CN106496366A - A kind of olefin polymerization catalysis and its application - Google Patents
A kind of olefin polymerization catalysis and its application Download PDFInfo
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- CN106496366A CN106496366A CN201510566353.2A CN201510566353A CN106496366A CN 106496366 A CN106496366 A CN 106496366A CN 201510566353 A CN201510566353 A CN 201510566353A CN 106496366 A CN106496366 A CN 106496366A
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Abstract
The invention provides a kind of catalyst for olefinic polyreaction, the catalyst includes：A. solid catalyst, which contains Mg, Ti, halogen and at least one internal electron donor compound containing lone pair electrons；B. alkyl aluminum compound；C. many first external electron donors, including first kind external electron donor c1 and Equations of The Second Kind external electron donor c2, described c1 is silane compound, and c2 is phosphoric acid siloxane compound.When the catalyst of the present invention is used for propylene polymerization, gratifying polymerization activity, and high vertical structure directionality not only can be obtained, and the hydrogen response of catalyst is higher.
Description
Technical field
The present invention relates to a kind of catalyst for olefines polymerizing, and in particular to one kind is containing silane and phosphoric acid siliconization
The catalyst for olefines polymerizing of compound compounding and its application.
Background technology
It is well known that using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basis,
Can be used for olefinic polyreaction, particularly can obtain in there is the alpha-olefine polymerizing of 3 carbon or more carbon atoms
To higher yields and the polymer of higher stereospecificity, wherein electron donor compound is ingredient of solid catalyst
In one of requisite composition, and result in polyolefin catalyst with the development of internal electron donor compound
The replacement is continuously updated, for the research of external electron donor is also progressively deeply.At present, disclose in a large number
Multiple electron donor compounds, such as internal electron donor monocarboxylic esters or multi-carboxylate, ketone, monoether or many
Ether, diol ester, amine etc. and its derivant, external electron donor monocarboxylic esters, amine, siloxanes, amino silane
Deng and its derivant.The electron donor that reported at present is mostly oxygen-containing, nitrogen phosphate and sulfur, the compound of silicon.
In these polymerization catalysts, electron donor is to activity, stereoselectivity, molecular weight distribution and polymer performance
There is different degrees of impact.
By the present invention in that being compounded as external electron donor with silane and phosphoric acid siloxanes, combination property is obtained excellent
Good olefin polymer, when for propylene polymerization, compared with prior art, the catalyst is higher except having
Active and preferable stereotaxises ability, can obtain the polymerization beyond the region of objective existence of high isotactic index, also improve catalyst
Hydrogen response.
Content of the invention
For deficiency of the prior art, the invention provides outer the giving of a kind of silane-containing and phosphoric acid siloxanes compounding
The catalyst of electron, the catalyst not only have good activity and stereotaxises good, are conducive to obtaining height
The polymer of isotacticity, and hydrogen response is higher.
According to an aspect of the invention, there is provided a kind of catalyst for olefinic polyreaction, the catalysis
Agent includes ingredient of solid catalyst A, alkyl aluminum B and polynary external electron donor C, the ingredient of solid catalyst
A, including Mg, Ti, halogen and at least one internal electron donor compound containing lone pair electrons；
Component B is alkyl aluminum compound；
Component C is polynary external electron donor, including giving electricity outside first kind external electron donor c1 and Equations of The Second Kind
Daughter c2.Described first kind external electron donor c1 is silane compound；The outer electron of described Equations of The Second Kind
Body c2 is phosphoric acid siloxane compound.
According to the present invention, the polynary outer electron compounded using silane compound and phosphoric acid siloxane compound
The catalyst of body system, with good activity, hydrogen response and stereoselectivity.
According to a specific embodiment of the present invention, described Equations of The Second Kind external electron donor c2 is preferably general formula
(I) the phosphoric acid siloxane compound shown in, wherein R1、R2Can be identical or differ, be C1-C10's
The alkyl or cycloalkyl of straight or branched, 1≤n≤6..
Preferably, lead in formula I, R1And R2Identical or different, it is C1-C4Straight or branched alkyl；
1≤n≤3.Using the phosphoric acid silicone compounds shown in logical formula (I) as external donor compound, comprehensive
High activity, capacity of orientation and higher hydrogen response can be can show that preferably.Described silicon phosphate
Oxygen alkyl compound can be included but are not limited to：Solutions of dimethyl phosphoryl MTMS, diethylphosphoryl
MTMS, solutions of dimethyl phosphoryl ethyl trimethoxy silane, solutions of dimethyl phosphoryl methyltriethoxy silane
Alkane, diethylphosphoryl MTES, diethylphosphoryl ethyl trimethoxy silane, solutions of dimethyl phosphoryl
Ethyl triethoxysilane, diethylphosphoryl ethyl triethoxysilane, dipropyl phosphonoethyl triethoxysilicane
Alkane, solutions of dimethyl phosphoryl propyl trimethoxy silicane, diethylphosphoryl propyl-triethoxysilicane, diethylphosphoryl
Ethyl tripropoxy silane, dipropyl phosphinylidyne propyl-triethoxysilicane, dipropyl phosphonoethyl tripropoxy silicon
One kind or many in alkane, diethylphosphoryl propyl group tripropoxy silane and dipropyl phosphinylidyne propyl group tripropoxy silane
Kind.
