CN106496366B - 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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Abstract
The present invention provides a kind of catalyst for olefin polymerization, which includes: A. solid catalyst, contain Mg, Ti, halogen and at least one internal electron donor compound containing lone pair electrons；B. alkyl aluminum compound；C. more first external electron donors, including first kind external electron donor c1 and the second class external electron donor c2, the c1 are silane compound, c2 is phosphoric acid siloxane compound.When catalyst of the invention is used for propylene polymerization, not only available satisfactory polymerization activity and high vertical structure directionality, 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 contains silane and phosphoric acid silicone compounds
The catalyst for olefines polymerizing of compounding and its application.
Background technique
It is well known that can be used for using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basis
Olefin polymerization, especially in the alpha-olefine polymerizing with 3 carbon or more available higher yields and compared with
The polymer of high stereospecificity, wherein electron donor compound is one of essential ingredient in ingredient of solid catalyst,
And it is continuously updated the replacement as the development of internal electron donor compound results in polyolefin catalyst, for external electron donor
Research also gradually deeply.Currently, largely having disclosed a variety of electron donor compounds, such as internal electron donor unitary carboxylic
Acid esters or multi-carboxylate, ketone, monoether or polyether, diol ester, amine etc. and its derivative, external electron donor monocarboxylic esters, amine,
Siloxanes, amino silane etc. and its derivative.The electron donor reported is mostly the chemical combination of oxygen-containing, nitrogen phosphate and sulfur, silicon at present
Object.In these polymerization catalysts, electron donor has not activity, stereoselectivity, molecular weight distribution and polymer performance
With the influence of degree.
By the present invention in that silane and phosphoric acid siloxanes is used to compound as external electron donor, high comprehensive performance can be obtained
Olefin polymer, when being used for propylene polymerization, compared with prior art, the catalyst is except with higher active and preferable vertical
Body capacity of orientation can obtain outside the polymer of high isotactic index, also improve the hydrogen response of catalyst.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides the outer electrons that a kind of silane-containing and phosphoric acid siloxanes compound
The catalyst of body, the catalyst not only have good activity and stereotaxis good, are conducive to the polymerization for obtaining high isotactic
Object, and hydrogen response is higher.
According to an aspect of the invention, there is provided a kind of catalyst for olefin polymerization, the catalyst packet
A containing ingredient of solid catalyst, alkyl aluminum B and polynary external electron donor C, the ingredient of solid catalyst A, including Mg, Ti, halogen
With at least one internal electron donor compound containing lone pair electrons；
The component B is alkyl aluminum compound；
The component C is polynary external electron donor, including first kind external electron donor c1 and the second class external electron donor c2.
The first kind external electron donor c1 is silane compound；The second class external electron donor c2 is phosphoric acid type siloxane
Compound.
According to the present invention, the polynary external electron donor body compounded using silane compound and phosphoric acid siloxane compound
The catalyst of system has good activity, hydrogen response and stereoselectivity.
A specific embodiment according to the present invention, the second class external electron donor c2 is preferably general formula (I)
Shown in phosphoric acid siloxane compound, wherein R1、R2Can be identical or not identical, it is C1-C10Linear chain or branched chain alkyl or ring
Alkyl, 1≤n≤6.
Preferably, in general formula (I), R1And R2It is identical or different, it is C1-C4Linear chain or branched chain alkyl；1≤n≤3.It adopts
Using phosphoric acid silicone compounds shown in logical formula (I), as external donor compound, comprehensive performance is preferable, can show that height
Activity, capacity of orientation and higher hydrogen response.The phosphoric acid siloxane compound may include but not only limit
In: solutions of dimethyl phosphoryl methyltrimethoxysilane, diethylphosphoryl methyltrimethoxysilane, solutions of dimethyl phosphoryl ethyl trimethoxy
Base silane, solutions of dimethyl phosphoryl methyltriethoxysilane, diethylphosphoryl methyltriethoxysilane, diethylphosphoryl ethyl three
Methoxy silane, solutions of dimethyl phosphoryl ethyl triethoxysilane, diethylphosphoryl ethyl triethoxysilane, dipropyl phosphinylidyne second
Ethyl triethoxy silicane alkane, solutions of dimethyl phosphoryl propyl trimethoxy silicane, diethylphosphoryl propyl-triethoxysilicane, diethyl phosphorus
Acyl ethyl tripropoxy silane, dipropyl phosphinylidyne propyl-triethoxysilicane, dipropyl phosphonoethyl tripropoxy silane, diethyl
One of base phosphinylidyne propyl tripropoxy silane and dipropyl phosphinylidyne propyl tripropoxy silane are a variety of.
