CN104558287A - Catalyst component for olefin polymerization as well as catalyst - Google Patents
Catalyst component for olefin polymerization as well as catalyst Download PDFInfo
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- CN104558287A CN104558287A CN201310508884.7A CN201310508884A CN104558287A CN 104558287 A CN104558287 A CN 104558287A CN 201310508884 A CN201310508884 A CN 201310508884A CN 104558287 A CN104558287 A CN 104558287A
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Abstract
The invention discloses a catalyst component for olefin polymerization. The catalyst component comprises alkyl magnesium or an alcohol adduct thereof shown in a formula I, an internal electron donor compound a shown in a formula II, an internal electron donor compound b shown in a formula III and a reaction product of a titanium compound shown in a formula IV, wherein the average grain size D50 of the alkyl magnesium or the alcohol adduct thereof is 20-100 microns and the distribution index SPAN is less than 1.1. In the formula I, Et is ethyl, EHA is 2-ethylhexyl and m is greater than or equal to 0.001 but less than or equal to 0.5. The molar ratio of use levels of the internal electron donor compound a and the internal electron donor compound b is 1: 4 to 4: 1. The catalyst disclosed by the invention has the advantages of high polymerization activity, good stereotactic capacity and the like. The formulae are shown in the description.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of catalyst component for olefin and catalyzer.
Background technology
As everyone knows, Ziegler-Natta(Z-N) catalyzer, can be used for CH
2=CHR olefinic polyreaction, particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atom.As Ziegler-Natta(Z-N) catalyst component (or ingredient of solid catalyst) of the important component of catalyzer, using magnesium, titanium and internal electron donor as basal component.But various internal electron donor also can make product have some shortcomings while the corresponding polyolefin products certain features of imparting, thus limits their application.Researchist wishes the Z-N catalyzer finding over-all properties more excellent.
Concrete, the now widely used Z-N catalyzer containing phthalic ester internal electron donor has active high, the feature of resin good combination property, but phthalic ester is proved the Fertility that can injure the mankind, thus recently do not become study hotspot containing the Z-N catalyzer of phthalic ester internal electron donor.
Molecular weight distribution (MWD) affects mechanical property and the processing characteristics of polymkeric substance.High molecular weight moieties determines the long term mechanical strength of polymkeric substance to a great extent, and low molecular weight fraction determines its extrusion performance to a great extent.The disclosed Z-N catalyzer containing 1,3-diol ester internal electron donor of CN1213080C has active high, the feature that molecular weight distribution is wide, but its molecular weight distribution prepared is wide not enough, thus limits its application.The Z-N catalyzer of succinate-containing internal electron donor disclosed in EP990201172 and US60999436 has active high, stereotaxis ability is good, the feature that resulting polymers molecular weight distribution is wide, but this catalyzer is bad to molecular weight regulator (hydrogen is the molecular weight regulator the most often adopted) susceptibility, namely, when identical hydrogen usage, the melt flow rate (MFR) (MFR) (or claiming melting index) of polymkeric substance is on the low side; And for meeting injecting products, the especially processing request of thin wall parts, polymkeric substance often needs higher MFR.When production injection moulding homopolymer or anti-impact polymkeric substance, often wish that namely polymkeric substance has high MFR to have wide molecular weight distribution simultaneously.This polymkeric substance is considered to intensity that existing good processing characteristics also had and rigidity.
Take alkoxyl magnesium as the supported catalyst component of carrier, the propene polymer obtained, has particle form excellent, ultrafine powder content few (conference of ultrafine powder amount affects polymkeric substance continuous seepage), and taxis height waits premium properties.But, take alkoxyl magnesium as carrier, the catalyst for olefines polymerizing solid ingredient of excellent property be obtained, first must prepare the alkoxyl magnesium carrier of excellent property.The present inventor discloses a kind of compound alcohol alkoxyl magnesium carrier prepared for alkene catalyst and preparation method thereof in Chinese patent CN102453150A; React activity when the catalyst solid constituent of preparation and corresponding olefin polymerization catalysis are used for olefinic polymerization by this alkoxyl magnesium carrier, titanium compound and phthalate internal electron donor high, particle form excellence, ultrafine powder content is few, taxis is high olefin polymer can be obtained.But the polyolefin resin molecular weight distribution of this catalyst preparing is wide not enough.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of catalyst component for olefin (or claiming catalyst solid, ingredient of solid catalyst) and the catalyzer containing described catalyst component, the electron donor system (internal electron donor a and internal electron donor b) in described catalyst component has synergy.Described catalyzer is used for olefinic polymerization, and have polymerization activity high, stereotaxis ability is good, and hydrogen response is good, and molecular weight distribution is wide, and not containing phthalic ester in polymkeric substance; Especially, under high hydrogen concentration, the catalytic activity of catalyzer and the polymkeric substance degree of isotacticity of Geng Gao can be improved by a larger margin.
