of molecular weight if be catalyzer with the homogeneous phase title complex if make loaded catalyst then can prepare low-molecular-weight polymkeric substance.
Summary of the invention
The purpose of this invention is to provide the transition metal compound catalizer that contains pyridine in a kind of part, this catalyzer can make olefinic polymerization produce high-molecular weight polymer.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
A further object of the present invention provides the application of above-mentioned catalyzer in olefinic polymerization.
We find; the condenses that 2-formaldehyde pyridine compounds and their or 2-acyl pyridine compounds and amino benzenes derivates reaction generate can be used as part and transition metal halide forms title complex; pyridine in the described part can make transition metal complex more stable, and in the part on the phenyl ring substituent kind and position its catalytic activity and molecular weight of product are distributed with considerable influence.Substituting group on phenyl ring is in the time of 2,6, and group is when big, and what catalyzer had is active higher.In addition, the kind of promotor and consumption also influence the distribution of activity of such catalysts and molecular weight of product.After finding above-mentioned title complex and its characteristic in olefinic polymerization, finished the present invention.
Specifically, olefin polymerization catalysis provided by the invention, the general expression that has is: [N, N] MX
n, [N, N] is for having the pyridine-2-acyl group imine derivative of following structural formula in the formula:
On pyridine and the phenyl ring one or more substituting group can be arranged in the described structural formula, single substituting group on pyridine and the phenyl ring or multi-substituent R
1And R
2Be selected from hydrogen, C independently of one another
1～C
6Alkyl, C
1～C
6Perfluoroalkyl or C
7～C
14Aralkyl, R
3Be selected from hydrogen, C
1～C
6Alkyl, C
1～C
6Perfluoroalkyl or C
7～C
14Aralkyl; M in the described general expression is selected from the transition metal of IVB family or VB family, preferred titanium, zirconium or vanadium; N is 2～5 integer; X is selected from halogen, oxygen, C
1～C
24Alkyl, alkoxyl group, siloxy or aralkyl, can be identical or different, preferred chlorine, bromine, C
1～C
12Alkyl or alkoxyl group.
In described part pyridine-2-acyl group imine derivative [N, N], be positioned at the substituent R on the pyridine
1Preferred hydrogen, C
1～C
4Alkyl, C
1～C
4Perfluoroalkyl or C
7～C
14Aralkyl, substituent number can have a plurality of, is preferably 1～3, its position preferably is positioned at 4 or 6 of pyridine.Substituent R on the phenyl ring
2Preferred C
1～C
4Alkyl, C
1～C
4Perfluoroalkyl or C
7～C
14Aralkyl, substituent number can have a plurality of, has been preferably 1～3 substituting group, its position preferably is positioned at 2,4,6 of phenyl ring.Above-mentioned R
1And R
2More preferably hydrogen, methyl, ethyl, propyl group, butyl, phenyl or benzyl.Described R
3Preferred hydrogen, C
1～C
4Alkyl, C
1～C
4Perfluoroalkyl or C
7～C
14Aralkyl, be preferably hydrogen, C
1～C
4Alkyl, C
1～C
4Perfluoroalkyl or benzyl, be preferably hydrogen, methyl, phenyl or benzyl.
[N, N] object lesson of indefiniteness of part has: N-(2-ethylphenyl) pyridine-2-formaldehyde imines, N-(2-n-propyl phenyl) pyridine-2-formaldehyde imines, N-(2-isopropyl phenyl) pyridine-2-formaldehyde imines, N-(2-n-butylphenyl) pyridine-2-formaldehyde imines, N-(2-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-benzyl phenyl) pyridine-2-formaldehyde imines;
N-(2, the 6-3,5-dimethylphenyl) pyridine-2-formaldehyde imines, N-(2,6-diethyl phenyl) pyridine-2-formaldehyde imines, N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines, N-(2,6-diisobutyl phenyl) pyridine-2-formaldehyde imines, N-(2, the 6-di-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2,6-dibenzyl phenyl) pyridine-2-formaldehyde imines, N-(2, the 4-3,5-dimethylphenyl) pyridine-2-formaldehyde imines, N-(2,4-diethyl phenyl) pyridine-2-formaldehyde imines, N-(2, the 4-diisopropyl phenyl) pyridine-2-formaldehyde imines, N-(2,4-diisobutyl phenyl) pyridine-2-formaldehyde imines, N-(2, the 4-di-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2,4-dibenzyl phenyl) pyridine-2-formaldehyde imines;