According to a preferred embodiment of the present invention, in the polynary external electron donor, described c1's and c2
Mol ratio is (1-20):(20-500), preferably (1-10):(20-100), more preferably (1-5):
(20-50).In the molar ratio range, be conducive to the catalyst for obtaining higher performance.
According to a particular embodiment of the invention, the internal electron donor compound is selected from containing O, N, P, S atom
Compound in one or more, the preferably compound containing O atom, further preferably selected from ethers,
One or more in esters, 2, 2-Oxydiphenol class, phenolic ester class and ketone compounds, is still further preferably selected from diol ester
One or more in compound, phthalate compound, diether compounds and succinate compound.
Described glycol ester compounds are the glycol ester compounds as internal electron donor commonly used in the art, specifically
Example is included between 2,4-PD dibenzoate, two p-methylbenzoic acid ester of 2,4-PD, 2,4-PD two
Methyl benzoic acid ester, two o-toluic acid ester of 2,4-PD, two p-ethylbenzoic acid ester of 2,4-PD, 2,4-
Pentanediol two aligns propylbenzoic acid ester, two cumfrey ester of 2,4-PD, 2,4-PD two to different
Butylbenzoic acid ester, 2,4-PD two to n-butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 2,4-PD,
3- methyl -2,4-PD dibenzoate, 3- ethyls -2,4-PD dibenzoate, 3- n-pro-pyls -2,4- penta 2
Alcohol dibenzoate, two p-methylbenzoic acid ester of 3- ethyls -2,4-PD, 3- ethyls -2,4-PD two are to second
Yl benzoic acid ester, 3- ethyls -2,4-PD two align propylbenzoic acid ester, 3- ethyls -2,4-PD two to different
Propylbenzoic acid ester, 3- ethyls -2,4-PD two are to isobutyl-benzene formic acid esters, 3- ethyls -2,4-PD two pairs
N-butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 3- ethyls -2,4-PD, 3- normal-butyls -2,4-PD
Dibenzoate, 3,3- dimethyl -2,4-PD dibenzoate, the chloro- 2,4-PD dibenzoates of 3-, 3-
Bromo- 2,4-PD dibenzoate, 3,5- heptandiol dibenzoates, two p-methylbenzoic acid ester of 3,5- heptandiols,
Two p-ethylbenzoic acid ester of 3,5- heptandiols, 3,5- heptandiols two align propylbenzoic acid ester, 3,5- heptandiols two pairs
Isopropyl acid ester, 3,5- heptandiols two are to isobutyl-benzene formic acid esters, 3,5- heptandiols two to n-butylbenzoic acid
Ester, two p-tert-butyl benzoic acid ester of 3,5- heptandiols, 4- methyl -3,5- heptandiol dibenzoates, 4,4- dimethyl
- 3,5- heptandiol dibenzoates, 4- ethyl -3,5- heptandiol dibenzoates, 4- ethyl -3,5- heptandiols two are to first
Yl benzoic acid ester, two p-ethylbenzoic acid ester of 4- ethyl -3,5- heptandiols, 4- ethyl -3,5- heptandiols two are to propyl group
Benzoate, 4- ethyl -3,5- heptandiols two are to butylbenzoic acid ester, 4- ethyl -3,5- heptandiols two to the tert-butyl group
Benzoate, 4- n-pro-pyl -3,5- heptandiol dibenzoates, 4- normal-butyl -3,5- heptandiol dibenzoates,
One or more in the chloro- 3,5- heptandiols dibenzoates of 4-, the bromo- 3,5- heptandiols dibenzoates of 4-.
Described phthalate compound is the neck phthalic acid as internal electron donor commonly used in the art
Ester compounds, its instantiation include dimethyl phthalate, diethyl phthalate, phthalic acid
Di-n-propyl ester, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate,
The just own ester of amyl phthalate, di-iso-amyl phthalate, phthalic acid two, phthalic acid
Two dissident's esters, dinoctyl phthalate, diisooctyl phthalate, two Bian ester of phthalic acid, four
Methylphthalic acid dimethyl ester, tetramethyl diethyl phthalate, tetramethyl n-propyl phthalate,
Tetramethyl diisopropyl phthalate, tetramethyl n-butyl phthalate, tetramethyl phthalic acid two
Isobutyl ester, tetramethyl amyl phthalate, tetramethyl di-iso-amyl phthalate, tetramethyl neighbour's benzene
The just own ester of dioctyl phthalate two, tetramethyl o-phthalic acid ester, tetramethyl dinoctyl phthalate, four
Methylphthalic acid di-isooctyl, two Bian ester of tetramethyl phthalic acid, tetrabromophthalate dimethyl ester,
Tetrabromophthalate diethylester, tetrabromophthalate di-n-propyl ester, tetrabromophthalate diisopropyl ester,
Tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, two n-pentyl ester of tetrabromophthalate,
The just own ester of tetrabromophthalate diisoamyl ester, tetrabromophthalate two, two dissident's ester of tetrabromophthalate,
In tetrabromophthalate di-n-octyl, two Bian ester of tetrabromophthalate di-isooctyl and tetrabromophthalate
One or more.
