CN104558287B - Catalyst component for olefin and catalyst - Google Patents
Catalyst component for olefin and catalyst Download PDFInfo
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- CN104558287B CN104558287B CN201310508884.7A CN201310508884A CN104558287B CN 104558287 B CN104558287 B CN 104558287B CN 201310508884 A CN201310508884 A CN 201310508884A CN 104558287 B CN104558287 B CN 104558287B
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Abstract
The invention discloses a kind of catalyst component for olefin, it includes the alkyl magnesium shown in formula I or the product of internal electron donor compound a shown in its alcohol adduct, Formula II, internal electron donor compound b shown in formula III and the titanium compound shown in formula IV；Wherein, mean diameter D50 of the alkyl magnesium shown in formula I or its alcohol adduct is 20 100um, profile exponent SPAN<1.1, in Formulas I, Et is ethyl, and EHA is 2 ethylhexyls, 0.001≤m≤0.5;Described internal electron donor compound a is 1 with the mol ratio of internal electron donor compound b consumption:4‑4:1.Catalyst provided by the present invention has the advantages of polymerization activity is high, and stereotaxises ability is good.Mg(OEt)2‑m(OEHA)m（I）
Description
Technical field
The present invention relates to catalyst field is and in particular to a kind of catalyst component for olefin and catalyst.
Background technology
It is known that Ziegler-Natta（Z-N）Catalyst, can be used for CH2=CHR olefinic polyreaction, particularly exists
Have in 3 carbon or the alpha-olefine polymerizing of more carbon atom and can obtain higher yields and the polymer of higher stereospecificity.
As Ziegler-Natta（Z-N）The catalytic component of the important component of catalyst（Or ingredient of solid catalyst）, be with magnesium,
Titanium and internal electron donor are as basis.But, various internal electron donors are necessarily special in the corresponding polyolefin products of imparting
Also product can be made to have some shortcomings, thus limiting their application while point.Research worker wishes to find combination property
More excellent Z-N catalyst.
Specifically, the now widely used active height of Z-N catalyst containing phthalic acid ester internal electron donor, tree
The feature of fat good combination property, but phthalic acid ester is proved injure the fertility of the mankind, thus recently do not contain adjacent benzene
The Z-N catalyst of dicarboxylic acid esters internal electron donor becomes study hotspot.
Molecular weight distribution（MWD）The mechanical performance of impact polymer and processing characteristics.High molecular weight moieties are to a great extent
The upper long term mechanical strength determining polymer, and low molecular weight fraction determines its extrusion performance to a great extent.
The disclosed active height of Z-N catalyst containing 1,3- diol ester internal electron donor of CN1213080C, molecular weight distribution
Wide feature, but the molecular weight distribution of its preparation is wide not enough, thus limiting its application.EP990201172 and
The active height of Z-N catalyst of succinate-containing internal electron donor disclosed in US60999436, stereotaxises ability is good, gained
The wide feature of molecular weight distribution, but this catalyst is to molecular weight regulator（Hydrogen is the molecular-weight adjusting being most frequently with
Agent）Sensitivity is bad, that is, in identical hydrogen usage, the melt flow rate (MFR) (MFR) of polymer（Or title melt index）Low；
And be to meet injecting products, the especially processing request of thin wall parts, polymer generally requires higher MFR.Producing injection
With when homopolymer or anti-impact polymer it is often desirable to polymer has high MFR to have wide molecular weight distribution simultaneously.This polymerization
Thing is considered intensity and the rigidity that existing good processing characteristics has also had.
Supported catalyst component with alkoxyl magnesium as carrier, obtained acrylic polymers, there is particle shape excellent
Good, ultra-fine powder content is few（Micropowder amount conference impact polymer continuously produces）, the premium properties such as stereoregularity height.However,
With alkoxyl magnesium as carrier, the catalyst for olefines polymerizing solid constituent of function admirable to be obtained is it may first have to prepare performance
Excellent alkoxyl magnesium carrier.The present inventor discloses one kind in Chinese patent CN102453150A and urges for alkene
Compound alcohol alkoxyl magnesium carrier of agent preparation and preparation method thereof；By this alkoxyl magnesium carrier, titanium compound and O-phthalic
When the catalyst solid constituent of esters of gallic acid internal electron donor reaction preparation and corresponding olefin polymerization catalysis are used for olefinic polymerization
Activity is high, can obtain the olefin polymer that particle shape is excellent, ultra-fine powder content is few, stereoregularity is high.However, this catalysis
The vistanex molecular weight distribution of agent preparation is wide not enough.
Content of the invention
For deficiency of the prior art, the invention provides a kind of catalyst component for olefin（Or title catalyst
Solid, ingredient of solid catalyst）And the catalyst containing described catalytic component, the electron donor body in described catalytic component
System（Internal electron donor a and internal electron donor b）There is synergism.Described catalyst is used for olefinic polymerization, has polymerization activity
Height, stereotaxises ability is good, and hydrogen response is good, molecular weight distribution width, and does not contain phthalic acid ester in polymer；
Especially under high hydrogen concentration, the catalysis activity of catalyst and the polymer isotacticity of Geng Gao can be improved by a larger margin.
According to an aspect of the invention, it is provided a kind of catalyst component for olefin, it is included shown in formula I
Internal electron donor compound a shown in alkoxyl magnesium or its alcohol adduct, Formula II, internal electron donor compound b shown in formula III and
The product of the titanium compound shown in formula IV；Wherein, described internal electron donor compound a and internal electron donor compound b
The mol ratio of consumption is 1:4-4:1；Mean diameter D50 of the alkoxyl magnesium shown in formula I or its alcohol adduct is 20-100um, divides
Cloth index SPAN<1.1,
Mg(OEt)2-m(OEHA)m（I）
In Formulas I, Et is ethyl, and EHA is 2- ethylhexyl, and 0.001≤m≤0.5, preferably 0.001≤m≤0.25 are more excellent
Select 0.001≤m≤0.1；
In Formula II, R1And R2Can be identical or differ, selected from hydrogen, C1-C14The alkyl of straight or branched, C3-C10Cycloalkyl,
C6-C10Aryl, C7-C10Alkaryl or aralkyl；R3And R4Can be identical or differ, selected from C1-C10Straight or branched alkyl, C3-
C10Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl or C7-C20Aralkyl；
In formula III, group R5And R6It is same to each other or different to each other, selected from C1-C20Line style or the alkyl of side chain, alkylene, ring
Alkyl, aryl, aralkyl and alkaryl；Group R7-R10It is same to each other or different to each other, be hydrogen or C1-C20Line style or side chain alkane
Base, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl；Described R5And R6Hetero atom can optionally be contained；
TiXn(OR13)4-n（IV）
In formula IV, X is halogen；R13For C1-C20Alkyl, n be 0-4 integer.
According to catalytic component of the present invention, R7-R9It is all hydrogen, R10It is selected from and there is C3-C20Primary, secondary or tertiary alkyl
Group, cycloalkyl, aryl, aralkyl and alkaryl.
In the present invention, SPAN=（D90-D10）/D50, wherein D90Represent the particle diameter being 90% corresponding to cumulative percentage, D10Table
Show the particle diameter being 10% corresponding to cumulative percentage, D50Represent the particle diameter that corresponding running summary of the points scored is 50%.
Alkoxyl magnesium according to Formulas I of the present invention, wherein Formulas I only represent described ethyoxyl and 2- ethyl hexyl oxy
Composition content, the not concrete structure of representation alkoxy magnesium.Specifically, as Mg (OEt) (OEHA) only represents alkoxyl magnesium chemical combination
In thing, ethyoxyl and the mol ratio of 2- ethyl hexyl oxy are 1, and it both can be the diethoxy magnesium and two that mol ratio is 1（2- second
The own oxygen of base）The mixture of magnesium or ethyoxyl（2- ethyl hexyl oxy）Magnesium compound, can also be the mixture of three；
It can be the mixed of the alkoxyl magnesium compound composition of the various structures that the ethyoxyl mole ratio total with 2- ethyl hexyl oxy is 1
Compound.