According to a preferred embodiment of the present invention, in the polynary external electron donor, the molar ratio of the c1 and c2
For (1-20): (20-500), preferably (1-10): (20-100), further preferably (1-5): (20-50).At described mole
Than the catalyst in range, being conducive to obtain higher performance.
According to a particular embodiment of the invention, the internal electron donor compound be selected from containing O, N, P, S atom compound
One of or it is a variety of, preferably containing the compound of O atom, further preferably be selected from ethers, esters, phenolic ether class, phenolic ester class
With one of ketone compounds or a variety of, it is still further preferably selected from glycol ester compounds, phthalate compound, two
One of ether compound and succinate compound are a variety of.
The glycol ester compounds are the glycol ester compounds as internal electron donor commonly used in the art, specific example
Including 2,4-PD dibenzoate, two p-methylbenzoic acid ester of 2,4-PD, two m-methyl benzoic acid of 2,4-PD
Ester, two o-toluic acid ester of 2,4-PD, two p-ethylbenzoic acid ester of 2,4-PD, 2,4-PD two are to n-propyl
Benzoic ether, two cumfrey ester of 2,4-PD, 2,4-PD two are to isobutyl-benzene formic acid esters, 2,4-PD
Two pairs of n-butylbenzoic acid esters, two p-tert-butyl benzoic acid ester of 2,4-PD, 3- methyl -2,4-PD dibenzoate,
3- ethyl -2,4-PD dibenzoate, 3- n-propyl -2,4-PD dibenzoate, 3- ethyl -2,4-PD two
P-methylbenzoic acid ester, two p-ethylbenzoic acid ester of 3- ethyl -2,4-PD, 3- ethyl -2,4-PD two are to n-propyl
Benzoic ether, two cumfrey ester of 3- ethyl -2,4-PD, 3- ethyl -2,4-PD two are to isobutyl-benzene first
Acid esters, 3- ethyl -2,4-PD two to n-butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 3- ethyl -2,4-PD,
3- normal-butyl -2,4-PD dibenzoate, 3,3- dimethyl -2,4-PD dibenzoate, the chloro- 2,4-PD of 3-
The bromo- 2,4-PD dibenzoate of dibenzoate, 3-, 3,5- heptandiol dibenzoate, 3,5- heptandiol two are to methyl
Benzoic ether, two p-ethylbenzoic acid ester of 3,5- heptandiol, 3,5- heptandiol two are to n-propylbenzene formic acid esters, 3,5- heptandiol two
Cumfrey ester, 3,5- heptandiol two to isobutyl-benzene formic acid esters, 3,5- heptandiol two to n-butylbenzoic acid ester, 3,
Two p-tert-butyl benzoic acid ester of 5- heptandiol, 4- methyl -3,5- heptandiol dibenzoate, 4,4- dimethyl -3,5- heptandiol
Dibenzoate, 4- ethyl -3,5- heptandiol dibenzoate, two p-methylbenzoic acid ester of 4- ethyl -3,5- heptandiol, 4- second
Two p-ethylbenzoic acid ester of base -3,5- heptandiol, two n-propyl benzoate's ester of 4- ethyl -3,5- heptandiol, 4- ethyl -3,5- heptan
Glycol two is to butylbenzoic acid ester, two p-tert-butyl benzoic acid ester of 4- ethyl -3,5- heptandiol, 4- n-propyl -3,5- heptandiol
Dibenzoate, 4- normal-butyl -3,5- heptandiol dibenzoate, the chloro- 3,5- heptandiol dibenzoate of 4-, the bromo- 3,5- of 4-
One or more of heptandiol dibenzoate.
The phthalate compound is the neck phthalic acid esterification as internal electron donor commonly used in the art
Object is closed, specific example includes repefral, diethyl phthalate, n-propyl phthalate, adjacent benzene
Dioctyl phthalate diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, amyl phthalate, adjacent benzene
The just own ester of dioctyl phthalate diisoamyl ester, phthalic acid two, o-phthalic acid ester, di-n-octyl phthalate, adjacent benzene
Dioctyl phthalate di-isooctyl, two Bian ester of phthalic acid, tetramethyl repefral, tetramethyl phthalic acid diethyl
Ester, tetramethyl n-propyl phthalate, tetramethyl diisopropyl phthalate, the positive fourth of tetramethyl phthalic acid two
Ester, tetramethyl diisobutyl phthalate, tetramethyl amyl phthalate, tetramethyl phthalic acid diisoamyl
The just own ester of ester, tetramethyl phthalic acid two, tetramethyl o-phthalic acid ester, tetramethyl phthalic acid two are just pungent
Ester, tetramethyl diisooctyl phthalate, two Bian ester of tetramethyl phthalic acid, tetrabromophthalate dimethyl ester, tetrabromo
Diethyl phthalate, tetrabromophthalate di-n-propyl ester, tetrabromophthalate diisopropyl ester, tetrabromophthalate
Di-n-butyl, tetrabromophthalate diisobutyl ester, two n-pentyl ester of tetrabromophthalate, tetrabromophthalate diisoamyl
The just own ester of ester, tetrabromophthalate two, two dissident's ester of tetrabromophthalate, tetrabromophthalate di-n-octyl, tetrabromo
One of two Bian ester of diisooctyl phthalate and tetrabromophthalate is a variety of.