According to an aspect of the present invention, provide a kind of catalyst component for olefin, it comprises the reaction product of the alkoxyl magnesium shown in general formula I or its alcohol adduct, the internal electron donor compound a shown in formula II, the titanium compound shown in the internal electron donor compound b shown in formula III and general formula I V; Wherein, the mol ratio of described internal electron donor compound a and internal electron donor compound b consumption is 1:4-4:1; The median size D50 of the alkoxyl magnesium shown in general formula I or its alcohol adduct is 20-100um, dispersion index SPAN<1.1,
Mg(OEt)
2-m(OEHA)
m（I）
In formula I, Et is ethyl, and EHA is 2-ethylhexyl, 0.001≤m≤0.5, preferably 0.001≤m≤0.25, more preferably 0.001≤m≤0.1;
In formula II, R
1and R
2can be identical or not identical, be selected from hydrogen, C
1-C
14the alkyl of straight or branched, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl or aralkyl; R
3and R
4can be identical or not identical, be selected from C
1-C
10straight or branched alkyl, C
3-C
10cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl or C
7-C
20aralkyl;
In formula III, radicals R
5and R
6be same to each other or different to each other, be selected from C
1-C
20line style or the alkyl of side chain, alkylene, cycloalkyl, aryl, aralkyl and alkaryl; Radicals R
7-R
10being same to each other or different to each other, is hydrogen or C
1-C
20line style or the alkyl of side chain, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl; Described R
5and R
6optionally can contain heteroatoms;
TiX
n(OR
13)
4-n（IV）
In formula IV, X is halogen; R
13for C
1-C
20alkyl, n is the integer of 0-4.
According to catalyst component of the present invention, R
7-R
9be all hydrogen, R
10be selected from and there is C
3-C
20primary, secondary or tertiary alkyl group, cycloalkyl, aryl, aralkyl and alkaryl.
In the present invention, SPAN=(D
90-D
10)/D
50, wherein D
90represent that corresponding to cumulative percentage is the particle diameter of 90%, D
10represent that corresponding to cumulative percentage is the particle diameter of 10%, D
50represent that corresponding running summary of the points scored is the particle diameter of 50%.
Alkoxyl magnesium according to formula I of the present invention, its Chinese style I only represents the composition content of described oxyethyl group and 2-ethyl hexyl oxy, not the concrete structure of representation alkoxy magnesium.Concrete, as in Mg (OEt) (OEHA) only expression alkoxyl magnesium compound, the mol ratio of oxyethyl group and 2-ethyl hexyl oxy is 1, the mixture of its both can be mol ratio be diethoxy magnesium and two (2-ethyl hexyl oxygen) magnesium of 1, also can be oxyethyl group (2-ethyl hexyl oxy) magnesium compound, can also be the mixture of three; The mixture that the alkoxyl magnesium compound of its can be the total mole ratio of oxyethyl group and 2-ethyl hexyl oxy be various structures of 1 forms.
According to a preferred embodiment of catalyst component of the present invention, the mol ratio of described internal electron donor compound a and b consumption is 2:3-3:2.In described molar ratio range, there is more excellent over-all properties.
According to catalyst component of the present invention, internal electron donor compound a shown in described formula I is as being selected from following compound: 2,3-di-isopropyl-2-cyano group dimethyl succinate, 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl, 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester, 2,3-di-isopropyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-isopropyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=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 di-n-propyl ester, 2,3-diisobutyl-2-cyano group diisopropyl ester amber acid, 2,3-diisobutyl-2-cyano group succinic acid di-n-butyl, 2,3-diisobutyl-2-cyano group succinic acid diisobutyl esters, 2,3-diisobutyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-diisobutyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=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 diisopropyl ester amber acid, 2,3-di-sec-butyl-2-cyano group succinic acid di-n-butyl, 2,3-di-sec-butyl-2-cyano group succinic acid diisobutyl esters, 2,3-di-sec-butyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-sec-butyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-bicyclopentyl-2-cyano group dimethyl succinate, 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 esters, 2,3-bicyclopentyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-bicyclopentyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-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 diisopropyl ester amber acid, 2,3-dicyclohexyl-2-cyano group succinic acid di-n-butyl, 2,3-dicyclohexyl-2-cyano group succinic acid diisobutyl esters, 2,3-dicyclohexyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-dicyclohexyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl); Be preferably selected from 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl and 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester.
The described internal electron donor compound a with logical formula I is by the method preparation disclosed in international patent application no PCT/CN2010/000202.