N-(2-methyl-6-ethylphenyl) pyridine-2-formaldehyde imines, N-(2-methyl-6-isopropyl phenyl) pyridine-2-formaldehyde imines, N-(2-methyl-6-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-methyl-6-tert butyl phenyl) pyridine-2-formaldehyde imines, N-(2-methyl-6-benzyl phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-6-isopropyl phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-6-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-6-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-6-benzyl phenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-6-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-6-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-6-benzyl phenyl) pyridine-2-formaldehyde imines, N-(2-isobutyl--6-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-isobutyl--6-benzyl phenyl) pyridine-2-formaldehyde imines, N-(the 2-tertiary butyl-6-benzyl phenyl) pyridine-2-formaldehyde imines;
N-(2-methyl-4-ethylphenyl) pyridine-2-formaldehyde imines, N-(2-methyl-4-isopropyl phenyl) pyridine-2-formaldehyde imines, N-(2-methyl-4-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-methyl-4-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-methyl-4-benzyl phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-4-isopropyl phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-4-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-4-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-4-benzyl phenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-4-isobutyl phenenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-4-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-4-benzyl phenyl) pyridine-2-formaldehyde imines, N-(2-isobutyl--4-tert-butyl-phenyl) pyridine-2-formaldehyde imines, N-(2-isobutyl--4-benzyl phenyl) pyridine-2-formaldehyde imines, N-(the 2-tertiary butyl-4-benzyl phenyl) pyridine-2-formaldehyde imines;
N-(2,4, the 6-trimethylphenyl) pyridine-2-formaldehyde imines, N-(2,4,6-triethyl phenyl) pyridine-2-formaldehyde imines, N-(2,4,6-triisopropyl phenyl) pyridine-2-formaldehyde imines, N-(2,4,6-triisobutyl phenyl) pyridine-2-formaldehyde imines, N-(2,4,6-tri-tert phenyl) the pyridine-2-formaldehyde imines, N-(2,4,6-dibenzyl phenyl) pyridine-2-formaldehyde imines, N-(2-methyl-4,6-diethyl phenyl) pyridine-2-formaldehyde imines, N-(2-ethyl-4, the 6-3,5-dimethylphenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-4,6-3,5-dimethylphenyl) pyridine-2-formaldehyde imines, N-(2-sec.-propyl-4,6-diethyl phenyl) pyridine-2-formaldehyde imines, N-(2,4-two different base-6-aminomethyl phenyls) pyridine-2-formaldehyde imines, N-(2,4-di-t-butyl-6-aminomethyl phenyl) pyridine-2-formaldehyde imines, N-(2,4-dibenzyl-6-aminomethyl phenyl) pyridine-2-formaldehyde imines.
N-(2, the 6-3,5-dimethylphenyl) pyridine-2-acetimide, N-(2,6-diethyl phenyl) pyridine-2-acetimide, N-(2, the 6-diisopropyl phenyl) pyridine-2-acetimide, N-(2,6-diisobutyl phenyl) pyridine-2-acetimide, N-(2, the 6-di-tert-butyl-phenyl) pyridine-2-acetimide, N-(2,6-dibenzyl phenyl) pyridine-2-acetimide, N-(2, the 4-3,5-dimethylphenyl) pyridine-2-acetimide, N-(2,4-diethyl phenyl) pyridine-2-acetimide, N-(2, the 4-diisopropyl phenyl) pyridine-2-acetimide, N-(2,4-diisobutyl phenyl) pyridine-2-acetimide, N-(2, the 4-di-tert-butyl-phenyl) pyridine-2-acetimide, N-(2,4-dibenzyl phenyl) pyridine-2-acetimide;
N-(2,4, the 6-trimethylphenyl) pyridine-2-acetimide, N-(2,4,6-triethyl phenyl) pyridine-2-acetimide, N-(2,4,6-triisopropyl phenyl) pyridine-2-acetimide, N-(2,4,6-triisobutyl phenyl) pyridine-2-acetimide, N-(2,4,6-tri-tert phenyl) pyridine-2-acetimide, N-(2,4,6-dibenzyl phenyl) pyridine-2-acetimide, N-(2-methyl-4,6-diethyl phenyl) pyridine-2-acetimide, N-(2-ethyl-4, the 6-3,5-dimethylphenyl) pyridine-2-acetimide, N-(2-sec.-propyl-4,6-3,5-dimethylphenyl) pyridine-2-acetimide, N-(2-sec.-propyl-4,6-diethyl phenyl) pyridine-2-acetimide, N-(2,4-two different base-6-aminomethyl phenyls) pyridine-2-acetimide, N-(2,4-di-t-butyl-6-aminomethyl phenyl) pyridine-2-acetimide, N-(2,4-dibenzyl-6-aminomethyl phenyl) pyridine-2-acetimide.