According to a preferred embodiment of catalytic component of the present invention, described internal electron donor compound a and b use
The mol ratio of amount is 2:3-3:2.In described molar ratio range, there is more excellent combination property.
According to catalytic component of the present invention, internal electron donor compound a shown in described Formulas I is such as selected from following
Compound：2,3- diisopropyl -2- cyano group dimethyl succinate, 2,3- diisopropyl -2- cyano group diethyl succinate, 2,3- bis-
Isopropyl -2- cyano group succinic acid di-n-propyl ester, 2,3- diisopropyl -2- cyano group diisopropyl ester amber acid, 2,3- diisopropyl -2-
Cyano group succinic acid di-n-butyl, 2,3- diisopropyl -2- cyano group succinic acid diisobutyl ester, 2,3- diisopropyl -2- cyano group fourth two
Acid -1- methyl ester -4- ethyl ester（R1=methyl, R2=ethyl）, 2,3- diisopropyl -2- cyano group succinic acid -1- ethyl ester -4- methyl ester（R1=
Ethyl, R2=methyl）, 2,3- diisopropyl -2- cyano group succinic acid -1- N-butyl -4- ethyl ester（R1=normal-butyl, R2=ethyl）、2,
3- diisopropyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyl（R1=ethyl, R2=normal-butyl）, 2,3- diisobutyl -2- cyano group
Dimethyl succinate, 2,3- diisobutyl -2- cyano group diethyl succinate, 2,3- diisobutyl -2- cyano group succinic acid two positive third
Ester, 2,3- diisobutyl -2- cyano group diisopropyl ester amber acid, 2,3- diisobutyl -2- cyano group succinic acid di-n-butyl, 2,3- bis-
Isobutyl group -2- cyano group succinic acid diisobutyl ester, 2,3- diisobutyl -2- cyano group succinic acid -1- methyl ester -4- ethyl ester（R1=methyl, R2
=ethyl）, 2,3- diisobutyl -2- cyano group succinic acid -1- ethyl ester -4- methyl ester（R1=ethyl, R2=methyl）, 2,3- diisobutyl-
2- cyano group succinic acid -1- N-butyl -4- ethyl ester（R1=normal-butyl, R2=ethyl）, 2,3- diisobutyl -2- cyano group succinic acid -1- second
Ester -4- N-butyl（R1=ethyl, R2=normal-butyl）, 2,3- di-sec-butyl -2- cyano group dimethyl succinate, 2,3- di-sec-butyl -2-
Cyano group diethyl succinate, 2,3- di-sec-butyl -2- cyano group succinic acid di-n-propyl ester, 2,3- di-sec-butyl -2- cyano group succinic acid
Diisopropyl ester, 2,3- di-sec-butyl -2- cyano group succinic acid di-n-butyl, 2,3- di-sec-butyl -2- cyano group succinic acid diisobutyl ester,
2,3- di-sec-butyl -2- cyano group succinic acid -1- methyl ester -4- ethyl ester（R1=methyl, R2=ethyl）, 2,3- di-sec-butyl -2- cyano group fourth
Diacid -1- ethyl ester -4- methyl ester（R1=ethyl, R2=methyl）, 2,3- di-sec-butyl -2- cyano group succinic acid -1- N-butyl -4- ethyl ester
（R1=normal-butyl, R2=ethyl）, 2,3- di-sec-butyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyl（R1=ethyl, R2=positive fourth
Base）, 2,3- bicyclopentyl -2- cyano group dimethyl succinate, 2,3- bicyclopentyl -2- cyano group diethyl succinate, 2,3- bicyclo-
Amyl group -2- cyano group succinic acid di-n-propyl ester, 2,3- bicyclopentyl -2- cyano group diisopropyl ester amber acid, 2,3- bicyclopentyl -2- cyanogen
Base succinic acid di-n-butyl, 2,3- bicyclopentyl -2- cyano group succinic acid diisobutyl ester, 2,3- bicyclopentyl -2- cyano group succinic acid -
1- methyl ester -4- ethyl ester（R1=methyl, R2=ethyl）, 2,3- bicyclopentyl -2- cyano group succinic acid -1- ethyl ester -4- methyl ester（R1=second
Base, R2=methyl）, 2,3- bicyclopentyl -2- cyano group succinic acid -1- N-butyl -4- ethyl ester（R1=normal-butyl, R2=ethyl）、2,3-
Bicyclopentyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyl（R1=ethyl, R2=normal-butyl）, 2,3- dicyclohexyl -2- cyano group fourth
Acid dimethyl, 2,3- dicyclohexyl -2- cyano group diethyl succinate, 2,3- dicyclohexyl -2- cyano group succinic acid di-n-propyl ester,
2,3- dicyclohexyl -2- cyano group diisopropyl ester amber acid, 2,3- dicyclohexyl -2- cyano group succinic acid di-n-butyl, 2,3- bicyclo-
Hexyl -2- cyano group succinic acid diisobutyl ester, 2,3- dicyclohexyl -2- cyano group succinic acid -1- methyl ester -4- ethyl ester（R1=methyl, R2=
Ethyl）, 2,3- dicyclohexyl -2- cyano group succinic acid -1- ethyl ester -4- methyl ester（R1=ethyl, R2=methyl）, 2,3- dicyclohexyl -2-
Cyano group succinic acid -1- N-butyl -4- ethyl ester（R1=normal-butyl, R2=ethyl）, 2,3- dicyclohexyl -2- cyano group succinic acid -1- second
Ester -4- N-butyl（R1=ethyl, R2=normal-butyl）；It is preferably selected from 2,3- diisopropyl -2- cyano group diethyl succinate, 2,3- bis-
Isopropyl -2- cyano group succinic acid di-n-propyl ester, 2,3- diisopropyl -2- cyano group diisopropyl ester amber acid, 2,3- diisopropyl -2-
Cyano group succinic acid di-n-butyl and 2,3- diisopropyl -2- cyano group succinic acid diisobutyl ester.
Described has formula（Ⅰ）Internal electron donor compound a press international patent application no PCT/CN2010/000202
Disclosed method preparation.