Described diether compound is the diether compound as internal electron donor commonly used in the art, and which has
Body example includes 2,2- dimethyl -1,3- dimethoxy propanes, 2,2- diethyl -1,3- dimethoxy propanes, 2,2- bis-
Propyl group -1,3- dimethoxy propanes, 2,2- diisopropyl -1,3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxies
Base propane, 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- diamyl -1,3- dimethoxy propanes, 2,2- bis-
Isopentyl -1,3- dimethoxy propanes, 2- methyl -2- ethyl -1,3- dimethoxy propanes, 2- methyl-2-propyl -1,3-
Dimethoxy propane, 2- methyl -2- isopropyl -1,3- dimethoxy propanes, 2- methyl -2- butyl -1,3- dimethoxys
Propane, 2- methyl -2- isobutyl group -1,3- dimethoxy propanes, 2- methyl -2- amyl group -1,3- dimethoxy propanes, 2-
Methyl -2- isopentyl -1,3- dimethoxy propanes, 2- ethyl -2- propyl group -1,3- dimethoxy propanes, 2- ethyl -2- are different
Propyl group -1,3- dimethoxy propanes, 2- ethyl -2- butyl -1,3- dimethoxy propanes, 2- ethyl -2- isobutyl group -1,3-
Dimethoxy propane, 2- ethyl -2- amyl group -1,3- dimethoxy propanes, 2- ethyl -2- isopentyl -1,3- dimethoxys
Propane, 2- propyl group -2- isopropyl -1,3- dimethoxy propanes, 2- propyl group -2- butyl -1,3- dimethoxy propanes, 2-
Propyl group -2- isobutyl group -1,3- dimethoxy propanes, 2- propyl group -2- amyl group -1,3- dimethoxy propanes, 2- propyl group -2- are different
Amyl group -1,3- dimethoxy propanes, 2- isopropyl -2- isobutyl group -1,3- dimethoxy propanes, 2- isopropyl -2- amyl groups
- 1,3- dimethoxy propanes, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2- butyl -2- isobutyl group -1,3-
Dimethoxy propane, 2- butyl -2- amyl group -1,3- dimethoxy propanes, 2- butyl -2- isopentyl -1,3- dimethoxys
Propane, 2- isobutyl group -2- amyl group -1,3- dimethoxy propanes, 2- isobutyl group -2- isopentyl -1,3- dimethoxy propanes,
2- isobutyl group -2- phenyl -1,3- dimethoxy propanes, 2- isopentyl -2- phenyl -1,3- dimethoxy propanes, 2- (2- first
Base butyl) -2- benzyl -1,3- dimethoxy propanes, 2- (2- ethyl-butyls) -2- phenyl -1,3- dimethoxy propanes, 2- (2-
Ethylhexyl) -2- phenyl -1,3- dimethoxy propanes, 2- methyl -2- phenyl -1,3- dimethoxy propanes, 2- ethyl -2-
Phenyl -1,3- dimethoxy propanes, 2- isobutyl group -2- benzyl -1,3- dimethoxy propanes, 2- isopentyl -2- benzyl -1,3-
Dimethoxy propane, 2- (2- methyl butyls) -2- benzyl -1,3- dimethoxy propanes, 2- (2- ethyl-butyls) -2- benzyls
- 1,3- dimethoxy propanes, 2- (2- ethylhexyls) -2- benzyl -1,3- dimethoxy propanes, 2- propyl group -2- benzyl -1,3-
Dimethoxy propane, 2- isopropyl -2- benzyl -1,3- dimethoxy propanes, 2- isobutyl group -2- (2- ethyl-butyls) -1,3-
Dimethoxy propane, 2- isopentyl -2- (2- ethyl-butyls) -1,3- dimethoxy propanes, 2- (2- methyl butyls) -2- (2-
Ethyl-butyl) -1,3- dimethoxy propanes, 2- (2- ethylhexyls) -2- (2- ethyl-butyls) -1,3- dimethoxy propanes,
2- methyl -2- (2- ethyl-butyls) -1,3- dimethoxy propanes, 2- ethyl -2- (2- ethyl-butyls) -1,3- dimethoxys third
Alkane, 2- isobutyl group -2- (2- methyl butyls) -1,3- dimethoxy propanes, 2- isopentyl -2- (2- methyl butyls) -1,3- two
Methoxy propane, 2- (2- ethyl-butyls) -2- (2- methyl butyls) -1,3- dimethoxy propanes, 2- (2- ethyl hexyls
Base) -2- (2- methyl butyls) -1,3- dimethoxy propanes, 2- isobutyl group -2- (2- methyl butyls) -1,3- dimethoxys third
Alkane, 2- isobutyl group -2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2- isopentyl -2- (2- ethylhexyls) -1,3- two
Methoxy propane, 2,2- bis- (2- methyl butyls) -1,3- dimethoxy propanes, 2- isopropyl -2- isopentyl -1,3-
Dimethoxy propane, bis- (2- ethylhexyls) -1,3- dimethoxy propanes of 2,2- and 9,9- bis- (methoxy) fluorenes
In one or more.