N-(2, the 6-3,5-dimethylphenyl) pyridine-2-benzoyl imines, N-(2,6-diethyl phenyl) pyridine-2-benzoyl imines, N-(2, the 6-diisopropyl phenyl) pyridine-2-benzoyl imines, N-(2,6-diisobutyl phenyl) pyridine-2-benzoyl imines, N-(2, the 6-di-tert-butyl-phenyl) pyridine-2-benzoyl imines, N-(2,6-dibenzyl phenyl) pyridine-2-benzoyl imines, N-(2, the 4-3,5-dimethylphenyl) pyridine-2-benzoyl imines, N-(2,4-diethyl phenyl) pyridine-2-benzoyl imines, N-(2, the 4-diisopropyl phenyl) pyridine-2-benzoyl imines, N-(2,4-diisobutyl phenyl) pyridine-2-benzoyl imines, N-(2, the 4-di-tert-butyl-phenyl) pyridine-2-benzoyl imines, N-(2,4-dibenzyl phenyl) pyridine-2-benzoyl imines;
N-(2,4, the 6-trimethylphenyl) pyridine-2-benzoyl imines, N-(2,4,6-triethyl phenyl) pyridine-2-benzoyl imines, N-(2,4,6-triisopropyl phenyl) pyridine-2-benzoyl imines, N-(2,4,6-triisobutyl phenyl) pyridine-2-benzoyl imines, N-(2,4,6-tri-tert phenyl) pyridine-2-benzoyl imines, N-(2,4,6-dibenzyl phenyl) pyridine-2-benzoyl imines, N-(2-methyl-4,6-diethyl phenyl) pyridine-2-benzoyl imines, N-(2-ethyl-4, the 6-3,5-dimethylphenyl) pyridine-2-benzoyl imines, N-(2-sec.-propyl-4,6-3,5-dimethylphenyl) pyridine-2-benzoyl imines, N-(2-sec.-propyl-4,6-diethyl phenyl) pyridine-2-benzoyl imines, N-(2,4-two different base-6-aminomethyl phenyls) pyridine-2-benzoyl imines, N-(2,4-di-t-butyl-6-aminomethyl phenyl) pyridine-2-benzoyl imines, N-(2,4-dibenzyl-6-aminomethyl phenyl) pyridine-2-benzoyl imines.
Catalyzer of the present invention is pyridine-2-acyl group imine derivative and transistion metal compound MX
nThe title complex that forms, [N, the N] part that preferred above-mentioned indefiniteness exemplifies and the halogenide or the oxyhalogenide of titanium, zirconium or vanadium are as TiCl
4, ZrCl
4, VCl
3, VCl
4Or VOCl
3The title complex that forms.
Catalyzer of the present invention can adopt following method preparation, and this method comprises:
(1) with transistion metal compound MX
nMix with excessive ether solvent, be heated to reflux temperature and fully contact, collect solid and dry, obtain the adducts of transistion metal compound and ether solvents.
(2) in organic solvent, the adducts that makes and pyridine-2-acyl group imine derivative [N, N] such as are pressed at amount contact reacts under reflux temperature of mol ratio, the solid-liquid phase is separated in the cooling back, and solid drying is promptly got catalyzer [N, N] MX
n
In the step of method for preparing adducts (1), MX
nWith the weight ratio of ether solvent be 1: 10～30 times, in preferred 0.5～24 hour of the reaction times under reflux temperature, be preferably 1～10 hour.In (2) step, the amount of organic solvent should be 10～30 times of reactant gross weight, in preferred 1～96 hour of the reaction times of reactant under reflux temperature, is preferably 2～72 hours.Reaction finishes, and treats system cooling back separate solid from system, and is drying to obtain catalyzer at 10～100 ℃.Can adopt the washing or the method for recrystallization further to improve the purity of catalyzer, the solvent of washing or recrystallization adopts C
4～C
12Alkane or halohydrocarbon, or C
4～C
12The mixture and the ethers of alkane, as pentane, hexane, sherwood oil, methylene dichloride, chloroform, ether.
Described preparation method (1) used preferred tetrahydrofuran (THF) of ether solvent or glycol dimethyl ether of step.In addition, also can adopt beta-diketon or 'beta '-ketoester compounds and MX
nReaction generates adducts, and generates catalyzer with this adducts and pyridine-2-acyl group imine derivative.