According to catalytic component of the present invention, internal electron donor compound b shown in described Formula II be such as selected from
Lower compound：2,3- is double（2- ethyl-butyl）Succinic acid diethyl ester, 2,3- diethyl -2- isopropyl succinic acid diethyl ester,
2,3- diisopropyl succinic acid diethyl ester, 2,3- di-t-butyl succinic acid diethyl ester, 2,3- diisobutyl succinic acid diethyl
Base ester, 2,3-（Double trimethyl silyls）Succinic acid diethyl ester, 2-（3,3,3- trifluoro propyl）- 3- methylsuccinic acid diethyl
Base ester, 2,3- di neo-pentyl succinic acid diethyl ester, 2,3- diisoamyl succinic acid diethyl ester, 2,3-（1- trifluoromethyl-second
Base）Succinic acid diethyl ester, 2- isopropyl -3- isobutyl group succinic acid diethyl ester, the 2- tert-butyl group -3- isopropyl succinic acid diethyl
Base ester, 2- isopropyl -3- cyclohexyl succinic acid diethyl ester, 2- isopentyl -3- cyclohexyl succinic acid diethyl ester, 2,2,3,3-
Tetramethyl succinic acid diethyl ester, 2,2,3,3- tetraethyl succinic acid diethyl ester, 2,2,3,3- tetrapropyl succinic acid diethyl
Ester, 2,3- diethyl -2,3- diisopropyl disuccinic acid diethyl ester, 2,3- are double（2- ethyl-butyl）Succinic acid diisobutyl
Ester, 2,3- diethyl -2- isopropyl di-iso-octyl succinate, 2,3- diisopropyl di-iso-octyl succinate, 2,3- di-t-butyl
Succinic acid diisobutyl ester, 2,3- diisobutyl succinic acid diisobutyl ester, 2,3-（Double trimethyl silyls）Succinic acid two
Isobutyl, 2-（3,3,3- trifluoro propyl）- 3- methylsuccinic acid diisobutyl ester, 2,3- di neo-pentyl succinic acid diisobutyl
Ester, 2,3- diisoamyl succinic acid diisobutyl ester, 2,3-（1- trifluoromethyl-ethyl）Succinic acid diisobutyl ester, 2- isopropyl
Base -3- isobutyl group succinic acid diisobutyl ester, the 2- tert-butyl group -3- isopropyl succinic acid diisobutyl ester, 2- isopropyl -3- hexamethylene
Base succinic acid diisobutyl ester, 2- isopentyl -3- cyclohexyl succinic acid diisobutyl ester, 2,2,3,3- tetramethyl succinic acid two are different
Butyl ester, 2,2,3,3- tetraethyl succinic acid diisobutyl ester, 2,2,3,3- tetrapropyl succinic acid diisobutyl ester, 2,3- diethyl
Base -2,3- diisopropyl disuccinic acid diisobutyl ester；It is preferably selected from 2,3- diisopropyl succinic acid diethyl ester, 2,3- bis- uncle
Butyl succinic acid diethyl ester, 2,3- diisobutyl succinic acid diethyl ester and 2,3- diisopropyl di-iso-octyl succinate.
Described has formula（II）Internal electron donor compound b can as disclosed in CN1240729C method preparation.
To those skilled in the art, can easily reason out, all above-claimed cpd a and b both can be with pure
Optical isomeric form using it is also possible to the mixture of enantiomer or diastereomer and enantiomer
Mixture form using.When using a kind of pure isomer, generally adopt ordinary skill known in the art or work
Skill come to make they separate.Particularly a part of the compounds of this invention a or compound b can be respectively with pure raceme or meso
Form, or the form of their mixture is using.
According to a preferred embodiment of the present invention, in the formula of described titanium compound, X is chlorine, bromine or iodine；R13For C1-
C5Alkyl；Described titanium compound is preferably selected from tetraalkoxy titanium, titanium tetrahalide, three alkyl groups in the halogenalkoxy titaniums, dihalo- dialkoxy titanium
With single halogen tri-alkoxy titanium；Preferably titanium tetrahalide compound.Described tetraalkoxy titanium preferably is selected from following compound at least one
Kind：Titanium tetramethoxide, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums,
Four cyclohexyloxy titaniums or four phenoxide titaniums.Described titanium tetrahalide preferably is selected from least one in following compound：Titanium tetrachloride, four
Titanium bromide or titanium tetra iodide.Described three alkyl groups in the halogenalkoxy titaniums preferably are selected from least one in following compound：Trichloromethoxy titanium, three
Chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide or tribromo ethanolato-titanium.Described dihalo- dialkoxy titanium preferably is selected from
At least one in following compound：Dichloro dimethoxy titanium, dichlorodiethyl epoxide titanium, dichloro two positive propoxy titanium, dichloro two
Titanium isopropoxide or dibromo diethoxy titanium.Described single halogen tri-alkoxy titanium preferably is selected from least one in following compound：
One chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titanium or a chlorine three titanium isopropoxide.Specific at one
In embodiment, described titanium compound is titanium tetrachloride.
According to catalyst of the present invention（Solid）One specific embodiment of component, based in described alkyl magnesium or its alcohol adduct
Magnesium, the amount of described titanium compound is 0.5-100mol, preferably 1-50mol；The compound a of described internal electron donor and b's is total
Measure as 0.005-10mol, preferably 0.01-1mol.
According to alkoxyl magnesium carrier of the present invention, micro magnesium halide may be contained（As MgI2Or MgCl2）Or its alcohol closes
Thing, but if should be higher than that 90%, preferably above 95%, more preferably more than 98% with the cubage purity of Formulas I magnesium compound.
Importantly, the content of magnesium ethylate and different octyloxy magnesium controls requirement in alkoxyl magnesium carrier of the present invention
0.001≤m≤0.5.M value is excessive, and the reaction of carrier preparation can become too weak, and particle size is also required by the difficult to reach present invention
OK range；M value is too small, then the reaction of carrier preparation can excessively acutely be difficult to control to, the distribution of sizes of carrier particle
（SPAN value）Also can broaden, have influence on ultra-fine powder content and the bulk density of final catalyst activity and prepared polymer.Always
It, if departing from this compositing range, the catalyst of resulting vehicle preparation is all difficult to show the effect of the present invention, not preferably.More excellent
Select 0.001≤m≤0.25, particularly preferred 0.001≤m≤0.1.
Under preferable case, described spherical alkoxyl magnesium carrier mean diameter 25～80um；Particle diameter distribution index SPAN<
1.05.
According to alkoxyl magnesium carrier of the present invention, by magnesium metal, ethanol, isooctanol（2-Ethylhexyl Alcohol）With mixing halogenation
Agent is reacted under an inert atmosphere and is prepared.Described mixing halogenating agent is the combination of halogen and halogen compounds, described halogen and
The indefiniteness of halogen compounds selects：Iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide,
Calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodixde, ethyoxyl magnesium iodide, methoxyl group magnesium iodide, isopropyl iodide
Change magnesium, hydrogen chloride, chloracetyl chloride etc..
According to the preparation of alkoxyl magnesium carrier of the present invention, the wherein combination of the mixing preferred iodine of halogenating agent and magnesium chloride.
The weight ratio preferably 1 of iodine and magnesium chloride：0.05～0.05:1, more preferably 0.1:1～1:0.02.
According to the preparation of alkoxyl magnesium carrier of the present invention, wherein the rubbing of magnesium metal and the halogen atom mixing in halogenating agent
That ratio is 1:0.0002～1:0.2, preferably 1:0.001～1:0.08；The weight of alcohol total amount and magnesium is than for 4:1～50:1, preferably
6:1～25:1；Mol ratio X of wherein ethanol and isooctanol is 3 (2-m)/m>X>(2-m)/m.The water to alcohol used for the present invention
Content is not particularly limited, in order that the alkoxyl magnesium obtaining has better performance it is desirable to moisture is more few better.
In alcohol, water content general control controls in below 200ppm in below 1000ppm, preferably water content.
In the present invention, the magnesium being used is magnesium metal, and in the case that its reactivity worth is good, whatsoever shape is all
Of course, even if can the using of the shape such as graininess, silk ribbon shape or powder.In order to promote putting down of the alkoxyl magnesium generating
All size are maintained in suitable scope, and particle shape is excellent, and preferably magnesium metal is the ball of 10～360 μm of mean diameter
Shape particle, the more preferably spheroidal particle of mean diameter 50～300 μ Μ.In addition, the surface of magnesium metal is not particularly limited, but
The surface of magnesium metal forms the envelopes such as hydroxide, and the total amount of activated carbon can be made to decline, reacts slack-off, preferably always the containing of activated carbon
Amount>95%, the more preferably total content of activated carbon>98%.
Heretofore described inert atmosphere, preferably blanket of nitrogen, argon atmospher.
According to the preparation of alkoxyl magnesium carrier of the present invention, can alternatively be used inertia in preparation process organic molten
Agent.In the present invention, described atent solvent can be selected from least one in the alkane of C6～C10 or aromatic hydrocarbons, preferably hexane, heptan
At least one in alkane, octane, decane, benzene,toluene,xylene or derivatives thereof etc..