According to catalyst component of the present invention, the internal electron donor compound b shown in described formula II is as being selected from following compound: two (2-ethyl-butyl) the succsinic acid diethyl ester of 2,3-, 2,3-diethyl-2-sec.-propyl succsinic acid diethyl ester, 2,3-di-isopropyl succsinic acid diethyl ester, 2,3-di-t-butyl succsinic acid diethyl ester, 2,3-diisobutyl succsinic acid diethyl ester, the two trimethyl silyl of 2,3-() succsinic acid diethyl ester, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid diethyl ester, 2,3-di neo-pentyl succsinic acid diethyl ester, 2,3-diisoamyl succsinic acid diethyl ester, 2,3-(1-trifluoromethyl-ethyl) succsinic acid diethyl ester, 2-sec.-propyl-3-isobutyl-succsinic acid diethyl ester, the 2-tertiary butyl-3-sec.-propyl succsinic acid diethyl ester, 2-sec.-propyl-3-cyclohexyl succsinic acid diethyl ester, 2-isopentyl-3-cyclohexyl succsinic acid diethyl ester, 2,2,3,3-tetramethyl-succsinic acid diethyl ester, 2,2,3,3-tetraethyl-succsinic acid diethyl ester, 2,2,3,3-tetrapropyl succsinic acid diethyl ester, 2,3-diethyl-2,3-di-isopropyl disuccinic acid diethyl ester, two (2-ethyl-butyl) the succsinic acid diisobutyl ester of 2,3-, 2,3-diethyl-2-sec.-propyl di-iso-octyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-t-butyl succsinic acid diisobutyl ester, 2,3-diisobutyl succsinic acid diisobutyl ester, the two trimethyl silyl of 2,3-() succsinic acid diisobutyl ester, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid diisobutyl ester, 2,3-di neo-pentyl succsinic acid diisobutyl ester, 2,3-diisoamyl succsinic acid diisobutyl ester, 2,3-(1-trifluoromethyl-ethyl) succsinic acid diisobutyl ester, 2-sec.-propyl-3-isobutyl-succsinic acid diisobutyl ester, the 2-tertiary butyl-3-sec.-propyl succsinic acid diisobutyl ester, 2-sec.-propyl-3-cyclohexyl succsinic acid diisobutyl ester, 2-isopentyl-3-cyclohexyl succsinic acid diisobutyl ester, 2,2,3,3-tetramethyl-succsinic acid diisobutyl ester, 2,2,3,3-tetraethyl-succsinic acid diisobutyl ester, 2,2,3,3-tetrapropyl succsinic acid diisobutyl ester, 2,3-diethyl-2,3-di-isopropyl disuccinic acid diisobutyl ester, be preferably selected from 2,3-di-isopropyl succsinic acid diethyl ester, 2,3-di-t-butyl succsinic acid diethyl ester, 2,3-diisobutyl succsinic acid diethyl ester and 2,3-di-isopropyl di-iso-octyl succinate.
The described internal electron donor compound b with general formula (II) can by the method preparation disclosed in CN1240729C.
To those skilled in the art, can easily reason out, all above-claimed cpd a and b both can use with pure optical isomeric form, also can use with the form of the mixture of the mixture of enantiomer or diastereomer and enantiomer.When using a kind of pure isomer, ordinary skill known in the art or technique is usually adopted to make them be separated.Particularly a part of the compounds of this invention a or compound b can respectively with pure racemize or mesomeric form, or the form of their mixture uses.
According to a preferred embodiment of the present invention, in the general formula of described titanium compound, X is chlorine, bromine or iodine; R
13for C
1-C
5alkyl; Described titanium compound is preferably selected from four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-dialkoxy titanium and single halogen tri-alkoxy titanium; Preferred titanium tetrahalide compound.At least one of described four titan-alkoxides preferably in following compound: tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, four cyclohexyloxy titaniums or four phenoxide titaniums.At least one of described titanium tetrahalide preferably in following compound: titanium tetrachloride, titanium tetrabromide or titanium tetra iodide.At least one of described three halogen titan-alkoxides preferably in following compound: trichloromethoxy titanium, tri-chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide or tribromo ethanolato-titanium.At least one of described dihalo-dialkoxy titanium preferably in following compound: dichloro dimethoxy titanium, dichlorodiethyl oxygen base titanium, dichloro two positive propoxy titanium, dichloro diisopropoxy titanium or dibromo diethoxy titanium.The described at least one of single halogen tri-alkoxy titanium preferably in following compound: a chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titanium or chlorine three titanium isopropoxide.In a specific embodiment, described titanium compound is titanium tetrachloride.
According to a specific embodiment of catalyzer of the present invention (solid) component, based on the magnesium in described alkyl magnesium or its alcohol adduct, the amount of described titanium compound is 0.5-100mol, preferred 1-50mol; The compound a of described internal electron donor and the total amount of b are 0.005-10mol, are preferably 0.01-1mol.
According to alkoxyl magnesium carrier of the present invention, may containing micro-magnesium halide (as MgI
2or MgCl
2) or its alcohol adduct, if but should higher than 90% with the cubage purity of formula I magnesium compound, preferably higher than 95%, more preferably more than 98%.