Catalyzer of the present invention also can be prepared by second method, promptly directly by MX
nAnd pyridine-2-acyl group imine derivative [N, N] ligand compound by etc. the amount of mol ratio in organic solvent, react and be prepared, reaction finishes, and collects solid and also is drying to obtain catalyzer.
10～30 times of temperature of reaction that the amount of organic solvent preferably is controlled at the reactant gross weight in second kind of preparation method are-80～100 ℃, preferred 0～50 ℃; Preferred 1～96 hour of reaction times was preferably 2～72 hours, after having reacted, can adopt evaporating solvent or filtering method to separate the solid-liquid phase.Method with washing or recrystallization improves catalyzer purity.
Organic solvent described in the above-mentioned preparation catalyzer method is C
1～C
4Alcohol, C
6～C
12Aromatic hydroxy compound, particular methanol, ethanol, toluene or dimethylbenzene, wherein organic solvent also can be selected acetonitrile for use in second kind of preparation method.If gained catalyzer [N, N] MX
nBe dissolved in solvent, the most handy toluene of solid catalyst or the C that obtain after then solvent being removed
4～C
12Alkane wash.
Pyridine in the described method-2-acyl group imine derivative [N; N] can be synthetic by the method that those skilled in the art are familiar with; mix as 2-formaldehyde pyridines or 2-acyl pyridine compounds are added in the organic solvents with anils 1: 1 in molar ratio～1.5, organic solvent is C
4～C
12Alcohol, or C
6～C
12Compound fragrant hydrocarbon, as methyl alcohol, ethanol, toluene, dimethylbenzene.Add a small amount of organic aliphatic acid or sulfonic compound such as formic acid then in mixture, p-methyl benzenesulfonic acid etc. are heated to the abundant contact reacts of reflux temperature as catalyzer, separate the solid-liquid phase then, and dry gained solid promptly gets [N, N] ligand compound.The amount of organic solvent should be 10～30 times of reactant weight in this preparation process, the reflux temperature is generally 30～90 ℃, reaction times was generally 1～96 hour, and preferred 2～72 hours, the most handy aforesaid low-carbon alkanes of the solid that obtains after the reaction or halohydrocarbon carried out recrystallization.
Contain one or more substituent R on the 2-formaldehyde pyridines that above-mentioned preparation [N, N] part is used or the pyridine of 2-acyl pyridine compounds
1, its position preferably is positioned at 4 or 6 of pyridine.Can contain one or more substituent R equally on the phenyl ring of used anils
2, its position of substitution preferably is positioned at 2,4,6 of phenyl ring.The alkyl that above-mentioned 2-acyl pyridine compounds links to each other with carbonyl is R
3R wherein
1, R
2, R
3Identical with the implication in [N, N] ligand structure formula.In addition, used MX in the catalyst preparation process
nIn each symbol implication also with the catalyzer expression formula.
Catalyzer of the present invention is applicable to the homopolymerization and the copolymerization of alpha-olefin, needing with aikyiaiurnirsoxan beta, aluminum alkyls, alkyl aluminum halide or their mixture during polymerization is promotor, during polymerization in the promotor mol ratio of aluminium and transition metal be 5～5000, preferred 10～2500, be preferably 20～1000.Polymeric reaction condition is 0～200 ℃, is preferably 20～100 ℃; Pressure is 0.01～10.0MPa, preferred 0.1～5.0MPa.
Described promotor preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, a Chlorodimethyl aluminium, aluminium diethyl monochloride or any two or more the mixture in them.
Be used for the preferred C of polymeric 'alpha '-olefin monomers
2～C
14Alkene is as ethene, propylene, vinylbenzene or the mixture of the two arbitrarily between them.Polyolefin products such as polyethylene or polystyrene be can produce with catalyzer of the present invention, ethene and other alpha-olefin also can be produced, as the copolymerized product of propylene, butylene, hexene.
Polymerization technique can adopt solution polymerization, and as slurry polymerization, the solvent during polymerization can be selected organic solvents such as alkane, aromatic hydrocarbons or halogenated alkane for use.Also available catalyzer of the present invention adopts the gas phase bulk technique to produce olefin polymer.
Catalyst ligand of the present invention is pyridine-2-acyl group imine derivative, between two nitrogen-atoms wherein conjugated link(age) is arranged, and the lone-pair electron of two nitrogen-atoms can form stable bidentate title complex with transition metal.Because the central ion of catalyzer of the present invention is IVB or VB group 4 transition metal, disclosed with USP5932670 is that the catalyzer of coordination center is compared with nickel, can make the high polyolefine of the polymerization degree, and the consumption of promotor is less.Under the same conditions, the poly weight-average molecular weight that makes with catalyzer of the present invention can reach more than 1,000,000, and is the catalyzer of coordination center with nickel, can only make ethylene oligomer or molecular weight and be 20,000 oligopolymer.