According to the preparation of alkoxyl magnesium carrier of the present invention, halogenating agent Adding Way has no particular limits, Ke Yirong
Solution adds it is also possible to be directly added in magnesium metal and alcohol with solid or liquid form in alcohol, can also be using in heating gold
During belonging to magnesium and alcoholic solution, the method for instillation halogenating agent alcoholic solution, thus be prepared the reaction of carrier.
According to the preparation of alkoxyl magnesium carrier of the present invention, wherein magnesium metal, alcohol, halogenating agent and atent solvent plus
Enter, can initially put into disposable for reactant it is also possible to select to put into by several times.Putting into raw material by several times can prevent from instantaneously producing
Substantial amounts of hydrogen, and prevent the spittle due to alcohol that instantaneously substantial amounts of hydrogen produces and causes or halogenating agent, from safety perspective
From the point of view of reaction uniformity, preferably this feed way.The number of times of segmentation can be according to the scale of reactor and various
The consumption of material is determining.
According to the preparation of alkoxyl magnesium carrier of the present invention, described reaction temperature is 30-90 DEG C, preferably 30-80 DEG C, more
Preferably 50-75 DEG C.The time of described reaction is 2～30 hours.In practical operation, the hydrogen that can be produced by observing response
Discharge stop judging that reaction terminates.
After the completion of reaction, the end product alkoxyl magnesium carrier obtaining can be with kept dry it is also possible to be suspended in for making
In inert diluent used during the catalyst solid constituent of standby lower step.
According to catalytic component of the present invention, based on the magnesium in described alkoxyl magnesium or its alcohol adduct, described titanizing
Compound amount is 0.5-100mol, preferably 1-50mol；The total amount of the compound a of described internal electron donor and b is rubbed for 0.005-10
You, preferably 0.01-1 mole.
According to catalyst solid constituent of the present invention, magnesium compound（As alkoxyl magnesium compound）, electron donor chemical combination
Thing a, electron donor compound b and titanium compound can by any way haptoreaction preparing catalyst solid constituent.For example, may be used
To be prepared by the following method：
Method one：
1. alkoxyl magnesium carrier, electron donor compound a, electron donor compound b and inert diluent are configured to hang
Supernatant liquid, the mixture reaction then being formed with titanium compound and inert diluents, is filtered；2. gained solid content adds titanium compound
Continue reaction with the mixture of inert diluent, filter；3. repeat the 2nd step to react 2-4 time；3. washed above-mentioned solid with atent solvent
Shape thing obtains catalyst solid constituent.
Method two：
1. will be dilute to the mixture of alkoxyl magnesium carrier, part electron donor compound a and electron donor compound b and inertia
Release agent and be configured to suspension, the mixture reaction then being formed with titanium compound and inert diluents, is filtered；2. gained solid content
Add the mixing that the mixture of titanium compound, inert diluent and remaining electron compound a and electron donor compound b is formed
Thing continues reaction, filters；3. gained solid content continuously adds titanium compound and the mixture of inert diluent continues reaction, mistake
Filter；4. repeat the 3rd step to react 2-4 time；5. wash above-mentioned solid content with atent solvent and obtain catalyst solid constituent.
Method three：
1. alkoxyl magnesium carrier and inert diluent are configured to suspension, then with titanium compound and inert diluents shape
The mixture reaction becoming, adds electron donor compound a and electron donor compound b, continues reaction, filters；2. gained solid
Thing adds the mixture continuation reaction that titanium compound and inert diluent are formed, and filters；3. repeat the 2nd step to react 2-4 time；4. use
Atent solvent washs above-mentioned solid content and obtains catalyst solid constituent.
Method four：
1. will be dilute to the mixture of alkoxyl magnesium carrier, part electron donor compound a and electron donor compound b and inertia
Release agent and be configured to suspension, the mixture reaction then being formed with titanium compound and inert diluents, add remaining electron donor
Compound a and the mixture of electron donor compound b, continue reaction, filter；2. gained solid content adds titanium compound and inertia
The mixture that diluent is formed continues reaction, filters；3. repeat the 2nd step to react 2-4 time；4. above-mentioned solid is washed with atent solvent
Thing obtains catalyst solid constituent.
According to the preparation of catalyst solid constituent of the present invention, the consumption of described inert diluent is with respect to alkoxyl magnesium
The mol ratio of the magnesium in compound（0.5～100）:1；Preferably（1～50）:1.Preferably inert diluent is toluene.
According to the preparation of catalyst solid constituent of the present invention, magnesium compound（As alkoxyl magnesium compound）, titanizing close
Thing, inert diluent and electron donor compound a and electron donor compound b are preferably according to following conditioned response：Reaction temperature
For -40～200 DEG C, more preferably -20～150 DEG C；Response time is 1 minute～20 hours, more preferably 5 minutes～8 hours.
According to the preparation of catalyst solid constituent of the present invention, preferably washing atent solvent is hexane.For washing
Method there is no particular limitation, preferably decantation, filter etc. mode.The usage amount of atent solvent, wash time, washing times do not have
It is particularly limited to, be usually used 1～1000 mole with respect to the compound of 1 mole of magnesium, preferably 10～500 moles of solvent,
Generally washing 1～24 hour, preferably 6～10 hours.In addition from the homogeneity of washing and the aspect of detersive efficiency, preferably exist
It is stirred in washing operation.
According to the present invention, each component containing in described catalyst solid constituent content can there is no particular limitation,
Can be conducive to carrying out the olefinic polymerization high melt flow rate (MFR) of acquisition and the wide olefin polymer of molecular weight distribution.Preferably feelings
Under condition, on the basis of the gross weight of described catalyst solid constituent, in described catalyst solid constituent, the content of titanium elements
（Or claim the Ti content in terms of titanium elements）For 1-8 weight %, the content of magnesium elements（Or claim the content of magnesium in terms of magnesium elements）For 10-
70 weight %, the content of halogen（Or claim the content of halogen in terms of halogens）For 20-90 weight %, described internal electron donor a and
The content of the total amount of internal electron donor b is 2-30 weight %, and the mol ratio of wherein internal electron donor a and internal electron donor b content is
1:4-4:1；Preferably, on the basis of the gross weight of described catalyst solid constituent, in described catalyst solid constituent, titanium unit
The content of element（Or claim the Ti content in terms of titanium elements）For 1.6-6 weight %, the content of magnesium elements（Or claim the magnesium in terms of magnesium elements
Content）For 15-40 weight %, the content of halogen（Or claim the content of halogen in terms of halogens）For 30-85 weight %, described interior give
The content of the total amount of electron a and internal electron donor b is 3-20 weight %, and wherein internal electron donor a and internal electron donor b rubs
That ratio is 1:4-3:1.
According to another aspect of the present invention, present invention also offers a kind of olefin polymerization catalysis, described catalyst
Product including following components：
A. above-mentioned catalytic component；
B. organo-aluminum compound；
C. optionally, dispatch from foreign news agency donor compound.
According to olefin polymerization catalysis of the present invention, the organo-aluminum compound as promoter can be olefinic polymerization
The organo-aluminum compound of the various promoters that can act as Ziegler-natta catalyst that field is commonly used.Preferably described have
Machine aluminium compound is formula AlR'n'X'3-n'Shown organo-aluminum compound, wherein, R' is selected from hydrogen, C1-C20Alkyl and C6-C20
Aryl；X' is halogen, and n' is the integer of 1-3.
Described organo-aluminum compound preferably is selected from least one in following compound：Trimethyl aluminium, triethyl aluminum, three different
Butyl aluminum, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter
At least one in ethylmercury chloride aluminum and ethyl aluminum dichloride, more preferably triethyl aluminum and/or triisobutyl aluminium.