The diether compound is the diether compound as internal electron donor commonly used in the art, specific real
Example includes 2,2- dimethyl -1,3- dimethoxy propane, 2,2- diethyl -1,3- dimethoxy propane, 2,2- dipropyl -1,3-
Dimethoxy propane, 2,2- diisopropyl -1,3- dimethoxy propane, 2,2- dibutyl -1,3- dimethoxy propane, 2,2- bis-
Isobutyl group -1,3- dimethoxy propane, 2,2- diamyl -1,3- dimethoxy propane, 2,2- diisoamyl -1,3- dimethoxy
Propane, 2- methyl -2- ethyl -1,3- dimethoxy propane, 2- methyl-2-propyl -1,3- dimethoxy propane, 2- methyl -2-
Isopropyl -1,3- dimethoxy propane, 2- methyl -2- butyl -1,3- dimethoxy propane, 2- methyl -2- isobutyl group -1,3- two
Methoxy propane, 2- methyl -2- amyl -1,3- dimethoxy propane, 2- methyl -2- isopentyl -1,3- dimethoxy propane, 2-
Ethyl -2- propyl -1,3- dimethoxy propane, 2- ethyl -2- isopropyl -1,3- dimethoxy propane, 2- ethyl -2- butyl -
1,3- dimethoxy propane, 2- ethyl -2- isobutyl group -1,3- dimethoxy propane, 2- ethyl -2- amyl -1,3- dimethoxy
Propane, 2- ethyl -2- isopentyl -1,3- dimethoxy propane, 2- propyl -2- isopropyl -1,3- dimethoxy propane, 2- third
Base -2- butyl -1,3- dimethoxy propane, 2- propyl -2- isobutyl group -1,3- dimethoxy propane, amyl -1 2- propyl -2-,
3- dimethoxy propane, 2- propyl -2- isopentyl -1,3- dimethoxy propane, 2- isopropyl -2- isobutyl group -1,3- dimethoxy
Base propane, 2- isopropyl -2- amyl -1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2-
Butyl -2- isobutyl group -1,3- dimethoxy propane, 2- butyl -2- amyl -1,3- dimethoxy propane, 2- butyl -2- isoamyl
Base -1,3- dimethoxy propane, 2- isobutyl group -2- amyl -1,3- dimethoxy propane, 2- isobutyl group -2- isopentyl -1,3- two
Methoxy propane, 2- isobutyl group -2- phenyl -1,3- dimethoxy propane, 2- isopentyl -2- phenyl -1,3- dimethoxy propane,
2- (2- methyl butyl) -2- benzyl -1,3- dimethoxy propane, 2- (2- ethyl-butyl) -2- phenyl -1,3- dimethoxy third
Alkane, 2- (2- ethylhexyl) -2- phenyl -1,3- dimethoxy propane, 2- methyl -2- phenyl -1,3- dimethoxy propane, 2- second
Base -2- phenyl -1,3- dimethoxy propane, 2- isobutyl group -2- benzyl -1,3- dimethoxy propane, 2- isopentyl -2- benzyl -
1,3- dimethoxy propane, 2- (2- methyl butyl) -2- benzyl -1,3- dimethoxy propane, 2- (2- ethyl-butyl) -2- benzyl
Base -1,3- dimethoxy propane, 2- (2- ethylhexyl) -2- benzyl -1,3- dimethoxy propane, 2- propyl -2- benzyl -1,3-
Dimethoxy propane, 2- isopropyl -2- benzyl -1,3- dimethoxy propane, 2- isobutyl group -2- (2- ethyl-butyl) -1,3- two
Methoxy propane, 2- isopentyl -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- (2- methyl butyl) -2- (2- ethyl
Butyl) -1,3- dimethoxy propane, 2- (2- ethylhexyl) -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- methyl -
2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- ethyl -2- (2- ethyl-butyl) -1,3- dimethoxy propane, 2- isobutyl
Base -2- (2- methyl butyl) -1,3- dimethoxy propane, 2- isopentyl -2- (2- methyl butyl) -1,3- dimethoxy propane,
2- (2- ethyl-butyl) -2- (2- methyl butyl) -1,3- dimethoxy propane, 2- (2- ethylhexyl) -2- (2- methyl butyl) -
1,3- dimethoxy propane, 2- isobutyl group -2- (2- methyl butyl) -1,3- dimethoxy propane, 2- isobutyl group -2- (2- ethyl
Hexyl) -1,3- dimethoxy propane, 2- isopentyl -2- (2- ethylhexyl) -1,3- dimethoxy propane, (the 2- methyl of 2,2- bis-
Butyl) -1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2,2- bis- (2- ethylhexyl) -
One or more of 1,3- dimethoxy propane and 9,9- bis- (methoxy) fluorenes.