Described succinate compound compound is the succinate chemical combination as internal electron donor commonly used in the art
Thing, its instantiation include as 2,3- diη-propyl diethyl succinates, 2,3- diisopropyl diethyl succinates,
2,3- di-n-butyl diethyl succinates, 2,3- diisobutyl diethyl succinates, 2,3- diη-propyls succinic acid two
Isobutyl ester, 2,3- diisopropyl di-iso-octyl succinates, 2,3- di-n-butyls di-iso-octyl succinate and 2,3- bis- are different
One or more in butyl di-iso-octyl succinate.
In the solid catalyst, based on the gross weight of solid catalyst, the internal electron donor content is
1wt%-25wt%, the content of titanium is 0.5wt%-8wt%, and the content of magnesium is 3wt%-25wt%；Preferably, institute
Internal electron donor content is stated for 5wt%-20wt%, the content of titanium is 1wt%-6wt%, the content of magnesium is
10wt%-20wt%.It is highly preferred that the content of the internal electron donor is 8wt%-12wt%, the content of titanium is
2wt%-4wt%, the content of magnesium is 15wt%-20wt%.
According to the present invention, described ingredient of solid catalyst, preferably comprising titanium compound, magnesium compound and on
The product of the internal electron donor compound that states.For prepare the catalyst solid constituent titanium compound,
The consumption of magnesium compound and internal electron donor compound is not particularly limited, and can be respectively the conventional use of this area
Amount.
In described ingredient of solid catalyst, described magnesium compound is selected from magnesium dihalide, alkoxyl magnesium alkyl
In the hydrate or alcohol adduct of magnesium magnesium dihalide and magnesium dihalide molecular formula, one of halogen atom is by hydrocarbon oxygen
The derivant replaced by base or halo oxyl；The alcohol adduct of preferably magnesium dihalide or magnesium dihalide.Concrete real
Example includes magnesium dichloride, dibrominated magnesium, magnesium diiodide and their alcohol adduct.
In described ingredient of solid catalyst, it is TiX that described titanium compound can select formulam(OR1)4-mChange
Compound, R in formula1For C1-C20Alkyl, X is halogen, 1≤m≤4.Instantiation include titanium tetrachloride,
Titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen
Base titanium, preferably one ethanolato-titanium of trichlorine, titanium tetrachloride.
Heretofore described ingredient of solid catalyst can be prepared in accordance with the following methods：
Method one：Prepare according to the method disclosed in patent CN1506384.First, by magnesium compound with organic
Alcoholic compound press 2-5 mol ratios and atent solvent mixing, be warming up to 120-150 DEG C, by magnesium/acid anhydride mol ratio 5-10,
Magnesium/silicon mol ratio 20-50 reaction 1-5 hours.
Then according to the alcohol adduct for being cooled to room temperature is added to by titanium/magnesium mol ratio 20-50 pre- is cooled to -15 to -40 DEG C
In compound titanium solution, 90-110 DEG C is warming up to, is added according to magnesium/internal electron donor mol ratio 2-10 interior to electricity
Donor compound, reacts 1-3 hours at 100-130 DEG C, filters to isolate solid particle.
Solid particle is added in compound titanium solution according still further to titanium/magnesium mol ratio 20-50, stirring and
100-130 DEG C of reaction 1.5-3 hour, filters to isolate solid particle.
Solid particle is finally washed with 50-80 DEG C of atent solvent, is obtained after drying.