Embodiment
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Preparation N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines vanadium trichloride [(
iPr
2Ph) PyH] VCl
3
(1) preparation N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines (
iPr
2Ph) PyH
With 2 of 10 mmoles, 6-diisopropyl aniline (Sweden, ACR S company) is dissolved in 20 ml methanol, adds the 2-pyridylaldehyde (Sweden, ACR S company) of 10 mmoles, adds 5 formic acid again.Be heated to 65 ℃ and refluxed 3 hours, be cooled to room temperature, under reduced pressure remove and desolvate, the gained solid is chilled to-50 ℃, wash twice, 30 ℃ of vacuum-drying with 10 milliliters-30 ℃ ethanol, 1.8 restrain N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines [(
iPr
2Ph) PyH], productive rate is 68 heavy %.
(2) preparation vanadium trichloride glycol dimethyl ether adducts [VCl
31.5DME]
1.5 gram vanadium trichlorides (Sweden, ACR S company) are added in 25 milliliters of glycol dimethyl ethers (Sweden, ACR S company), and 80 ℃ of stirrings refluxed 6 hours down.Be cooled to room temperature, filter, the gained solid washes twice with 10 milliliters of exsiccant hexanes, and vacuum-drying gets 2.6 gram red solid VCl
31.5DME.
(3) preparation catalyzer
With 1 mmole VCl
31.5DME be dissolved in 10 milliliters of methylene dichloride, stir and to add 10 milliliters of dichloromethane solutions that contain 1.05 mmole N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines down.Be heated to 80 ℃ and refluxed 12 hours, cooling is filtered, and the gained solid is respectively washed once with 5 milliliters of ether and hexane respectively, 30 ℃ of vacuum-dryings, 0.4 restrain catalyst A [(
iPr
2Ph) PyH] VCl
3, productive rate is 85 heavy %.The ultimate analysis value of catalyst A is (heavy %): vanadium 11.89, carbon 51.65, hydrogen 5.68, nitrogen 6.96.Infrared spectrum is presented at 1628.1cm
-1The characteristic peak of C=N appears in the place.
Example 2
Preparation N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines titanium tetrachloride [(
iPr
2Ph) PyH] TiCl
4
(1) preparation titanium tetrachloride tetrahydrofuran (THF) adducts [TiCl
42THF]
Ice bath also stirs down, splashes into the tetrahydrofuran (THF) of 4.5 mmoles in 20 milliliters of toluene solutions that contain 2.1 mmole titanium tetrachlorides, and room temperature reaction 4 hours filters, 30 ℃ of vacuum-drying 2 hours, 0.68 gram yellow solid TiCl
42THF, productive rate are 97 heavy %.
(2) preparation catalyzer
TiCl with 2.1 mmoles
42THF is added in 20 milliliters of methylene dichloride, stirring and dissolving, add again contain 2.1 mmoles (
iPr
2Ph) dichloromethane solution of PyH is 10 milliliters, and 25 ℃ were refluxed 18 hours down, and cooling is filtered, and solid is washed twice, 30 ℃ of vacuum-drying 2 hours with 10 milliliters of ether respectively, gets 0.72 gram yellow-green colour solid catalyst B[(
iPr
2Ph) PyH] TiCl
4, productive rate is 75 heavy %.
The ultimate analysis value of catalyst B is (heavy %): titanium 9.68, carbon 48.31, hydrogen 5.11, nitrogen 5.93.Infrared spectrum is presented at 1627.2cm
-1The characteristic peak of C=N appears in the place.
Example 3
Preparation N-(2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines zirconium tetrachloride [(
iPr
2Ph) PyH] ZrCl
4
(1) preparation zirconium tetrachloride tetrahydrofuran (THF) adducts [ZrCl
42THF]
Stir down, splash into the tetrahydrofuran (THF) of 4.1 mmoles in 20 milliliters of toluene solutions that contain 2 mmole zirconium tetrachlorides, 60 ℃ were reacted 4 hours, filtered, and solid gets 0.72 gram yellow solid ZrCl 30 ℃ of vacuum-dryings 2 hours
42THF.
(2) preparation catalyzer
With 2 mmole ZrCl
42THF adds in 20 milliliters of methylene dichloride, stirring and dissolving, add again contain 2.1 mmoles (
iPr
2Ph) dichloromethane solution of PyH is 10 milliliters, and 25 ℃ were refluxed 18 hours down, and cooling is filtered, and solid is washed twice, 30 ℃ of vacuum-drying 2 hours with 10 milliliters of ether respectively, gets 0.84 gram yellow solid catalyzer C[(
iPr
2Ph) PyH] ZrCl
4, productive rate is 82 heavy %.