The consumption of described organo-aluminum compound can be the conventional amount used of this area.In a specific embodiment, institute
The mol ratio stating organo-aluminum compound with catalyst solid constituent is calculated as 5 with aluminum/titanium:1-5000:1, preferably 20:1-1000:
1, more preferably 50:1-500:1.
Above-mentioned optionally mean that described catalyst can comprise component a and the product of b, also can comprise component a, b and c
Product.Described external electron donor component can be various external electron donors known in the industry, is not particularly limited.Described
External electron donor is preferably general formula R1″ m″R2″ n″Si(OR3″)4-m″-n″Shown organo-silicon compound, wherein, R1″And R2″Identical or
Difference, is each independently selected from halogen, hydrogen atom, C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20's
Haloalkyl；R3″Selected from C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；M'' and
N'' is respectively the integer of 0-3, and m''+n''<4
Preferably, organo-silicon compound are selected from least one in following compound：Trimethylmethoxysilane, diisopropyl
Base dimethoxysilane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxy
Silane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, uncle
Butyl isopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-uncle
Butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, bicyclopentyl dimethoxy
Base silane, cyclopentyl cyclohexyl dimethoxysilane, double（2- methylcyclopentyl）Dimethoxysilane, diphenyl dimethoxy silicon
Alkane, diphenyl diethoxy silane, phenyl triethoxysilane, MTMS, MTES, ethyl
Trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopropyl three second
TMOS, butyl trimethoxy silane, butyl triethoxysilane, trimethoxysilane, isobutyl group triethoxy
Silane, amyltrimethoxysilane, isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silicon
Alkane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, second
Thiazolinyl trimethoxy silane, VTES, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes；
These organo-silicon compound can be individually using it is also possible to be applied in combination two or more.It is highly preferred that Formula IV
Shown organo-silicon compound are selected from least one of following compound：Dicyclopentyl dimethoxyl silane, diisopropyl diformazan
TMOS, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl
In t-butyldimethoxysilane, tetraethoxysilane, propyl triethoxy base silane, isobutyl triethoxy silane at least
A kind of；
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.Concrete at one
Embodiment in, aluminum in described organo-aluminum compound and the mol ratio of described external donor compound are 0.1:1-500:1,
Preferably 1:1-300:1, more preferably 3:1-100:1.It means that when described external electron donor is organo-silicon compound, institute
The mol ratio stating organo-aluminum compound with organo-silicon compound is calculated as 0.1 with aluminum/silicon:1-500:1, preferably 1:1-300:1, more excellent
Select 3:1-100:1.
According to another aspect of the present invention, there is provided a kind of olefine polymerizing process, described alkene is in above-mentioned catalyst
It is polymerized in the presence of solid constituent or above-mentioned catalyst.
The olefine polymerizing process of the present invention can be used for all polymerizations of alkene it is also possible to be used for for multiple alkene carrying out copolymerization
Close.The method can be additionally used in preparing high isotactic, high fusion index polymer.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions are the temperature of olefinic polymerization is 0-150
DEG C, preferably 60-130 DEG C；Time is 0.1-5 hour, preferably 0.5-4 hour, and pressure is 0.01-10MPa, preferably 0.5-
5MPa.The consumption of catalyst can be the consumption of the various catalyst of prior art.
Alkene in the present invention, including such as formula CH2Alkene shown in=CHR, wherein R are hydrogen or C1-C12Alkyl, excellent
Elect hydrogen or C as1-C6Alkyl.Described CH2At least one in the preferably following compound of alkene shown in=CHR：Ethylene, propylene,
1- n-butene, 1- n-pentene, 1- n-hexylene, the positive octene of 1- and 4-methyl-1-pentene；More preferably in ethylene, propylene and 1-butylene
At least one.
In one specific embodiment of olefine polymerizing process in the present invention, the temperature of described polymerization is 85-130 DEG C,
Preferably 95-110 DEG C.
In the present invention, described catalyst solid constituent, organo-aluminum compound and external donor compound are being connect
First carry out pre-contact before tactile olefinic monomer, then contact with olefinic monomer again and carry out polyreaction.In the field of business also referred to as pre-
Contact or pre- complexation；The time of pre-contact is 0.1-30min, preferably 1-10 minute；The temperature of pre-contact is -20-80 DEG C, preferably
10-50℃.
According to olefine polymerizing process of the present invention（As reaction temperature is 85-130 DEG C）, preferred alkenes polymerization catalyst
The reaction of each component is carried out using the method for pre-contact.The time of pre-contact is 0.1-30min, preferably 1-10 minute；Pre-contact
Temperature be -20-80 DEG C, preferably 10-50 DEG C.
Further, it is also possible to by the olefin polymerization catalysis of the present invention first in olefinic monomer（On a small quantity）In the presence of carry out pre-polymerization
Close, then again the material obtaining after prepolymerization is contacted with olefinic monomer further and reacted.This technology is in the field of business to be referred to as
For " prepolymerization " technique, contribute to raising of polymerization catalyst activity and polymer bulk density etc..According to of the present invention
Olefin high-temperature polymerization method, olefin polymerization catalysis can be excellent using " prepolymerization " technique it is also possible to not adopt " prepolymerization " technique
Choosing adopts " prepolymerization " technique.Described prepolymerized multiplying power, that is, the polymer producing is 2- with the mass ratio of catalyst
3000gPP/gCat, preferably 3-2000gPP/gCat；The temperature of " prepolymerization " is -20-80 DEG C, preferably 10-50 DEG C.
In olefine polymerizing process of the present invention, described " pre-contact " technique and " pre- complexation " technique all alternatives make
With.Specifically, it is possible to implement the polymerization of " pre- complexation " technique is not adopted using " pre-contact " technique；Can also implement not
The polymerization of " pre- complexation " technique is adopted using " pre-contact " technique；Can also implement both to adopt " pre-contact " technique,
Polymerization using " pre- complexation " technique；Can also be and be added separately in olefinic monomer directly carry out polymerization instead by each component
Should, neither implement " pre-contact " nor implement " prepolymerization ".It is preferable to carry out both adopting " pre-contact " technique, be also adopted by " pre- network
The polymerization of conjunction " technique.
When catalytic component prepared by the present invention and catalyst are applied to olefinic polymerization, between being divided due to each group association
Same-action, not only high, the vertical structure capacity of orientation of catalyst activity is good, hydrogen response is good, and the molecular weight distribution width of polymer,
Isotacticity is high, bulk density is high, ultra-fine powder content is low；In addition, catalyst has higher safety coefficient（Without phthalic acid
Ester）.It is suitable for mechanical performance and processing characteristics are required according to the excellent combination property that the catalyst that the present invention provides shows
The exploitation of higher and eco-friendly Polyolefin Resin Grades.
Specific embodiment
The present invention is described in detail for tool with reference to embodiments.But the present invention is not limited by following embodiments.
In following examples, evaluate and test is carried out by the following method：
1）Breadth parameter of molecular weight distribution Mw/Mn：PL-GPC220 is produced using Polymer Laboratories company of Britain
Chromatograph of gel permeation combines the molecular weight distribution of IR5 type infrared detector determination sample, and chromatographic column is 3 series connection Plgel10 μ
M MIXED-B post, solvent and mobile phase are 1,2,4- trichloro-benzenes（Antioxidant containing 0.3g/1000ml 2,6- di-t-butyl is to first
Phenol）, 150 DEG C of column temperature, flow velocity 1.0ml/min, carried out pervasive using PL company EasiCal PS-1 Narrow distribution polystyrene standard specimen
Demarcate.