Method two：Prepare according to the method disclosed in patent CN85100997, first, magnesium compound is dissolved
In the dicyandiamide solution being made up of organic epoxy compound thing, organic phosphorus compound and inert diluent, formed uniform
Mix with titanium compound after solution, in the presence of precipitation additive, separate out solidss；This solids is using interior to electricity
Donor compound is processed so as to be attached on solidss, if necessary, then with titanium tetrahalide and inert diluents
Agent is processed to solidss, and wherein precipitation additive is organic acid anhydride, organic acid, ether, ketone, the one kind in ester,
Or their mixture.Specifically such as：Acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride,
Pyromellitic acid anhydride, acetic acid, propanoic acid, butanoic acid, acrylic acid, methacrylic acid, acetone, butanone, two
Benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, succinate, malonate, glutarate, 2,4-
Pentadiol ester, 3,5- heptandiol esters.
In terms of every mole of magnesium halide, organic epoxy compound thing is 0.2～10 mole to each component, organophosphors chemical combination
Thing is 0.1～3 mole, and precipitation additive is 0～1.0 mole, and titanium compound is 0.5～150 mole, internal electron donor
Compound is 0.02～0.5 mole.
Method three：Prepare according to the method disclosed in patent CN1091748.Chlorination magnesium alcoholate melt is in white oil
Disperse through high-speed stirred with the dispersant system of silicone oil, form emulsion, be discharged in coolant rapid cooling fixed
Type, forms chlorination magnesium alcoholate microsphere.Coolant is the relatively low inert hydrocarbon solvent of boiling point, such as petroleum ether, penta
Alkane, hexane, heptane etc..Gained chlorination magnesium alcoholate microsphere is scrubbed, dry for ball type carrier, its alcohol and chlorine
The mol ratio for changing magnesium is 2-3, preferably 2-2.5.Diameter of carrier is 10-300 microns, with 30-150 microns most
Good.
With excessive titanium tetrachloride in the above-mentioned ball type carrier of K cryogenic treatment, progressively heat up, add in processing procedure
Electron donor, with the multiple unoccupied place of atent solvent after process, obtains the spheric catalyst of solid powdery after drying.
Titanium tetrachloride is 20-200 with the mol ratio of magnesium chloride, preferably 30-60；Initiated process temperature is -30 to 0 DEG C,
It is preferred with -25 to -20 DEG C；Final process temperature is 80-136 DEG C, is preferred with 100-130 DEG C.
Gained spheric catalyst has following feature：Ti content (weight) 1.5-3.0%, internal electron donor chemical combination
Thing content 6.0-20.0%, chlorinity 52-60%, content of magnesium 10-20%, atent solvent content 1-6%, catalysis
Agent specific surface area is more than 250m2/g.
Method four：Available dialkoxy magnesium is added in arene compound and is stirred, and forms suspension；Suspension is used
Tetravalence titanium chloride is processed at -20 to 100 DEG C, and is reacted at 0-130 DEG C, in the process, at -20 to 130 DEG C
Internal electron donor is added to be reacted, the solid for obtaining is washed with arene compound；Then 0-130 DEG C
In aromatic hydrocarbon solvent, then with the process of tetravalence titanium chloride, finally washed with atent solvent, drained, obtained solid and urge
Agent.Wherein every mole dialkyl magnesium tetravalence titanium chloride 0.5-100mol, internal electron donor 0.01-10mol.
Method five：With TiCl4 or its arene solution at 80-130 DEG C to such as dialkoxy magnesium or two aryloxy group
Two magnesium hydrocarbyloxy compounds of magnesium etc carry out halogenation, and carrying out process with TiCl4 or its arene solution can repeat
One or many, and internal electron donor compound is added in processing as one or many.
Method six：Prepare according to the method disclosed in patent US4540679.Transistion metal compound is (preferably
Tetravalent titanium compound) and alkoxyl magnesium compound and electron donor carry out in atent solvent in certain proportion instead
Should, wherein transition metal is at least 0.5 with the mol ratio of magnesium elements:1, the consumption of internal electron donor compound
Up to 1.0 moles every gram of titanium atoms, atent solvent conveniently must be removed, and palpus dehydration, deoxidation and removing easily make
The gas of catalyst poisoning, reaction carry out at -10 to 170 DEG C, the response time be a few minutes to a few houres.
Prepare the method for the ingredient of solid catalyst also just like by magnesium compound, electron donor etc. in diluent
Emulsion is formed, is added titanium compound to make its fixation obtain spherical solid, treated is obtained ingredient of solid catalyst.
In what a kind of preparation method above-mentioned in office, required internal electron donor compound both can be with compound
Form is added；Can also add in other manners, as can by using internal electron donor compound be suitable for
Precursor is in situ to be obtained, and the front physical ability is become in required by for example known chemical reaction such as esterification etc.
Electron donor compound.
According to a particular embodiment of the invention, described silane compound is silanes chemical combination commonly used in the art
Thing, such as can be selected from Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane,
Diisopropyl dimethoxy silane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, n-pro-pyl
One in trimethoxy silane, second, isobutyl dimethoxy silane, diphenyldimethyl silane and tetraalkoxysilane
Plant or multiple
The alkyl aluminum compound is preferably formula AlR 'tX3-t, in formula, R ' is selected from hydrogen and C1-C20Alkyl, X
For halogen, 1≤t≤3.