The ultimate analysis value of catalyzer C is (heavy %): zirconium 16.78, carbon 43.64, hydrogen 4.96, nitrogen 4.92.Infrared spectrum is presented at 1626.5cm
-1The characteristic peak of C=N appears in the place.
Example 4
Preparation N-(2, the 6-diisopropyl phenyl)-6-picoline-2-formaldehyde imines vanadium trichloride [(
iPr
2Ph)-and MePyH] VCl
3
(1) preparation N-(2, the 6-diisopropyl phenyl)-6-picoline-2-formaldehyde imines (
iPr
2Ph)-MePyH
With 2 of 10 mmoles, the 6-diisopropyl aniline is dissolved in 20 ml methanol, adds the 6-picoline-2-formaldehyde (Sweden, ACR S company) of 10 mmoles, adds 5 formic acid again.Be heated to 60 ℃ and refluxed 4 hours, be cooled to room temperature, under reduced pressure remove and desolvate, the gained solid is chilled to-50 ℃, wash twice, 30 ℃ of vacuum-drying with 10 milliliters-30 ℃ ethanol, 2.0 restrain (
iPr
2Ph)-and MePyH, productive rate is 71 heavy %.
(2) preparation catalyzer
With 1 mmole VCl
31.5DME be dissolved in 10 milliliters of methylene dichloride, stir, add again contain 1.05 mmoles (
iPr
2Ph)-10 milliliters of the dichloromethane solutions of 6-MePyH.Be heated to 80 ℃ and refluxed 12 hours, cooling is filtered, and the gained solid is respectively washed once with 5 milliliters of ether and hexane respectively, and 30 ℃ of vacuum-dryings get 0.39 gram solid catalyst D[(
iPr
2Ph)-and 6-MePyH] VCl
3, productive rate is 89 heavy %.
The ultimate analysis value of catalyzer D is (heavy %): vanadium 10.95, carbon 52.60, hydrogen 5.90, nitrogen 6.13.Infrared spectrum is presented at 1628.7cm
-1The characteristic peak of C=N appears in the place.
Example 5
Preparation N-(2,4, the 6-trimethylphenyl) pyridine-2-formaldehyde imines vanadium trichloride ([(Me
3Ph) PyH] VCl
3).
(1) preparation N-(2,4, the 6-trimethylphenyl) pyridine-2-formaldehyde imines ((Me
3Ph) PyH)
The 2 (Sweden, ACR S company) of 10 mmoles is dissolved in 20 ml methanol, adds the 2-pyridylaldehyde of 10 mmoles, add 5 formic acid again.Be heated to 45 ℃ and refluxed 36 hours, be cooled to room temperature, under reduced pressure remove and desolvate, the gained solid is chilled to-50 ℃, wash twice, 30 ℃ of vacuum-drying, get 1.3 gram (Me with 10 milliliters-30 ℃ ethanol
3Ph) PyH, productive rate are 60 heavy %.
(2) preparation catalyzer
With 1 mmole VCl
3Be added in 10 milliliters of second eyeballs, stirring down, adding contains 1.05 mmole (Me
3Ph) the second eyeball solution of PyH is 10 milliliters.Be heated to 80 ℃ and refluxed 24 hours, cooling is filtered, and the gained solid is respectively washed once with 5 milliliters of ether and hexane respectively, and 30 ℃ of vacuum-dryings get 0.35 gram solid catalyst E[(Me
3Ph) PyH] VCl
3, productive rate is 92 heavy %.
The ultimate analysis value of catalyzer E is (heavy %): vanadium 12.78, carbon 47.64, hydrogen 4.76, nitrogen 7.92.Infrared spectrum is presented at 1628.9cm
-1The characteristic peak of C=N appears in the place.
Example 6～10
Following example carries out polyreaction with catalyzer of the present invention, the preparation polyethylene.
Adopt the normal pressure slurry polymerization.Used promotor is that the concentration of U.S. Albemarle company production methylaluminoxane (MAO) is the toluene solution of 10 heavy %.