The succinate compound compound is the succinate compound as internal electron donor commonly used in the art,
Specific example includes such as 2,3- diη-propyl diethyl succinate, 2,3- diisopropyl diethyl succinate, 2,3- di-n-butyl
Diethyl succinate, 2,3- diisobutyl diethyl succinate, 2,3- diη-propyl di-iso-octyl succinate, 2,3- diisopropyl
One of di-iso-octyl succinate, 2,3- di-n-butyl di-iso-octyl succinate and 2,3- diisobutyl di-iso-octyl succinate
Or it is several.
In the solid catalyst, the total weight based on solid catalyst, the internal electron donor content is 1wt%-
25wt%, the content of titanium are 0.5wt%-8wt%, and the content of magnesium is 3wt%-25wt%；Preferably, the internal electron donor contains
Amount is 5wt%-20wt%, and the content of titanium is 1wt%-6wt%, and the content of magnesium is 10wt%-20wt%.It is highly preferred that described
The content of internal electron donor is 8wt%-12wt%, and the content of titanium is 2wt%-4wt%, and the content of magnesium is 15wt%-20wt%.
According to the present invention, the ingredient of solid catalyst preferably includes titanium compound, magnesium compound and above-mentioned interior
The reaction product of electron donor compound.Be used to prepare the titanium compound of the catalyst solid constituent, magnesium compound and it is interior to
The dosage of electron compound is not particularly limited, and can be respectively the conventional amount used of this field.
In the ingredient of solid catalyst, the magnesium compound is selected from magnesium dihalide, alkoxy Mei ﹑ Wan Ji Mei ﹑ bis-
One of halogen atom is by oxyl or halogenated oxyl in the hydrate or alcohol adduct and magnesium dihalide molecular formula of magnesium halide
Displaced derivative；The preferably alcohol adduct of magnesium dihalide or magnesium dihalide.Specific example includes magnesium dichloride, dibrominated
Magnesium, magnesium diiodide and their alcohol adduct.
In the ingredient of solid catalyst, it is TiX that general formula, which can be selected, in the titanium compoundm(OR1)4-mCompound,
R in formula1For C1-C20Alkyl, X is halogen, 1≤m≤4.Specific example includes titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four
Titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine, preferably four chlorinations
Titanium.
Heretofore described ingredient of solid catalyst can be prepared in accordance with the following methods:
Method one: it is prepared according to method disclosed in patent CN1506384.Firstly, by magnesium compound and organic alcohol compound
Object is mixed by 2-5 molar ratio and atent solvent, 120-150 DEG C is warming up to, by magnesium/acid anhydride molar ratio 5-10, magnesium/silicon mol ratio 20-
50 reactions 1-5 hours.
Then the alcohol adduct for being cooled to room temperature is added to the pre- titanium for being cooled to -15 to -40 DEG C according to titanium/magnesium molar ratio 20-50
In compound solution, it is warming up to 90-110 DEG C, internal electron donor compound is added according to magnesium/internal electron donor molar ratio 2-10,
100-130 DEG C reaction 1-3 hours, filter to isolate solid particle.
Solid particle is added in compound titanium solution according still further to titanium/magnesium molar ratio 20-50, is stirred and in 100-130
DEG C reaction 1.5-3 hours, filter to isolate solid particle.
Solid particle finally is washed with 50-80 DEG C of atent solvent, is obtained after dry.
Method two: it is prepared according to method disclosed in patent CN85100997, firstly, being dissolved in magnesium compound by organic
Epoxide, organic phosphorus compound and inert diluent composition dicyandiamide solution in, formed homogeneous solution after with titanium compound
Solids is precipitated in the presence of precipitation additive in mixing；This solids is handled using internal electron donor compound, makes its load
It invests on solids, when necessary, then with titanium tetrahalide and inert diluent solids is handled, wherein precipitation additive is to have
One of machine acid anhydrides, organic acid, ether, ketone, ester or their mixture.Specifically such as: acetic anhydride, phthalic anhydride, fourth two
Acid anhydrides, maleic anhydride, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, first and second
Ketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, succinate, malonate, glutarate, 2,4-PD ester, 3,
5- heptandiol ester.