Importantly, content control overflow 0.001≤m≤0.5 of magnesium ethylate and different octyloxy magnesium in alkoxyl magnesium carrier of the present invention.M value is excessive, and reaction prepared by carrier can become too weak, and size of particles is also difficult to reach OK range of the presently claimed invention; M value is too small, then the reaction that prepared by carrier can too acutely be difficult to control, and the distribution of sizes (SPAN value) of carrier particle also can broaden, and has influence on ultrafine powder content and the tap density of final catalyst activity and prepared polymkeric substance.In a word, if depart from this compositing range, catalyzer prepared by gained carrier is all difficult to show effect of the present invention, not preferably.More preferably 0.001≤m≤0.25, particularly preferably 0.001≤m≤0.1.
Under preferable case, described spherical alkoxyl magnesium carrier median size 25 ~ 80um; Size distribution index SPAN<1.05.
According to alkoxyl magnesium carrier of the present invention, reacted under an inert atmosphere by MAGNESIUM METAL, ethanol, isooctyl alcohol (2-Ethylhexyl Alcohol) and Mixed bittern agent and prepare.Described Mixed bittern agent is the combination of halogen and halogen compounds, and the indefiniteness of described halogen and halogen compounds is selected: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, Repone K, Potassium Bromide, potassiumiodide, calcium chloride, Calcium Bromide, calcium iodide, mercury chloride, mercuric bromide, red mercury iodide, oxyethyl group magnesium iodide, methoxyl group magnesium iodide, sec.-propyl magnesium iodide, hydrogenchloride, chloroacetyl chloride etc.
According to the preparation of alkoxyl magnesium carrier of the present invention, the wherein combination of the preferred iodine of Mixed bittern agent and magnesium chloride.The weight ratio of iodine and magnesium chloride is preferably 1:0.05 ~ 0.05:1, is more preferably 0.1:1 ~ 1:0.02.
According to the preparation of alkoxyl magnesium carrier of the present invention, the mol ratio of the halogen atom wherein in MAGNESIUM METAL and Mixed bittern agent is 1:0.0002 ~ 1:0.2, preferred 1:0.001 ~ 1:0.08; The weight ratio of alcohol total amount and magnesium is 4:1 ~ 50:1, preferred 6:1 ~ 25:1; Wherein the mol ratio X of ethanol and isooctyl alcohol is 3 (2-m)/m>X> (2-m)/m.The water-content of the present invention to alcohol used is not particularly limited, and in order to make the alkoxyl magnesium of acquisition have better performance, requires that moisture content is more few better.In alcohol, water-content general control is at below 1000ppm, and preferably water content controls at below 200ppm.
In the present invention, the magnesium used is MAGNESIUM METAL, when its reactivity worth is good, whatsoever shape can, even if can the using of particulate state, silk ribbon shape or the shape such as Powdered.In order to the Average Particle Diameters of the alkoxyl magnesium impelling generation remains in suitable scope, and particle form is excellent, and preferable alloy magnesium is the spheroidal particle of median size 10 ~ 360 μm, more preferably the spheroidal particle of median size 50 ~ 300 μ Μ.In addition, the surface of MAGNESIUM METAL is not particularly limited, but forms the tunicles such as oxyhydroxide on the surface of MAGNESIUM METAL, the total amount of activated carbon can be made to decline, react slack-off, the total content >95% of preferred activated carbon, more preferably the total content >98% of activated carbon.
Inert atmosphere described in the present invention, preferred nitrogen atmosphere, argon atmospher.
According to the preparation of alkoxyl magnesium carrier of the present invention, in preparation process, can alternatively be used inert organic solvents.In the present invention, described inert solvent can be selected from least one in the alkane of C6 ~ C10 or aromatic hydrocarbons, at least one in preferred hexane, heptane, 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, can be dissolved in alcohol and add, also can directly join in MAGNESIUM METAL and alcohol with solid or liquid form, can also adopt in the process of heating of metal magnesium and alcoholic solution, the method of 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 the adding of MAGNESIUM METAL, alcohol, halogenating agent and inert solvent, can, at first by disposable for reactant input, gradation also can be selected to drop into.Gradation drops into the hydrogen that raw material can prevent instantaneous generation a large amount of, and prevents the spittle of alcohol or the halogenating agent caused because instantaneous a large amount of hydrogen produces, and considers, preferred this feed way from the angle of safety perspective and reaction homogeneity.The number of times of segmentation can be determined according to the consumption of the scale of reactor and various material.
According to the preparation of alkoxyl magnesium carrier of the present invention, described temperature of reaction is 30-90 DEG C, preferred 30-80 DEG C, more preferably 50-75 DEG C.The time of described reaction is 2 ~ 30 hours.In actually operating, the discharge of the hydrogen that can be produced by observing response stops judging that reaction terminates.
After having reacted, the final product alkoxyl magnesium carrier obtained can kept dry, in inert diluent used when also can be suspended in the catalyst solid constituent for the preparation of lower step.