With 250 milliliters of reaction flask nitrogen replacement three times that agitator is housed, with ethene displacement twice, feed ethene again, add 50 milliliters of exsiccant toluene.Stir down and be warming up to 30 ℃, the toluene solution of adding MAO adds reaction flask after catalyzer is dissolved in a certain amount of MAO toluene solution, and catalyst consumption is 1.0 * 10
-5Mole, it is 500: 1 that total consumption of MAO toluene solution should make Al/M.30 ℃ were reacted 0.5 hour, used excess ethyl alcohol earlier then, used the small amount of hydrochloric acid termination reaction again.Reactant was continued to stir in excess ethyl alcohol 1 hour, filters, and use ethanol, water, washing with alcohol polymerisate successively, 60 ℃ of following vacuum-drying 4 hours, polymkeric substance.Each example catalyst system therefor and activity and polymer property see Table 1.Polymkeric substance weight-average molecular weight Mw and molecular weight distribution M
w/ M
nIs the solvent gel chromatography at 135 ℃ with the orthodichlorobenzene, and used chromatographic instrument model is PL-GPC200 (production of Britain polymer laboratories company).
Comparative Examples 1
With the disclosed N-of USP5932670 (2, the 6-diisopropyl phenyl) pyridine-2-formaldehyde imines Nickel Bromide [(
iPr
2Ph) PyH] NiBr
2Be catalyzer, be numbered K.Method and condition according to example 6 are carried out polyreaction, and the result has only absorbed 170 milliliters of ethylene gas, and catalyst activity is lower.
Comparative Examples 2
With the disclosed N-of USP5932670 (2, the 6-diisopropyl phenyl)-6-methyl-pyridine-2-formaldehyde imines Nickel Bromide [(
iPr
2Ph) MePyH] NiBr
2Be catalyzer, be numbered L.Method and condition according to example 6 are carried out polyreaction, and the result only absorbs the ethylene gas of trace, and catalyst activity sees Table 1.
Table 1
| Instance number | The catalyzer numbering | The catalyzer skeleton symbol | Catalyst activity when mole M (gram polyethylene /) | Mw， (×10 4) | M w/M n |
| 6 | A | [( iPr 2Ph)PyH]VCl 3 | 1.2×10 5 | 105 | 6.96 |
| 7 | B | [( iPr 2Ph)PyH]TiCl 4 | 1.3×10 5 | 121 | 20.46 |
| 8 | C | [( iPr 2Ph)PyH]ZrCl 4 | 3.2×10 4 | 93 | 15.78 |
| 9 | D | [( iPr 2Ph)-MePyH]VCl 3 | 2.6×10 4 | 112 | 7.45 |
| 10 | E | [(Me 3Ph)PyH]VCl 3 | 1.2×10 5 | 103 | 6.51 |
| Comparative Examples 1 | K | [( iPr 2Ph)PyH]NiBr 2 | 4.4×10 4 | Oligopolymer | - |
| Comparative Examples 2 | L | [( iPr 2Ph)-MePyH]NiBr 2 | 40 | Oligopolymer | - |
M in table 1 and the example 6～10 represents vanadium, titanium or zirconium
Claims (15)
1, a kind of olefin polymerization catalysis, the general expression that has is: [N, N] MX
n, [N, N] is for having the pyridine-2-acyl group imine derivative of following structural formula in the formula:
On pyridine and the phenyl ring one or more substituting group can be arranged in the described structural formula, single substituting group on pyridine and the phenyl ring or multi-substituent R
1And R
2Be selected from hydrogen or C independently of one another
1～C
6Alkyl, R
3Be selected from hydrogen or C
1～C
6Alkyl;
M in the described general expression is selected from the transition metal of IVB family or VB family,
N is 2～5 integer,
X is selected from halogen.
2, according to the described catalyzer of claim 1, it is characterized in that described R
1, R
2And R
3Be selected from hydrogen or C respectively
1～C
4Alkyl, M is selected from titanium, zirconium or vanadium, X is selected from chlorine or bromine.
3, according to the described catalyzer of claim 1, it is characterized in that described R
1Be methyl, and be positioned at 4 or 6 of pyridine, R
2Be C
1～C
4Alkyl, and be positioned at 2,4 or 6 of phenyl ring, R
3Be hydrogen or C
1～C
4Alkyl.
4,, it is characterized in that 1～3 substituting group, described substituent R are arranged on pyridine and the phenyl ring according to claim 1 or 3 described catalyzer
1And R
2Be selected from methyl, ethyl, propyl group or butyl respectively, R
3Be hydrogen or methyl.