According to a particular embodiment of the invention, the alkyl aluminum compound is selected from：Triethyl aluminum, tri-propyl aluminum,
Three n-butylaluminums, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen two are different
In butyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminum and ethyl aluminum dichloride one
Plant or multiple, one or more preferably in triethyl aluminum, triisobutyl aluminium.
According to catalyst of the present invention, component A is calculated as 1 with the mol ratio of component B with titanium/aluminum:
(5-5000), preferably 1:(20-500), component A is calculated as 1 with the mol ratio of component C with titanium/component C:(0-500),
It is preferred that 1:(3-100).
According to another aspect of the present invention, the present invention also provides one kind as CH2=CHR olefinic polymerizations are anti-
The application of the catalyst that answers.
According to the present invention, described catalyst can be directly added in reactor to be used in polymerization process.Or,
Prepolymerization was carried out before first polymer reactor is added and obtains pre-polymerized catalyst.In the present invention, " pre-
Polymerization catalyst " refers to the catalyst with relatively low transforming degree through polymerization procedure.According to the present invention, described pre-polymerization
Close catalyst carries out the prepolymer of prepolymerization gained, pre-polymerization multiple comprising above-mentioned ingredient of solid catalyst and alkene
For 0.1-1000g olefin polymers/g ingredients of solid catalyst.
In described prepolymerization, the alkene includes alpha-olefin, preferably ethylene or propylene.Specifically, adopt
The mixture that one or more alpha-olefin of 20mol% is up to ethylene or its surplus carries out prepolymerization.It is preferred that
Ground, the transforming degree of pre-polymerized catalyst components is for about 0.2-500 gram of polymer/gram ingredient of solid catalyst.
Described prepolymerization temperature is -20 to 80 DEG C, preferably 0-50 DEG C, carries out in a liquid or in gas phase.
Prepolymerization step can as continuous polymerization technique in a part of carry out online, or in intermittently operated independently
Carry out.For the polymer that preparation amount is 0.5-20g/g catalytic components, it is preferable that the batch pre-polymerization with ethylene.
Polymerization pressure is 0.01-10MPa.
Described olefinic polyreaction is carried out according to known polymerization, can be carried out in liquid phase or gas phase,
Or can also carry out under the operation of liquid and gas polymerization stage combination.Reactive polymeric temperature is 0-150 DEG C,
It is preferred that 60-90 DEG C.Slurry process, gas-phase fluidized-bed is included using conventional technique, wherein R is hydrogen or C1-C6
Alkyl, the alkene instantiation is in ethylene, propylene, 1-butylene, 4-methyl-1-pentene and the 1- hexenes
One or more, be preferably used in the homopolymerization of propylene with or propylene and other alkene combined polymerization.
The catalyst of the present invention is also applied for the copolymer for producing polyethylene and ethylene and alpha-olefin, wherein alpha-olefin
One or more in propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
The present invention is by compounding compound as the catalyst use of external electron donor using silane and phosphoric acid siloxanes
In olefinic polymerization, especially during propylene polymerization, high activity is shown, and with very high vertical structure directionality,
Meanwhile, show the hydrogen response higher than silane compound external electron donor of the prior art.
Specific embodiment
Technical scheme is described further with reference to embodiment, but is not constituted to the present invention's
Any restriction.
Test and sign：
(1) polymer isotactic index II：(heptane boiling extracting 6 hours) is determined using heptane extraction process：2
Gram dry polymer samples, are placed in extractor after being extracted 6 hours with boiling heptane, by residue dry to
The polymer weight (g) of constant weight gained is isotactic index with 2 ratio.
(2) melt index MI：Using fusion index instrument under 230 DEG C, 2.16kg pressure, according to ASTM
D1238-99《The standard test method that thermoplasticity fusing flow rate is determined with extruding plasticimeter》Determine.
Embodiment 1
First, the preparation of ingredient of solid catalyst
250mL reactions after reflux condenser, mechanical agitator and thermometer being housed and is sufficiently displaced from through nitrogen
In device, dehydrated alcohol 36.5mL, anhydrous magnesium chloride 21.3g is added, stirring is lower to heat up, and magnesium chloride all dissolves
Add white oil 75mL, silicone oil 75mL afterwards, maintain 120 DEG C of certain times.In the band that another volume is 500mL
Have in the reaction bulb of high speed agitator, be previously added the silicone oil of 112.5mL white oils and same volume, be preheating to
, aforementioned mixture is pressed in second reactor rapidly, maintain 120 DEG C 3 to be stirred with 3500rmp by 120 DEG C
Minute, the 3rd reactor for being previously added 1600mL hexanes and having cooled to -25 DEG C is transferred the material under stirring
In, until material transfer is finished, final temperature is less than 0 DEG C.Sucking filtration, is washed with hexane, vacuum drying,
Spherical particle chlorination magnesium alcoholate 41g is obtained, the carrier of 100-400 mesh after sieving, is taken, test carrier is analyzed
Consist of MgCl2 2.36C2H5OH.