According to catalyst component of the present invention, based on the magnesium in described alkoxyl magnesium or its alcohol adduct, described titanium compound amount is 0.5-100mol, preferred 1-50mol; The compound a of described internal electron donor and the total amount of b are 0.005-10 mole, are preferably 0.01-1 mole.
According to catalyst solid constituent of the present invention, magnesium compound (as alkoxyl magnesium compound), electron donor compound a, electron donor compound b and titanium compound contact reacts can carry out Kaolinite Preparation of Catalyst solid ingredient by any way.Such as, can prepare by the following method:
Method one:
1. alkoxyl magnesium carrier, electron donor compound a, electron donor compound b and inert diluent are mixed with suspension, the mixture reaction then formed with titanium compound and inert diluents, filter; 2. gained solid substance adds the mixture continuation reaction of titanium compound and inert diluent, filters; 3. repeat the 2nd step reaction 2-4 time; 3. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
Method two:
1. the mixture of alkoxyl magnesium carrier, part electron donor compound a and electron donor compound b and inert diluent are mixed with suspension, the mixture reaction then formed with titanium compound and inert diluents, filter; 2. the mixture that gained solid substance adds titanium compound, the mixture of inert diluent and all the other electron compound as and electron donor compound b is formed continues reaction, filters; 3. gained solid substance continues the mixture continuation reaction adding titanium compound and inert diluent, filters; 4. repeat the 3rd step reaction 2-4 time; 5. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
Method three:
1. alkoxyl magnesium carrier and inert diluent are mixed with suspension, the mixture reaction then formed with titanium compound and inert diluents, add electron donor compound a and electron donor compound b, continue reaction, filter; 2. gained solid substance adds the mixture continuation reaction of titanium compound and inert diluent formation, filters; 3. repeat the 2nd step reaction 2-4 time; 4. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
Method four:
1. the mixture of alkoxyl magnesium carrier, part electron donor compound a and electron donor compound b and inert diluent are mixed with suspension, then the mixture reaction formed with titanium compound and inert diluents, add the mixture of all the other electron donor compound as and electron donor compound b, continue reaction, filter; 2. gained solid substance adds the mixture continuation reaction of titanium compound and inert diluent formation, filters; 3. repeat the 2nd step reaction 2-4 time; 4. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
According to the preparation of catalyst solid constituent of the present invention, the consumption of described inert diluent is relative to the mol ratio (0.5 ~ 100) of the magnesium in alkoxyl magnesium compound: 1; Preferably (1 ~ 50): 1.Preferred inert diluent is toluene.
According to the preparation of catalyst solid constituent of the present invention, magnesium compound (as alkoxyl magnesium compound), titanium compound, inert diluent and electron donor compound a and electron donor compound b are preferably according to following conditioned response: temperature of reaction is-40 ~ 200 DEG C, more preferably-20 ~ 150 DEG C; Reaction times is 1 minute ~ 20 hours, is more preferably 5 minutes ~ 8 hours.
According to the preparation of catalyst solid constituent of the present invention, preferred washing inert solvent is hexane.For the method for washing, there is no particular limitation, the modes such as preferred decant, filtration.The usage quantity of inert solvent, washing time, washing times are not particularly limited, and usually use 1 ~ 1000 mole relative to the compound of 1 mole of magnesium, are preferably the solvent of 10 ~ 500 moles, usually wash 1 ~ 24 hour, preferably 6 ~ 10 hours.In addition from the homogeneity of washing and the aspect of detersive efficiency, preferably stir in washing operation.
According to the present invention, each component contained in described catalyst solid constituent content can there is no particular limitation, can be conducive to carrying out olefinic polymerization and obtain high melt flow rate (MFR) and the wide olefin polymer of molecular weight distribution.Under preferable case, with the gross weight of described catalyst solid constituent for benchmark, in described catalyst solid constituent, the content (or claiming in the titanium content of titanium elements) of titanium elements is 1-8 % by weight, the content (or claiming in the Mg content of magnesium elements) of magnesium elements is 10-70 % by weight, the content (or claiming in the content of halogen of halogens) of halogen is 20-90 % by weight, the content of the total amount of described internal electron donor a and internal electron donor b is 2-30 % by weight, and wherein the mol ratio of internal electron donor a and internal electron donor b content is 1:4-4:1; Preferably, with the gross weight of described catalyst solid constituent for benchmark, in described catalyst solid constituent, the content (or claiming in the titanium content of titanium elements) of titanium elements is 1.6-6 % by weight, the content (or claiming in the Mg content of magnesium elements) of magnesium elements is 15-40 % by weight, the content (or claiming in the content of halogen of halogens) of halogen is 30-85 % by weight, the content of the total amount of described internal electron donor a and internal electron donor b is 3-20 % by weight, and wherein the mol ratio of internal electron donor a and internal electron donor b is 1:4-3:1.