5, the described Preparation of catalysts method of a kind of claim 1 comprises:
(1) with transistion metal compound MX
nMix with excessive ether solvent, be heated to reflux temperature and fully contact, collect solid and dry, obtain the adducts of transistion metal compound and ether solvents, described MX
nMiddle M is selected from the transition metal of IVB family or VB family, and n is 2～5 integer, and X is selected from halogen,
(2) in organic solvent, the adducts that makes and pyridine-2-acyl group imine derivative [N, N] such as are pressed at amount contact reacts under reflux temperature of mol ratio, the solid-liquid phase is separated in the cooling back, and solid drying is promptly got catalyzer [N, N] MX
n, described pyridine-2-acyl group imine derivative [N, N] has following structural formula:
On pyridine and the phenyl ring one or more substituting group can be arranged in the described structural formula, single substituting group on pyridine and the phenyl ring or multi-substituent R
1And R
2Be selected from hydrogen or C independently of one another
1～C
6Alkyl, R
3Be selected from hydrogen or C
1～C
6Alkyl.
6, in accordance with the method for claim 5, it is characterized in that described organic solvent is C
1～C
4Alcohol, C
6～C
12Aromatic hydroxy compound.
7, in accordance with the method for claim 6, it is characterized in that described organic solvent is methyl alcohol, ethanol, toluene or dimethylbenzene.
8, in accordance with the method for claim 5, it is characterized in that used compound MX in (1) step
nBe selected from the halogenide of titanium, zirconium or vanadium.
9, in accordance with the method for claim 5, it is characterized in that described ether solvent is selected from tetrahydrofuran (THF) or ethylene glycol diether.
10, the described Preparation of catalysts method of a kind of claim 1 is included in the organic solvent, makes transistion metal compound MX
nAnd pyridine-2-acyl group imine derivative [N, N] the amount contact reacts of mol ratio such as presses, and makes catalyzer [N, N] MX
n, described MX
nMiddle M is selected from the transition metal of IVB family or VB family, and n is 2～5 integer, and X is selected from halogen, and described pyridine-2-acyl group imine derivative [N, N] has following structural formula:
On pyridine and the phenyl ring one or more substituting group can be arranged in the described structural formula, single substituting group on pyridine and the phenyl ring or multi-substituent R
1And R
2Be selected from hydrogen or C independently of one another
1～C
6Alkyl, R
3Be selected from hydrogen or C
1～C
6Alkyl.
11, in accordance with the method for claim 10, it is characterized in that described organic solvent is C
1～C
4Alcohol, C
6～C
12Aromatic hydroxy compound.
12, in accordance with the method for claim 11, it is characterized in that described organic solvent is ethanol, methyl alcohol, toluene or dimethylbenzene.
13, in accordance with the method for claim 10, it is characterized in that described MX
nBe selected from the halogenide of titanium, zirconium or vanadium.
14, a kind of olefine polymerizing process, comprise that with the described catalyzer of claim 1 be Primary Catalysts, with aikyiaiurnirsoxan beta, aluminum alkyls, alkyl aluminum halide or any two or more the mixture in them is promotor, make alpha-olefin polymerization under polymerizing condition, the Al/M mol ratio is 5～5000 during polymerization, and described M is selected from the transition metal of IVB family or VB family.
15, in accordance with the method for claim 14, it is characterized in that described aikyiaiurnirsoxan beta is a methylaluminoxane, aluminum alkyls is triethyl aluminum, triisobutyl aluminium, and alkyl aluminum halide is an aluminium diethyl monochloride, and the Al/M mol ratio is 20～1000 during polymerization.
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|---|---|---|---|
| CN 00109743 CN1115348C (en) | 2000-07-05 | 2000-07-05 | Polyolefin catalyst containing azabenzene in ligand and its preparing process and application |
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| CN101397349B (en) * | 2007-09-28 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Ti system wide/double peak olefin polymerization catalyst, preparation and use |
| RU2505549C2 (en) * | 2010-12-31 | 2014-01-27 | Открытое акционерное общество "СИБУР Холдинг" (ОАО "СИБУР Холдинг") | Vanadium catalyst system for copolymerisation of ethylene with alpha-olefins (versions) and method of producing ethylene and alpha-olefin copolymer (versions) |
| ITUB20155498A1 (en) | 2015-11-11 | 2017-05-11 | Versalis Spa | PYRIDIN-IMMINIC COMPLEX OF VANADIUM, CATALYTIC SYSTEM INCLUDING THE PIRIDIN-IMMINIC COMPLEX OF VANADIUM AND PROCEDURE FOR THE (CO) POLYMERISATION OF CONJUGATED DIENES. |
| CN114805429A (en) * | 2022-04-21 | 2022-07-29 | 中国科学院青岛生物能源与过程研究所 | Pyridine imine vanadium complex, preparation method thereof and application thereof in conjugated olefin polymerization |
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