Take above-mentioned MgCl2 2.36C2H5OH ball type carrier 7g to be slowly added into equipped with 150mL titanium tetrachlorides simultaneously
It is cooled in -20 DEG C of reaction bulb in advance, is progressively warming up to 40 DEG C, adds internal electron donor compound 2,4- pentanediols two
Benzoate 6mmol；After being continuously heating to 130 DEG C of maintenances 2 hours, sucking filtration.120mL TiCl4 are added,
130 DEG C are progressively warming up to, are maintained 2 hours, is washed with hexane 60mL and repeatedly into filtrate, occur without chloride ion
Till, filter cake is vacuum dried, and obtains ingredient of solid catalyst.
2nd, propylene polymerization
The catalytic component of above-described embodiment is carried out propylene polymerization respectively.Propylene polymerization program is：Volume is 5L
Stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, add AlEt32.5mmol, polynary outer electron
Body compound C 0.l mmol, polynary external donor compound C are diethylphosphoryl propyl-triethoxysilicane
With dicyclopentyl dimethoxyl silane, mol ratio is 1:1, add the ingredient of solid catalyst of above-mentioned preparation
8-10mg and 1.2L hydrogen, is passed through liquid propene 2.3L, is warming up to 70 DEG C, maintains this temperature 1 hour；
Cooling, pressure release obtain powder.Aggregated data is shown in Table 1.
Embodiment 2
With embodiment 1, difference is that interior Donor compound is 2,4- pentanediols two (to n-pro-pyl) benzoic acid
Ester, polynary external donor compound are diethylphosphoryl ethyl triethoxysilane and dicyclopentyl dimethoxyl
Silane, mol ratio are 3:1, aggregated data is shown in Table 1.
Embodiment 3
With embodiment 1, difference is interior Donor compound for 3- methyl -2,4- glycol dibenzoates,
Polynary external donor compound is solutions of dimethyl phosphoryl ethyl trimethoxy silane and dicyclopentyl dimethoxyl silicon
Alkane, mol ratio are 1:5, aggregated data is shown in Table 1.
Embodiment 4
With embodiment 1, difference is interior Donor compound for n-butyl phthalate, polynary outer
Electron donor compound is diethylphosphoryl ethyl triethoxysilane and Cyclohexyl Methyl Dimethoxysilane, rubs
You are than being 1:1, aggregated data is shown in Table 1.
Embodiment 5
With embodiment 1, difference is interior Donor compound for diisobutyl phthalate, polynary outer
Electron donor compound is solutions of dimethyl phosphoryl propyl trimethoxy silicane and Cyclohexyl Methyl Dimethoxysilane, rubs
You are than being 6:1, aggregated data is shown in Table 1.
Embodiment 6
With embodiment 1, difference is interior Donor compound for 2,3- diisopropyl diethyl succinates,
Polynary external donor compound is diethylphosphoryl ethyl triethoxysilane and n-pro-pyl trimethoxy silane,
Mol ratio is 4:1, aggregated data is shown in Table 1.
Embodiment 7
With embodiment 1, difference is interior Donor compound for 9,9- dimethoxy-methyl fluorenes, polynary outer
Electron donor compound is diethylphosphoryl ethyl triethoxysilane and second, isobutyl dimethoxy silane, mole
Than for 1:4, aggregated data is shown in Table 1.
Embodiment 8 (contrast)
With embodiment 1, difference is that interior Donor compound, for 2,4- glycol dibenzoates, is given outward
Electron compound is diethylphosphoryl propyl-triethoxysilicane, and aggregated data is shown in Table 1.
Embodiment 9 (contrast)
With embodiment 1, difference is interior Donor compound for diisobutyl phthalate, outward to electricity
Donor compound is solutions of dimethyl phosphoryl propyl trimethoxy silicane, and aggregated data is shown in Table 1.
Embodiment 10 (contrast)
With embodiment 1, difference is interior Donor compound for 2,3- diisopropyl diethyl succinates,
External donor compound is diethylphosphoryl ethyl triethoxysilane, and aggregated data is shown in Table 1.
Embodiment 11 (contrast)
With embodiment 1, difference is interior Donor compound for 9,9- dimethoxy-methyl fluorenes, outward to electricity
Donor compound is diethylphosphoryl ethyl triethoxysilane, and aggregated data is shown in Table 1.
Comparative example 1
With embodiment 1, difference is that interior Donor compound, for 2,4- glycol dibenzoates, is given outward
Electron compound is dicyclopentyl dimethoxyl silane, adds hydrogen to be respectively 1.2L and 7.2L, aggregate number
According to being shown in Table 1 and 2.