According to another aspect of the present invention, present invention also offers a kind of olefin polymerization catalysis, described catalyzer comprises the reaction product of following component:
A. above-mentioned catalyst component;
B. organo-aluminium compound;
C. optionally, dispatch from foreign news agency donor compound.
According to olefin polymerization catalysis of the present invention, the various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst that the organo-aluminium compound as promotor can be commonly used for field of olefin polymerisation.Preferred described organo-aluminium compound is general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3.
At least one of described organo-aluminium compound preferably in following compound: at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, more preferably triethyl aluminum and/or triisobutyl aluminium.
The consumption of described organo-aluminium compound can be the conventional amount used of this area.In a specific embodiment, the mol ratio of described organo-aluminium compound and catalyst solid constituent counts 5:1-5000:1 with aluminium/titanium, is preferably 20:1-1000:1, is more preferably 50:1-500:1.
Above-mentionedly optionally mean the reaction product that described catalyzer can comprise component a and b, also can comprise the reaction product of component a, b and c.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 R
1 " m "r
2 " n "si (OR
3 ")
4-m "-n "shown silicoorganic compound, wherein, R
1 "and R
2 "identical or different, be selected from halogen, hydrogen atom, C independently of one another
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3 "be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M'' and n'' is respectively the integer of 0-3, and m''+n''<4
Preferably, silicoorganic compound are selected from least one in following compound: trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes, these silicoorganic compound can individually use, and also two or more can be combinationally used.More preferably, the silicoorganic compound shown in formula VI are selected from least one in following compound: at least one in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane, propyl triethoxy base silane, isobutyl triethoxy silane;
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.In a specific embodiment, the mol ratio of the aluminium in described organo-aluminium compound and described external donor compound is 0.1:1-500:1, preferred 1:1-300:1, more preferably 3:1-100:1.This just means, when described external electron donor is silicoorganic compound, the mol ratio of described organo-aluminium compound and silicoorganic compound counts 0.1:1-500:1 with aluminium/silicon, preferred 1:1-300:1, more preferably 3:1-100:1.
According to another aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the existence of above-mentioned catalyst solid constituent or above-mentioned catalyzer.
Olefine polymerizing process of the present invention may be used for all polymerizations of alkene, also may be used for multiple alkene to carry out copolymerization.The method also can be used for preparing high isotactic, high fusion index polymkeric substance.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions is the temperature of olefinic polymerization is 0-150 DEG C, preferred 60-130 DEG C; Time is 0.1-5 hour, preferred 0.5-4 hour, and pressure is 0.01-10MPa, is preferably 0.5-5MPa.The consumption of catalyzer can be the consumption of the various catalyzer of prior art.
Alkene in the present invention, comprises as general formula CH
2alkene shown in=CHR, wherein R is hydrogen or C
1-C
12alkyl, be preferably hydrogen or C
1-C
6alkyl.Described CH
2at least one in the preferred following compound of alkene shown in=CHR: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; More preferably at least one in ethene, propylene and 1-butylene.
In a specific embodiment of olefine polymerizing process in the present invention, the temperature of described polymerization is 85-130 DEG C, preferred 95-110 DEG C.
In the present invention, described catalyst solid constituent, organo-aluminium compound and external donor compound were first carried out pre-contact before contacting olefinic monomer, and then contact with olefinic monomer and carry out polyreaction.In the field of businessly also be referred to as pre-contact or pre-complexing; The time of pre-contact is 0.1-30min, preferred 1-10 minute; The temperature of pre-contact is-20-80 DEG C, preferred 10-50 DEG C.
According to olefine polymerizing process of the present invention (if temperature of reaction is 85-130 DEG C), the reaction of preferred alkenes polymerizing catalyst each component adopts the method for pre-contact to carry out.The time of pre-contact is 0.1-30min, preferred 1-10 minute; The temperature of pre-contact is-20-80 DEG C, preferred 10-50 DEG C.
In addition, olefin polymerization catalysis of the present invention first can also be carried out prepolymerization under the existence of olefinic monomer (on a small quantity), and then the material obtained after prepolymerization is contacted with olefinic monomer further react.This technology is in the field of business is referred to as " prepolymerization " technique, contributes to the raising etc. of polymerization catalyst activity and polymer bulk density.According to olefin high-temperature polymerization method of the present invention, olefin polymerization catalysis can adopt " prepolymerization " technique, also can not adopt " prepolymerization " technique, preferably adopts " prepolymerization " technique.Described prepolymerized multiplying power, the polymkeric substance namely produced and the mass ratio of catalyzer are 2-3000gPP/gCat, preferred 3-2000gPP/gCat; The temperature of " prepolymerization " is-20-80 DEG C, preferred 10-50 DEG C.
In olefine polymerizing process of the present invention, described " pre-contact " technique and " pre-complexing " technique are all alternative to be used.Concrete, can implement to adopt " pre-contact " technique and the polymerization process that do not adopt " pre-complexing " technique; Also can implement not adopt " pre-contact " technique and the polymerization process adopting " pre-complexing " technique; Also can implement both to have adopted " pre-contact " technique, also adopt the polymerization process of " pre-complexing " technique; Can also be each component is joined in olefinic monomer respectively directly carry out polyreaction, namely neither implement " pre-contact " and also do not implement " prepolymerization ".Preferred enforcement both adopted " pre-contact " technique, also adopted the polymerization process of " pre-complexing " technique.