For each component in terms of every mole of magnesium halide, organic epoxy compound object is 0.2~10 mole, and organic phosphorus compound is
0.1~3 mole, precipitation additive is 0~1.0 mole, and titanium compound is 0.5~150 mole, internal electron donor compound 0.02
~0.5 mole.
Method three: it is prepared according to method disclosed in patent CN1091748.Chlorination magnesium alcoholate melt is in white oil and silicone oil
Dispersant system in disperse through high-speed stirred, form emulsion, be discharged into rapid cooling and shaping in coolant liquid, form magnesium chloride alcohol
Close object microballoon.Coolant liquid is the lower inert hydrocarbon solvent of boiling point, such as petroleum ether, pentane, hexane, heptane.Gained magnesium chloride
Alcohol adduct microballoon is washed, it is dry be ball type carrier, the molar ratio of alcohol and magnesium chloride is 2-3, preferably 2-2.5.Carrier grain
Diameter is 10-300 microns, best with 30-150 microns.
It with excessive titanium tetrachloride in the above-mentioned ball type carrier of low-temperature treatment, gradually heats up, is added during processing to electricity
Daughter obtains the spheric catalyst of solid powdery after dry with the multiple unoccupied place of atent solvent after processing.Titanium tetrachloride and chlorination
The molar ratio of magnesium is 20-200, preferably 30-60；Initiated process temperature is -30 to 0 DEG C, is preferred with -25 to -20 DEG C；Final place
Managing temperature is 80-136 DEG C, is preferred with 100-130 DEG C.
Gained spheric catalyst has the feature that Ti content (weight) 1.5-3.0%, internal electron donor compound content
6.0-20.0%, chlorinity 52-60%, content of magnesium 10-20%, atent solvent content 1-6%, specific surface area of catalyst are greater than
250m2/g。
Method four: it can be added in arene compound and be stirred with dialkoxy magnesium, form suspension；Suspension tetravalence chlorine
Change titanium -20 to 100 DEG C handle, and 0-130 DEG C react, in the process, -20 to 130 DEG C of addition internal electron donors into
Row reaction, obtained solid are washed with arene compound；Then at 0-130 DEG C in aromatic hydrocarbon solvent, then with tetravalence chlorination
Titanium processing, is finally washed with atent solvent, is drained, obtain solid catalyst.Wherein every mole of 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 magnesium it
Two magnesium hydrocarbyloxy compounds of class carry out halogenation, and carrying out processing with TiCl4 or its arene solution can be repeated one or more times, and
Internal electron donor compound is added in one or many such processing.
Method six: it is prepared according to method disclosed in patent US4540679.Transistion metal compound (preferably titanic
Compound) and alkoxyl magnesium compound reacted in atent solvent in certain proportion with electron donor, wherein transition gold
The molar ratio for belonging to element and magnesium elements is at least 0.5:1, and the dosage of internal electron donor compound is up to 1.0 moles of every gram of titanium originals
Son, atent solvent must facilitate removal, and palpus dehydration, deoxidation and removing easily make the gas of catalyst poisoning, react -10 to 170
DEG C carry out, the reaction time be a few minutes to a few houres.
The method of the ingredient of solid catalyst is prepared also just like by magnesium compound, electron donor etc. is formed in diluent
Lotion, titanium compound, which is added, makes its fixation obtain spherical solid, treated to obtain ingredient of solid catalyst.
In what above-mentioned a kind of preparation method in office, required internal electron donor compound both can be in the form of compound
It is added；It can also be added, can such as be obtained in situ by using the precursor that internal electron donor compound is suitble in other manners,
The preceding physical efficiency becomes required internal electron donor compound for example, by known chemical reaction such as esterification.
According to a particular embodiment of the invention, the silane compound is silane compound commonly used in the art,
Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane, diisopropyl diformazan can be such as selected from
Oxysilane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, n-propyl trimethoxy silane, diisobutyl
It is one or more in dimethoxysilane, diphenyldimethyl silane and tetraalkoxysilane
The alkyl aluminum compound is preferably general formula AlR 'tX3-t, R ' is selected from hydrogen and C in formula1-C20Alkyl, X is 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 positive fourths
Base aluminium, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, a chlorine diethyl
One of aluminium, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride are a variety of, preferably triethyl aluminum, three different
One of butyl aluminium is a variety of.