2）Titanium atom content in catalyst solid constituent is according to purchased from An He alliance（Tianjin）Development in science and technology company limited
721 spectrophotometer tests.
3）The melt index of polymer is using model XRZ- purchased from Changchun new experimental instrument and equipment company limited
00 fusion index instrument method according to specified in GB/T3682-2000 measures.
4）Malvern MastersizerTM2000 normal hexane dispersant laser diffractometry measurement alkoxyl magnesiums and catalyst
Grain size, particle size distribution（Wherein, SPAN=（D90-D10）/D50）.
5）In catalyst component for olefin polymerization, internal electron donor content uses Agilent7890 gas Chromatographic Determination.
6）The mensure of the m value in carrier：Take 0.1 gram of carrier, add 10mL1.2mol/L aqueous hydrochloric acid solution, shake 24 hours
So that it is decomposed, use gas chromatogram quantitative ethanol therein and 2-Ethylhexyl Alcohol, be then calculated as follows m value：
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
7）The method of testing of polymer isotacticity includes：The polymer samples of 2 grams of dryings, were placed in extractor with heptan of seething with excitement
After alkane extracts 6 hours, residue drying to constant weight calculates isotacticity by below equation：
Isotacticity（%）Polymer quality/2 × 100 after=extracting.
8）Fine polymer powder content（%）：Sieve resulting polymers with 100 eye mesh screens, the small particle powder under sieve accounts for always
The percentage by weight of polymer.
Alkoxyl magnesium carrier（1）Mg(OEt)2-m(OEHA)mPreparation：
Be sufficiently displaced from after the 16L voltage-resistant reactor with agitator with nitrogen, in reactor add 10L ethanol,
300mL2- ethyl hexanol, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder.Stirring makes system be warming up to 75 DEG C of back flow reaction simultaneously,
Till no longer having hydrogen to discharge.Stopped reaction, uses 3L washing with alcohol, filters, is dried.The alkoxyl magnesium carrier obtaining.Institute
Obtain alkoxyl magnesium carrier D50=30.2um, Span value 0.81, m value 0.015.
Alkoxyl magnesium carrier（2）Mg(OEt)2Preparation：
Preparation method is identical with alkoxyl magnesium carrier a1, simply 300mL2- ethyl hexanol is replaced with 300mL ethanol.Institute
Obtain alkoxyl magnesium carrier D50=37.3um, Span value 1.51, m value is 0.
Embodiment 1
The preparation of catalyst solid constituent A1：
Take 10g alkoxyl magnesium compound（1）, 50mL toluene, 1.5mmol2,3- diisopropyl -2- cyano group succinic acid diethyl
Ester（Compound a, with reference to the preparation method preparation in CN101811983A）With 6.0mmol2,3- diisopropyl diethyl succinate
（Compound b, with reference to preparation method preparation in CN1585737A）It is configured to suspension.Repeating displacement through high pure nitrogen
In 300mL reactor, add toluene 40mL and titanium tetrachloride 60mL, be warming up to 80 DEG C, then the suspension preparing is added
In kettle, constant temperature 1 hour, it is to slowly warm up to 110 DEG C, constant temperature 2 hours, filter pressing obtains solid content.Gained solid content adds toluene 78mL
With the mixed liquor of titanium tetrachloride 52mL in 110 DEG C of stir process 1 hour, it is processed as 3 times.Filter pressing, the solid hexane of gained
Washing 4 times, each 150mL, filter pressing, drying, obtain final product catalyst solid constituent.In gained catalyst solid constituent A1, titanium atom contains
Amount 3.1wt%, 2,3- diisopropyl -2- cyano group diethyl succinate contents 1.5wt%, 2,3- diisopropyl succinate diethylesters
9.4wt%.
Olefinic polyreaction
5 liters of autoclave gas-phase propenes being connected with catalyst feeder, propylene and hydrogen feed line are sufficiently displaced from.Room
Add the hexane solution of 5mL triethyl aluminum in catalyst feeder under temperature（The concentration of triethyl aluminum is 0.5mol/L）, 1mL ring
Hexyl methyl dimethoxysilane（CHMMS）Hexane solution（The concentration of CHMMS is 0.1mol/L）, 10mL anhydrous hexane and
The above-mentioned catalytic component A1 preparing of 10-14mg, mixes 2 minutes（Pre- complexation）After be added to autoclave.Close autoclave,
Introducing standard rises the liquid propene of hydrogen and 2.4L；In 20 minutes, temperature is risen to 70 DEG C under agitation.It is polymerized anti-at 70 DEG C
After answering 1 hour, stop stirring, remove unpolymerized propylene monomer, collect and obtain polymer P.
The polymerization activity of olefin polymerization catalysis, melt index（MI）, polymer isotacticity（II）, polymer stacks
Long-pending density（BD）, molecular weight distribution and weight average molecular weight result as shown in table 2.
The polymerization activity of wherein catalyst is calculated by following formula：
Polymerization activity=polymer P quality（Kilogram）/ alkene catalyst component A1 mass（g）
Embodiment 2-4, comparative example 1-4：
, with embodiment 1, institute is different for catalyst solid constituent A2, A3, A4, B1, B2, B3, B4 preparation method and polymerization
Be 2,3- diisopropyl -2- cyano group diethyl succinate（a）With 2,3- diisopropyl diethyl succinate（b）Consumption.Institute
Obtain catalyst solid constituent and composition is shown in Table 1.
The step of olefinic polyreaction with embodiment 1, difference be respectively using catalyst solid constituent A2, A3, A4,
B1、B2.Data is shown in Table 2.
Comparative example 5
Catalyst solid constituent B5 preparation method is with embodiment 1, except that 2,3- diisopropyl -2- cyano group succinic acid
Diethylester（a）With 2,3- diisopropyl succinate diethylester（b）All replaced with dibutyl phthalate.Gained catalyst is solid
Body component and composition are shown in Table 1.With embodiment 1, difference is using catalyst solid constituent B5 olefine polymerizing process.Data
It is shown in Table 2.
Comparative example 6
The preparation of catalyst solid constituent B6：
The preparation method of catalyst solid constituent B6 is identical with A1 preparation method in embodiment 1, simply carries alkoxyl magnesium
Body (1) replaces with (2).Gained catalyst solid constituent and composition are shown in Table 1.With embodiment 1, difference exists olefine polymerizing process
In using catalyst solid constituent B6.Data is shown in Table 2.
Table 1
Table 2
Can be seen that from Tables 1 and 2 data：Under equal conditions, with using pure internal electron donor compound b, pure
The catalyst of internal electron donor compound a（B1 and B2）Compare, had according to the catalyst that the present invention provides good comprehensive
Can, wider molecular weight distribution, higher bulk density, higher catalysis activity and preferable melt index；Especially gained
The isotactic index ratio of polymer is used alone a kind of internal electron donor will be high, shows that the stereotaxises ability of catalyst is high, this
Also indicate that the catalyst providing according to the present invention shows certain cooperative effect.In addition, in the interior electron beyond the present invention
During the molar ratio range of body compound b and a, cannot get above-mentioned effect（B3-B4）.Adopt phthalic acid with prior art
The catalyst of ester（B5）Compare, not only increase the safety coefficient of catalyst, keeping high activity of catalyst and high isocratic same
When, also significantly widen the molecular weight distribution of polymer.In addition, with the catalyst prepared using common alkoxyl magnesium carrier（B6）
Compare, not only increase isotacticity and the bulk density of polymer；Meanwhile, greatly reduce the ultra-fine powder content of polymer.