Comparative example 2
With embodiment 1, difference is interior Donor compound for diisobutyl phthalate, outward to electricity
Donor compound is Cyclohexyl Methyl Dimethoxysilane, adds hydrogen to be respectively 1.2L and 7.2L, aggregate number
According to being shown in Table 1 and 2.
Comparative example 3
With embodiment 1, difference is interior Donor compound for 2,3- diisopropyl diethyl succinates,
External donor compound is n-pro-pyl trimethoxy silane, adds hydrogen to be respectively 1.2L and 7.2L, polymerization
Data are shown in Table 1 and 2.
1 propylene polymerization result of table
In table：DCPDMS is dicyclopentyl dimethoxyl silane；CHMMS is Cyclohexyl Methyl Dimethoxysilane；
NPTMS is n-pro-pyl trimethoxy silane；DIBDMS is second, isobutyl dimethoxy silane.
2 melt index of table
By data above it is known that the catalyst provided according to the present invention, multiple using silane and phosphoric acid siloxanes
The polynary external electron donor that matches somebody with somebody, with high polymerization activity, vertical structure capacity of orientation is good the characteristics of, can obtain high
The polymer of rule index；Meanwhile, also improve the hydrogen response of catalyst.According to the present invention, there is provided one
Plant on the premise of high polymerization activity and high isotactic index is ensured, improve the new catalysis of hydrogen response
Agent, can be used in olefinic polymerization, especially propylene polymerization, with broad application prospect.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in which is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of catalyst for olefinic polymerization, including following components：
A solid catalysts, comprising Mg, Ti, halogen and at least one interior electron containing lone pair electrons
Compound；
B alkyl aluminum compounds；
The many first external electron donors of C, including first kind external electron donor c1 and Equations of The Second Kind external electron donor c2, institute
The c1 for stating is silane compound, and c2 is phosphoric acid siloxane compound.
2. catalyst according to claim 1, it is characterised in that the c2 is the phosphorus of logical formula I
Sour siloxane compound,
Wherein R1And R2Identical or differ, it is C1-C10Straight or branched alkyl or cycloalkyl, 1≤n
≤6；Preferably, R1And R2Identical or different, it is C1-C4Straight or branched alkyl；1≤n≤3.
3. catalyst according to claim 1 and 2, it is characterised in that in the polynary external electron donor,
The mol ratio of c1 and c2 is (1-20):(20-500), preferably (1-10):(20-100), further excellent
Elect (1-5) as:(20-50).
4. the catalyst according to any one in claim 1-3, it is characterised in that the phosphoric acid silica
Alkyl compound selected from solutions of dimethyl phosphoryl MTMS, diethylphosphoryl MTMS,
Solutions of dimethyl phosphoryl ethyl trimethoxy silane, solutions of dimethyl phosphoryl MTES, diethylphosphoryl methyl
Triethoxysilane, diethylphosphoryl ethyl trimethoxy silane, solutions of dimethyl phosphoryl ethyl triethoxysilane,
Diethylphosphoryl ethyl triethoxysilane, dipropyl phosphonoethyl triethoxysilane, solutions of dimethyl phosphoryl propyl group
Trimethoxy silane, diethylphosphoryl propyl-triethoxysilicane, diethylphosphoryl ethyl tripropoxy silane,
Dipropyl phosphinylidyne propyl-triethoxysilicane, dipropyl phosphonoethyl tripropoxy silane, diethylphosphoryl propyl group
One or more in tripropoxy silane and dipropyl phosphinylidyne propyl group tripropoxy silane.
5. the catalyst according to any one in claim 1-4, it is characterised in that the interior electron
One or more in the compound containing O, N, P or S atom of body compound, preferably former containing O
The compound of son.
6. the catalyst according to any one in claim 1-5, it is characterised in that the interior electron
Body compound is selected from diol-lipid compound, phthalic acid ester, diether compound and succinate compound chemical combination
One or more in thing.
7. the catalyst according to any one in claim 1-6, it is characterised in that the silanes
Compound is selected from Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane, two different
Propyldimethoxy-silane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, n-pro-pyl front three
One kind in TMOS, second, isobutyl dimethoxy silane, diphenyldimethyl silane and tetraalkoxysilane
Or it is multiple.
8. the catalyst according to any one in claim 1-7, it is characterised in that component A with
The mol ratio of component B is calculated as 1 with titanium/aluminum:(5-1000), preferably 1:(20-250)；Component A and component
The mol ratio of C is calculated as 1 with titanium/component C:(0.1-100), preferably 1:(1-50).
9. the application in olefin polymerization of the catalyst according to any one in claim 1-8.
10. application according to claim 9, it is characterised in that the formula of the alkene is CH2=CHR,
Wherein, R is hydrogen or C1-C6Alkyl.
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