The molar ratio of the catalyst according to the present invention, the component A and component B are calculated as 1:(5-5000 with titanium/aluminium), it is excellent
Select 1:(20-500), the molar ratio of component A and component C are calculated as 1:(0-500 with titanium/component C), preferably 1:(3-100).
According to another aspect of the present invention, CH is used as the present invention also provides a kind of2=CHR olefin polymerization is urged
The application of agent.
According to the present invention, the catalyst can be directly added into reactor in polymerization process.Alternatively, being added
Prepolymerization is carried out before first polymer reactor obtains pre-polymerized catalyst.In the present invention, " pre-polymerized catalyst " refer to
Lower transforming degree passes through the catalyst of polymerization procedure.According to the present invention, the pre-polymerized catalyst includes above-mentioned solid
Catalytic component and alkene carry out the resulting prepolymer of prepolymerization, and pre-polymerization multiple is that 0.1-1000g olefin polymer/g solid is urged
Agent component.
In the prepolymerization, the alkene includes alpha-olefin, preferably ethylene or propylene.Specifically, using ethylene
Or its surplus is up to the mixture progress prepolymerization of one or more alpha-olefins of 20mol%.Preferably, prepolymerized catalysis
The transforming degree of agent component is about 0.2-500 grams polymer/gram ingredient of solid catalyst.
The prepolymerization temperature is -20 to 80 DEG C, preferably 0-50 DEG C, is carried out in a liquid or in gas phase.Pre-polymerization
A part that closing step can be used as in continuous polymerization technique carries out online, or independently carries out in intermittently operated.For preparation
Amount is the polymer of 0.5-20g/g catalytic component, it is preferable that the batch pre-polymerization with ethylene.Polymerization pressure is 0.01-
10MPa。
The olefin polymerization is carried out according to well known polymerization, can be carried out in liquid phase or gas phase, or
It can also be carried out under the operation that liquid and gas polymerization stage combines.Reactive polymeric temperature is 0-150 DEG C, preferably 60-90 DEG C.
It include slurry process using conventional technique, gas-phase fluidized-bed, wherein R is hydrogen or C1-C6Alkyl, alkene specific example choosing
From one of ethylene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexene or it is a variety of, it is preferable to use propylene homopolymerization
With or propylene and other alkene combined polymerization.
Catalyst of the invention is also applied for the copolymer of production polyethylene and ethylene and alpha-olefin, and wherein alpha-olefin is selected from
One of propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene are a variety of.
The present invention is used for alkene as the catalyst of external electron donor by using silane and phosphoric acid siloxanes compounding compound
When polymerized hydrocarbon, especially propylene polymerization, high activity is shown, and there is very high vertical structure directionality, meanwhile, it shows than existing
There is the higher hydrogen response of silane compound external electron donor in technology.
Specific embodiment
Technical solution of the present invention is described further below with reference to embodiment, but is not constituted to of the invention any
Limitation.
Test and characterization:
(1) polymer isotactic index II: using heptane extraction process measurement (heptane boiling extracting 6 hours): 2 grams dry poly-
Object sample is closed, is placed in extractor after being extracted 6 hours with boiling heptane, residue is dry to the resulting polymer weight of constant weight
(g) ratio with 2 is isotactic index.
(2) it melt index MI: using fusion index instrument under 230 DEG C, 2.16kg pressure, " is used according to ASTM D1238-99
Squeeze the standard test method of plastometer measurement thermoplasticity fusing flow rate " measurement.
Embodiment 1
One, the preparation of ingredient of solid catalyst
In the 250mL reactor equipped with reflux condenser, mechanical agitator and thermometer and after nitrogen is sufficiently displaced from,
Dehydrated alcohol 36.5mL, anhydrous magnesium chloride 21.3g is added, stirs lower heating, white oil 75mL, silicon is added after magnesium chloride whole dissolution
Oily 75mL maintains 120 DEG C of certain times.In the reaction flask with high speed agitator that another volume is 500mL, it is previously added
The silicone oil of 112.5mL white oil and same volume is preheating to 120 DEG C, and aforementioned mixture is pressed into second reactor rapidly, dimension
120 DEG C are held with 3500rmp stirring 3 minutes, is transferred the material under stirring and is previously added 1600mL hexane and has cooled to -25 DEG C
Third reactor in, until material transfer finish, final temperature be no more than 0 DEG C.It filters, is washed with hexane, be dried in vacuo, obtain
To spherical particle chlorination magnesium alcoholate 41g, the carrier of 100-400 mesh is taken after sieving, the group of analysis test carrier becomes MgCl2
2.36C2H5OH。
Take above-mentioned MgCl22.36C2H5OH ball type carrier 7g to be slowly added into equipped with 150mL titanium tetrachloride and be cooled in advance-
In 20 DEG C of reaction flask, 40 DEG C are gradually warming up to, internal electron donor compound 2,4- glycol dibenzoate 6mmol is added；
After being continuously heating to 130 DEG C of maintenances 2 hours, filter.120mL TiCl4 is added, is gradually warming up to 130 DEG C, is maintained 2 hours,
It is washed with hexane 60mL until repeatedly there is not chloride ion into filtrate, filter cake vacuum drying obtains ingredient of solid catalyst.