The alkene catalyst of present invention preparation is applied to polyolefin polymerization and has excellent combination property, shows certain
Synergism, not only high, the vertical structure capacity of orientation of catalyst activity is good, hydrogen response is good, and the molecular weight distribution of polymer
Wide, isotacticity is high, bulk density is high, ultra-fine powder content is low；In addition, catalyst has higher safety coefficient.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute any to the present invention
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.Within the scope of the claims the present invention can be made by regulation
Modification, and in without departing substantially from scope and spirit of the present invention, the present invention is revised.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 wherein disclosed particular case, on the contrary, this
Bright can be extended to other all methods and applications with identical function.
Claims (22)
1. a kind of catalyst component for olefin, it is included shown in the alkoxyl magnesium shown in formula I or its alcohol adduct, Formula II
The reaction of internal electron donor compound b shown in internal electron donor compound a, formula III and the titanium compound shown in formula IV is produced
Thing；Wherein, described internal electron donor compound a and the mol ratio of internal electron donor compound b consumption are 1:4-4:1；Formula I institute
Mean diameter D50 of the alkoxyl magnesium showing or its alcohol adduct is 20-100 μm, profile exponent SPAN<1.1,
Mg(OEt)2-m(OEHA)m(I)
In Formulas I, Et is ethyl, and EHA is 2- ethylhexyl, 0.001≤m≤0.5；
In Formula II, R1And R2Can be identical or differ, selected from hydrogen, C1-C14The alkyl of straight or branched, C3-C10Cycloalkyl, C6-C10
Aryl, C7-C10Alkaryl or aralkyl；R3And R4Can be identical or differ, selected from C1-C10Straight or branched alkyl, C3-C10Ring
Alkyl, C6-C20Aryl, C7-C20Alkaryl or C7-C20Aralkyl；
In formula III, group R5And R6It is same to each other or different to each other, selected from C1-C20Line style or the alkyl of side chain, alkylene, cycloalkanes
Base, aryl, aralkyl and alkaryl；Group R7-R10It is same to each other or different to each other, be hydrogen or C1-C20Line style or side chain alkyl,
Alkenyl, cycloalkyl, aryl, aralkyl or alkaryl；Described R5And R6Hetero atom can optionally be contained；
TiXn(OR13)4-n(IV)
In formula IV, X is halogen；R13For C1-C20Alkyl, n be 0-4 integer.
2. catalytic component according to claim 1 is it is characterised in that R7-R9It is all hydrogen, R10It is selected from and there is C3-C20's
Primary, secondary or tertiary alkyl group, cycloalkyl, aryl, aralkyl and alkaryl.
3. catalytic component according to claim 1 is it is characterised in that described internal electron donor compound a and b consumption
Mol ratio is 2:3-3:2.
4. the catalytic component according to any one in claim 1-3 is it is characterised in that give in shown in described Formulas I
Electron compound a is selected from following compound：2,3- diisopropyl -2- cyano group dimethyl succinate, 2,3- diisopropyl -2- cyanogen
Base diethyl succinate, 2,3- diisopropyl -2- cyano group succinic acid di-n-propyl ester, 2,3- diisopropyl -2- cyano group succinic acid two
Isopropyl ester, 2,3- diisopropyl -2- cyano group succinic acid di-n-butyl, 2,3- diisopropyl -2- cyano group succinic acid diisobutyl ester, 2,
3- diisopropyl -2- cyano group succinic acid -1- methyl ester -4- ethyl ester, 2,3- diisopropyl -2- cyano group succinic acid -1- ethyl ester -4- first
Ester, 2,3- diisopropyl -2- cyano group succinic acid -1- N-butyl -4- ethyl ester, 2,3- diisopropyl -2- cyano group succinic acid -1- second
Ester -4- N-butyl, 2,3- diisobutyl -2- cyano group dimethyl succinate, 2,3- diisobutyl -2- cyano group diethyl succinate,
2,3- diisobutyl -2- cyano group succinic acid di-n-propyl ester, 2,3- diisobutyl -2- cyano group diisopropyl ester amber acid, 2,3- bis- are different
Butyl -2- cyano group succinic acid di-n-butyl, 2,3- diisobutyl -2- cyano group succinic acid diisobutyl ester, 2,3- diisobutyl -2- cyanogen
Base succinic acid -1- methyl ester -4- ethyl ester, 2,3- diisobutyl -2- cyano group succinic acid -1- ethyl ester -4- methyl ester, 2,3- diisobutyl -
2- cyano group succinic acid -1- N-butyl -4- ethyl ester, 2,3- diisobutyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyl, 2,3- bis-
Sec-butyl -2- cyano group dimethyl succinate, 2,3- di-sec-butyl -2- cyano group diethyl succinate, 2,3- di-sec-butyl -2- cyano group
Succinic acid di-n-propyl ester, 2,3- di-sec-butyl -2- cyano group diisopropyl ester amber acid, 2,3- di-sec-butyl -2- cyano group succinic acid two
N-butyl, 2,3- di-sec-butyl -2- cyano group succinic acid diisobutyl ester, 2,3- di-sec-butyl -2- cyano group succinic acid -1- methyl ester -4-
Ethyl ester, 2,3- di-sec-butyl -2- cyano group succinic acid -1- ethyl ester -4- methyl ester, the positive fourth of 2,3- di-sec-butyl -2- cyano group succinic acid -1-
Ester -4- ethyl ester, 2,3- di-sec-butyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyl, 2,3- bicyclopentyl -2- cyano group succinic acid
Dimethyl ester, 2,3- bicyclopentyl -2- cyano group diethyl succinate, 2,3- bicyclopentyl -2- cyano group succinic acid di-n-propyl ester, 2,3-
Bicyclopentyl -2- cyano group diisopropyl ester amber acid, 2,3- bicyclopentyl -2- cyano group succinic acid di-n-butyl, 2,3- bicyclopentyl -
2- cyano group succinic acid diisobutyl ester, 2,3- bicyclopentyl -2- cyano group succinic acid -1- methyl ester -4- ethyl ester, 2,3- bicyclopentyl -2-
Cyano group succinic acid -1- ethyl ester -4- methyl ester, 2,3- bicyclopentyl -2- cyano group succinic acid -1- N-butyl -4- ethyl ester, 2,3- bicyclo- penta
Base -2- cyano group succinic acid -1- ethyl ester -4- N-butyl, 2,3- dicyclohexyl -2- cyano group dimethyl succinate, 2,3- dicyclohexyl -
2- cyano group diethyl succinate, 2,3- dicyclohexyl -2- cyano group succinic acid di-n-propyl ester, 2,3- dicyclohexyl -2- cyano group fourth two
Sour diisopropyl ester, 2,3- dicyclohexyl -2- cyano group succinic acid di-n-butyl, 2,3- dicyclohexyl -2- cyano group succinic acid two isobutyl
Ester, 2,3- dicyclohexyl -2- cyano group succinic acid -1- methyl ester -4- ethyl ester, 2,3- dicyclohexyl -2- cyano group succinic acid -1- ethyl ester -
4- methyl ester, 2,3- dicyclohexyl -2- cyano group succinic acid -1- N-butyl -4- ethyl ester, 2,3- dicyclohexyl -2- cyano group succinic acid -1-
Ethyl ester -4- N-butyl.
5. the catalytic component according to any one in claim 1-3 is it is characterised in that give in shown in described Formulas I
Electron compound a is selected from following compound：2,3- diisopropyl -2- cyano group diethyl succinate, 2,3- diisopropyl -2- cyanogen
Base succinic acid di-n-propyl ester, 2,3- diisopropyl -2- cyano group diisopropyl ester amber acid, 2,3- diisopropyl -2- cyano group succinic acid
Di-n-butyl and 2,3- diisopropyl -2- cyano group succinic acid diisobutyl ester.