Catalyst component prepared by the present invention and catalyst application are when olefinic polymerization, due between each component synergy, not only high, the vertical structure orientation property of catalyst activity is good, hydrogen response is good, and the molecular weight distribution of polymkeric substance is wide, degree of isotacticity is high, tap density is high, ultrafine powder content is low; In addition, catalyzer has higher safety coefficient (not containing phthalic ester).Be applicable to requiring exploitation that is higher and eco-friendly Polyolefin Resin Grades to mechanical property and processing characteristics according to the excellent over-all properties that catalyzer provided by the invention shows.
Embodiment
Below in conjunction with embodiment tool, the present invention is described in detail.But the present invention does not limit by following embodiment.
In following examples, evaluate and test and carry out by the following method:
1) Breadth parameter of molecular weight distribution Mw/Mn: adopt Polymer Laboratories company of Britain to produce the molecular weight distribution of PL-GPC220 gel permeation chromatograph in conjunction with IR5 type infrared detector working sample, chromatographic column is 3 series connection Plgel10 μm of MIXED-B post, solvent and moving phase are 1,2,4-trichlorobenzene is (containing 0.3g/1000ml oxidation inhibitor 2,6-ditertbutylparacresol), column temperature 150 DEG C, flow velocity 1.0ml/min, adopts PL company EasiCal PS-1 Narrow distribution polystyrene standard specimen to carry out universal calibration.
2) the titanium atom content in catalyst solid constituent is according to the 721 spectrophotometer tests purchased from An Hemeng (Tianjin) development in science and technology company limited.
3) melting index of polymkeric substance is that the model of use purchased from the new experimental instrument and equipment company limited in Changchun is for XRZ-00 fusion index instrument is according to the method mensuration specified in GB/T3682-2000.
4) Malvern Mastersizer
tM2000 normal hexane dispersion agent laser diffractometries measure grain size, size-grade distribution (wherein, the SPAN=(D90-D10)/D50 of alkoxyl magnesium and catalyzer).
5) in olefin polymerization catalyst components, internal electron donor content uses Agilent7890 gas Chromatographic Determination.
6) mensuration of the m value in carrier: get 0.1 gram of carrier, add 10mL1.2mol/L aqueous hydrochloric acid, shakes and makes it decompose in 24 hours, uses gas-chromatography quantitative, be then calculated as follows m value to ethanol wherein and 2-Ethylhexyl Alcohol:
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
7) testing method of polymkeric substance degree of isotacticity comprises: 2 grams of dry polymer samples, is placed in extractor and after 6 hours, residuum is dried to constant weight, by following formulae discovery degree of isotacticity with the extracting of boiling heptane:
Polymer quality/2 × 100 after degree of isotacticity (%)=extracting.
8) fine polymer powder content (%): with 100 eye mesh screen screening resulting polymers, the small particle size powder under sieve accounts for the weight percent of total polymer.
Alkoxyl magnesium carrier (1) Mg (OEt)
2-m(OEHA)
mpreparation:
After fully replacing the 16L voltage-resistant reactor with agitator with nitrogen, in reactor, add 10L ethanol, 300mL2-ethylhexanol, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder.Stir makes system be warming up to 75 DEG C of back flow reaction simultaneously, till no longer including hydrogen discharge.Stopped reaction, uses 3L washing with alcohol, filtration, drying.The alkoxyl magnesium carrier obtained.Gained 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, just 300mL2-ethylhexanol is replaced with 300mL ethanol.Gained alkoxyl magnesium carrier D50=37.3um, Span value 1.51, m value is 0.
Embodiment 1
The preparation of catalyst solid constituent A1:
Get 10g alkoxyl magnesium compound (1), 50mL toluene, 1.5mmol2,3-di-isopropyl-2-cyano group diethyl succinate (compound a, preparation method's preparation with reference in CN101811983A) and 6.0mmol2,3-di-isopropyl ethyl succinate (compound b, with reference to preparation method's preparation in CN1585737A) is mixed with suspension.Repeating through high pure nitrogen in the 300mL reactor of replacing, add toluene 40mL and titanium tetrachloride 60mL, be warming up to 80 DEG C, then add in still by the suspension prepared, constant temperature 1 hour, is slowly warming up to 110 DEG C, and constant temperature 2 hours, press filtration obtains solid substance.The mixed solution that gained solid substance adds toluene 78mL and titanium tetrachloride 52mL 110 DEG C of stir process 1 hour, so process 3 times.Press filtration, the solid of gained hexanes wash 4 times, each 150mL, press filtration, drying, obtain catalyst solid constituent.Titanium atom content 3.1wt% in gained catalyst solid constituent A1,2,3-di-isopropyl-2-cyano group diethyl succinate content 1.5wt%, 2,3-di-isopropyl succinate diethyl ester 9.4wt%.