Two, propylene polymerization
The catalytic component of above-described embodiment is subjected to propylene polymerization respectively.Propylene polymerization program are as follows: volume be 5L not
Become rusty steel reaction kettle, and after gaseous propylene is sufficiently displaced from, AlEt32.5mmol, polynary external donor compound C 0.l is added
Mmol, polynary external donor compound C be diethylphosphoryl propyl-triethoxysilicane and dicyclopentyl dimethoxyl silane,
Molar ratio is 1:1, adds ingredient of solid catalyst 8-10mg and the 1.2L hydrogen of above-mentioned preparation, 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, the difference is that interior Donor compound is 2,4- pentanediol two (to n-propyl) benzoic ether,
Polynary external donor compound is diethylphosphoryl ethyl triethoxysilane and dicyclopentyl dimethoxyl silane, molar ratio
For 3:1, aggregated data is shown in Table 1.
Embodiment 3
With embodiment 1, the difference is that interior Donor compound is 3- methyl -2,4- glycol dibenzoate, it is more
First external donor compound is solutions of dimethyl phosphoryl ethyl trimethoxy silane and dicyclopentyl dimethoxyl silane, and molar ratio is
1:5, aggregated data are shown in Table 1.
Embodiment 4
With embodiment 1, the difference is that interior Donor compound is n-butyl phthalate, polynary outer electron
Body compound is diethylphosphoryl ethyl triethoxysilane and Cyclohexyl Methyl Dimethoxysilane, molar ratio 1:1, polymerization
Data are shown in Table 1.
Embodiment 5
With embodiment 1, the difference is that interior Donor compound is diisobutyl phthalate, polynary outer electron
Body compound is solutions of dimethyl phosphoryl propyl trimethoxy silicane and Cyclohexyl Methyl Dimethoxysilane, molar ratio 6:1, polymerization
Data are shown in Table 1.
Embodiment 6
With embodiment 1, the difference is that interior Donor compound is 2,3- diisopropyl diethyl succinate, it is polynary outer
Electron donor compound is diethylphosphoryl ethyl triethoxysilane and n-propyl trimethoxy silane, and molar ratio 4:1 gathers
It closes data and is shown in Table 1.
Embodiment 7
With embodiment 1, the difference is that interior Donor compound is 9,9- dimethoxy-methyl fluorenes, polynary outer electron
Body compound is diethylphosphoryl ethyl triethoxysilane and second, isobutyl dimethoxy silane, molar ratio 1:4, aggregate number
According to being shown in Table 1.
Embodiment 8 (comparison)
With embodiment 1, the difference is that interior Donor compound is 2,4- glycol dibenzoate, external electron donor
Compound is diethylphosphoryl propyl-triethoxysilicane, and aggregated data is shown in Table 1.
Embodiment 9 (comparison)
With embodiment 1, the difference is that interior Donor compound is diisobutyl phthalate, external electron donor
Conjunction object is solutions of dimethyl phosphoryl propyl trimethoxy silicane, and aggregated data is shown in Table 1.
Embodiment 10 (comparison)
With embodiment 1, the difference is that interior Donor compound is 2,3- diisopropyl diethyl succinate, it is outer to electricity
Donor compound is diethylphosphoryl ethyl triethoxysilane, and aggregated data is shown in Table 1.
Embodiment 11 (comparison)
With embodiment 1, the difference is that interior Donor compound is 9,9- dimethoxy-methyl fluorenes, external electron donor
Conjunction object is diethylphosphoryl ethyl triethoxysilane, and aggregated data is shown in Table 1.
Comparative example 1
With embodiment 1, the difference is that interior Donor compound is 2,4- glycol dibenzoate, external electron donor
Compound is dicyclopentyl dimethoxyl silane, and it is respectively 1.2L and 7.2L that hydrogen, which is added, and aggregated data is shown in Table 1 and 2.
Comparative example 2
With embodiment 1, the difference is that interior Donor compound is diisobutyl phthalate, external electron donor
Conjunction object is Cyclohexyl Methyl Dimethoxysilane, and it is respectively 1.2L and 7.2L that hydrogen, which is added, and aggregated data is shown in Table 1 and 2.