6. the catalytic component according to any one in claim 1-3 is it is characterised in that give in shown in described Formula II
Electron compound b is selected from following compound：Double (2- ethyl-butyl) the succinic acid diethyl ester of 2,3-, 2,3- diethyl -2- are different
Propyl succinic acid diethyl ester, 2,3- diisopropyl succinic acid diethyl ester, 2,3- di-t-butyl succinic acid diethyl ester, 2,3-
Diisobutyl succinic acid diethyl ester, 2,3- (double trimethyl silyl) succinic acid diethyl ester, 2- (3,3,3- trifluoropropyl
Base) -3- methylsuccinic acid diethyl ester, 2,3- di neo-pentyl succinic acid diethyl ester, 2,3- diisoamyl succinic acid diethyl
Ester, 2,3- (1- trifluoromethyl-ethyl) succinic acid diethyl ester, 2- isopropyl -3- isobutyl group succinic acid diethyl ester, the tertiary fourth of 2-
Base -3- isopropyl succinic acid diethyl ester, 2- isopropyl -3- cyclohexyl succinic acid diethyl ester, 2- isopentyl -3- cyclohexyl amber
Amber acid diethyl ester, 2,2,3,3- tetramethyl succinic acid diethyl ester, 2,2,3,3- tetraethyl succinic acid diethyl ester, 2,2,3,
Double (the 2- ethyl of 3- tetrapropyl succinic acid diethyl ester, 2,3- diethyl -2,3- diisopropyl disuccinic acid diethyl ester, 2,3-
Butyl) succinic acid diisobutyl ester, 2,3- diethyl -2- isopropyl di-iso-octyl succinate, 2,3- diisopropyl succinic acid two
Isobutyl ester, 2,3- di-t-butyl succinic acid diisobutyl ester, 2,3- diisobutyl succinic acid diisobutyl ester, 2,3- (double front threes
Base silicyl) succinic acid diisobutyl ester, 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acid diisobutyl ester, 2,3- bis-
Neopentyl succinic acid diisobutyl ester, 2,3- diisoamyl succinic acid diisobutyl ester, 2,3- (1- trifluoromethyl-ethyl) succinum
Sour diisobutyl ester, 2- isopropyl -3- isobutyl group succinic acid diisobutyl ester, the 2- tert-butyl group -3- isopropyl succinic acid two isobutyl
Base ester, 2- isopropyl -3- cyclohexyl succinic acid diisobutyl ester, 2- isopentyl -3- cyclohexyl succinic acid diisobutyl ester, 2,2,
3,3- tetramethyl succinic acid diisobutyl ester, 2,2,3,3- tetraethyl succinic acid diisobutyl ester, 2,2,3,3- tetrapropyl succinum
Sour diisobutyl ester, 2,3- diethyl -2,3- diisopropyl disuccinic acid diisobutyl ester.
7. the catalytic component according to any one in claim 1-3 is it is characterised in that give in shown in described Formula II
Electron compound b is selected from following compound：2,3- diisopropyl succinic acid diethyl ester, 2,3- di-t-butyl succinic acid diethyl
Base ester, 2,3- diisobutyl succinic acid diethyl ester and 2,3- diisopropyl di-iso-octyl succinate.
8. the catalytic component according to any one in claim 1-3 is it is characterised in that described alkoxyl magnesium or its alcohol
25～80 μm of the mean diameter of compound；Particle diameter distribution index SPAN<1.05；0.001≤m≤0.25.
9. the catalytic component according to any one in claim 1-3 is it is characterised in that described alkoxyl magnesium or its alcohol
0.001≤m≤0.1 in compound.
10. the catalytic component according to any one in claim 1-3 it is characterised in that described titanium compound logical
In formula, X is chlorine, bromine or iodine；R13For C1-C5Alkyl, n be 0-4 integer.
11. catalytic components according to any one in claim 1-3 are it is characterised in that described titanium compound is selected from
Tetraalkoxy titanium, titanium tetrahalide, three alkyl groups in the halogenalkoxy titaniums, dihalo- dialkoxy titanium and single halogen tri-alkoxy titanium.
12. catalytic components according to any one in claim 1-3 are it is characterised in that with described catalyst solid
On the basis of the gross weight of component, the content of titanium elements is 1-8%, the content of magnesium elements is 10-70%, the content of halogen is 20-
90%th, the content of the total amount of described internal electron donor a and internal electron donor b be 2-30%, wherein internal electron donor a and interior to electricity
The mol ratio of daughter b content is 1:4-4:1.
13. catalytic components according to any one in claim 1-3 are it is characterised in that with described catalyst solid
On the basis of the gross weight of component, the content of titanium elements meter is 1.6-6%, the content of magnesium elements is 15-40%, the content of halogen is
30-85%, the content of the total amount of described internal electron donor a and internal electron donor b are 3-20 weight %, wherein internal electron donor a
Mol ratio with internal electron donor b is 1:4-3:1.
A kind of 14. catalyst for olefines polymerizing, it includes the product of following components：
A. the catalytic component described in any one in claim 1-13；
B. organo-aluminum compound；
C. optionally, external donor compound.
15. catalyst according to claim 14 are it is characterised in that described organo-aluminum compound is formula AlR'n'X'3-n'
Shown organo-aluminum compound, wherein, R' is selected from hydrogen, C1-C20Alkyl and C6-C20Aryl；X' is halogen, and n' is 1-3's
Integer.
16. catalyst according to claim 14 are it is characterised in that described external donor compound is general formula R1” m”
R2” n”Si(OR3”)4-m”-n”Shown organo-silicon compound, wherein, R1”And R2”Identical or different, be each independently selected from halogen,
Hydrogen atom, C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；R3”Selected from C1-C20Alkane
Base, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；M " and n " is respectively the integer of 0-3, and m "+n "<
4.
17. catalyst according to any one in claim 14-16 it is characterised in that described organo-aluminum compound with
The mol ratio of catalyst solid constituent is calculated as 5 with aluminum/titanium:1-5000:1；Aluminum in described organo-aluminum compound and outer electron
The mol ratio of body is 0.1:1-500:1.
18. catalyst according to any one in claim 14-16 it is characterised in that described organo-aluminum compound with
The mol ratio of catalyst solid constituent is calculated as 20 with aluminum/titanium:1-1000:1；Aluminum in described organo-aluminum compound and outer electron
The mol ratio of body is 1:1-300:1.
19. catalyst according to any one in claim 14-16 it is characterised in that described organo-aluminum compound with
The mol ratio of catalyst solid constituent is calculated as 50 with aluminum/titanium:1-500:1；Aluminum in described organo-aluminum compound and outer electron
The mol ratio of body is 3:1-100:1.
A kind of 20. olefine polymerizing process, catalytic component or right described in described alkene any one in claim 1-13
Require to be polymerized in the presence of catalyst described in any one in 14-19.
21. methods according to claim 20 are it is characterised in that the temperature of described polymerization is 85-130 DEG C.
22. methods according to claim 20 are it is characterised in that the temperature of described polymerization is 95-110 DEG C.
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| CN106608935B (en) * | 2015-10-27 | 2019-07-19 | 中国石油化工股份有限公司 | Catalytic component, catalyst and its application for olefinic polymerization |
| JP6670081B2 (en) * | 2015-11-24 | 2020-03-18 | 東邦チタニウム株式会社 | Method for producing catalyst for olefin polymerization |
| CN109679005A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1313869A (en) * | 1999-04-15 | 2001-09-19 | 巴塞尔技术有限公司 | Components and catalysts for the polymerization of olefins |
| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
| CN102603931A (en) * | 2011-01-19 | 2012-07-25 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313869A (en) * | 1999-04-15 | 2001-09-19 | 巴塞尔技术有限公司 | Components and catalysts for the polymerization of olefins |
| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
| CN102603931A (en) * | 2011-01-19 | 2012-07-25 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
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