Comparative example 3
With embodiment 1, the difference is that interior Donor compound is 2,3- diisopropyl diethyl succinate, it is outer to electricity
Donor compound is positive propyl trimethoxy silicane, and it is respectively 1.2L and 7.2L that hydrogen, which is added, and aggregated data is 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
Be positive propyl trimethoxy silicane；DIBDMS is second, isobutyl dimethoxy silane.
2 melt index of table
By above data it is known that the catalyst provided according to the present invention, is compounded using silane and phosphoric acid siloxanes
Polynary external electron donor has the characteristics that high polymerization activity, vertical structure capacity of orientation are good, can obtain the polymerization of high isotactic index
Object；Meanwhile also improving the hydrogen response of catalyst.According to the present invention, provide it is a kind of guarantee high polymerization activity and
Under the premise of high isotactic index, the new catalyst of hydrogen response is improved, it is poly- to can be used in olefinic polymerization, especially propylene
It closes, there is wide application prospect.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (12)
1. a kind of catalyst for olefinic polymerization, including following components:
A solid catalyst includes Mg, Ti, halogen and at least one interior Donor compound containing lone pair electrons；
B alkyl aluminum compound；
The more first external electron donors of C, including first kind external electron donor c1 and the second class external electron donor c2, the c1 are silane
Class compound, c2 are phosphoric acid siloxane compound；
The internal electron donor compound is selected from one of diol-lipid compound and diether compound or a variety of.
2. catalyst according to claim 1, which is characterized in that the c2 is the phosphoric acid type siloxane chemical combination of general formula (I)
Object,
Wherein R1And R2It is identical or not identical, it is C1-C10Linear chain or branched chain alkyl or cycloalkyl, 1≤n≤6.
3. catalyst according to claim 2, which is characterized in that R1And R2It is identical or different, it is C1-C4Linear chain or branched chain
Alkyl；1≤n≤3.
4. catalyst according to claim 1, which is characterized in that in the polynary external electron donor, mole of c1 and c2
Than for (1-20): (20-500).
5. catalyst according to claim 4, which is characterized in that in the polynary external electron donor, mole of c1 and c2
Than for (1-10): (20-100).
6. catalyst according to claim 4, which is characterized in that in the polynary external electron donor, mole of c1 and c2
Than for (1-5): (20-50).
7. catalyst according to claim 1, which is characterized in that the phosphoric acid siloxane compound is selected from dimethyl phosphorus
Acyl methyltrimethoxysilane, diethylphosphoryl methyltrimethoxysilane, solutions of dimethyl phosphoryl ethyl trimethoxy silane, diformazan
Base phosphoryl methyl triethoxysilane, diethylphosphoryl methyltriethoxysilane, diethylphosphoryl ethyl trimethoxy silane,
Solutions of dimethyl phosphoryl ethyl triethoxysilane, diethylphosphoryl ethyl triethoxysilane, dipropyl phosphonoethyl triethoxy
Silane, solutions of dimethyl phosphoryl propyl trimethoxy silicane, diethylphosphoryl propyl-triethoxysilicane, diethylphosphoryl ethyl 3 third
Oxysilane, dipropyl phosphinylidyne propyl-triethoxysilicane, dipropyl phosphonoethyl tripropoxy silane, diethylphosphoryl propyl
One of tripropoxy silane and dipropyl phosphinylidyne propyl tripropoxy silane are a variety of.
8. catalyst according to claim 1, which is characterized in that the silane compound is selected from cyclohexyl methyl diformazan
Oxysilane, diphenyl dimethoxy silicon, phenyltriethoxy silane, diisopropyl dimethoxy silane, dipropyl dimethoxy
Silane, dicyclopentyl dimethoxyl silane, n-propyl trimethoxy silane, second, isobutyl dimethoxy silane, diphenyl diformazan
One of base silane and tetraalkoxysilane are a variety of.
9. catalyst described in any one of -8 according to claim 1, which is characterized in that mole of the component A and component B
Than being calculated as 1:(5-1000 with titanium/aluminium)；The molar ratio of the component A and component C is calculated as 1:(0.1-100 with titanium/component C).
10. catalyst according to claim 9, which is characterized in that the molar ratio of the component A and component B is in terms of titanium/aluminium
For 1:(20-250)；The molar ratio of the component A and component C is calculated as 1:(1-50 with titanium/component C).
11. the application of catalyst described in any one of -10 in olefin polymerization according to claim 1.
12. application according to claim 11, which is characterized in that the general formula of the alkene is CH2=CHR, wherein R is hydrogen
Or C1-C6Alkyl.
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