Olefinic polyreaction
The 5 liters of autoclave gas-phase propenes being connected with catalyst feeder, propylene and hydrogen feed line are fully replaced.In catalyst feeder, add the hexane solution (concentration of triethyl aluminum is 0.5mol/L) of 5mL triethyl aluminum, the hexane solution (concentration of CHMMS is 0.1mol/L) of 1mL Cyclohexyl Methyl Dimethoxysilane (CHMMS), 10mL anhydrous hexane and the above-mentioned catalyst component A1 prepared of 10-14mg under room temperature, after mixing 2 minutes (pre-complexing), join autoclave.Close autoclave, the standard of introducing rises the liquid propene of hydrogen and 2.4L; In under agitation 20 minutes, temperature is risen to 70 DEG C.At 70 DEG C, polyreaction is after 1 hour, stops stirring, and removes unpolymerized propylene monomer, collects and obtains polymer P.
The polymerization activity of olefin polymerization catalysis, melt index (MI), polymkeric substance degree of isotacticity (II), polymer bulk density (BD), molecular weight distribution and weight-average molecular weight result as shown in table 2.
Wherein the polymerization activity of catalyzer is calculated by following formula:
Polymerization activity=polymer P quality (kilogram)/alkene catalyst component A1 quality (g)
Embodiment 2-4, comparative example 1-4:
Catalyst solid constituent A2, A3, A4, B1, B2, B3, B4 preparation method and polymerization process are with embodiment 1, and difference is the consumption of 2,3-di-isopropyl-2-cyano group diethyl succinate (a) and 2,3-di-isopropyls ethyl succinate (b).Gained catalyst solid constituent and composition are in table 1.
The step of olefinic polyreaction is with embodiment 1, and difference is to use catalyst solid constituent A2, A3, A4, B1, B2 respectively.Data are in table 2.
Comparative example 5
Catalyst solid constituent B5 preparation method is with embodiment 1, and difference is that 2,3-di-isopropyl-2-cyano group diethyl succinate (a) and 2,3-di-isopropyls succinate diethyl ester (b) all replace with dibutyl phthalate.Gained catalyst solid constituent and composition are in table 1.Olefine polymerizing process is with embodiment 1, and difference is to adopt catalyst solid constituent B5.Data are 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, is just replaced with (2) by alkoxyl magnesium carrier (1).Gained catalyst solid constituent and composition are in table 1.Olefine polymerizing process is with embodiment 1, and difference is to adopt catalyst solid constituent B6.Data are in table 2.
Table 1
Table 2
As can be seen from table 1 and table 2 data: under equal conditions, the internal electron donor compound b pure with use, the catalyzer (B1 with B2) of pure internal electron donor compound a are compared, according to catalyzer provided by the invention, there is good over-all properties, wider molecular weight distribution, higher tap density, higher catalytic activity and good melting index; Especially to be used alone a kind of internal electron donor all high for the isotactic index ratio of resulting polymers, and show that the stereotaxis ability of catalyzer is high, this also shows to demonstrate certain synergistic effect according to catalyzer provided by the invention.In addition, when exceeding the molar ratio range of internal electron donor compound b of the present invention and a, can not get above-mentioned effect (B3-B4).With adopting the catalyzer of phthalic ester (B5) to compare in prior art, not only increasing the safety coefficient of catalyzer, while maintenance high activity of catalyst and high degree, also greatly having widened the molecular weight distribution of polymkeric substance.In addition, compare with the catalyzer (B6) using common alkoxyl magnesium carrier to prepare, not only increase degree of isotacticity and the tap density of polymkeric substance; Meanwhile, the ultrafine powder content of polymkeric substance is greatly reduced.
Alkene catalyst prepared by the present invention is applied to polyolefin polymerization and has excellent over-all properties, demonstrate certain synergy, not only high, the vertical structure orientation property of catalyst activity is good, hydrogen response is good, and the molecular weight distribution of polymkeric substance is wide, degree of isotacticity is high, tap density is high, ultrafine powder content is low; In addition, catalyzer has higher safety coefficient.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (12)
1. a catalyst component for olefin, it comprises the reaction product of the alkoxyl magnesium shown in general formula I or its alcohol adduct, the internal electron donor compound a shown in formula II, the titanium compound shown in the internal electron donor compound b shown in formula III and general formula I V; Wherein, the mol ratio of described internal electron donor compound a and internal electron donor compound b consumption is 1:4-4:1; The median size D50 of the alkoxyl magnesium shown in general formula I or its alcohol adduct is 20-100um, dispersion index SPAN<1.1,
Mg(OEt)
2-m(OEHA)
m（I）
In formula I, Et is ethyl, and EHA is 2-ethylhexyl, 0.001≤m≤0.5;
In formula II, R
1and R
2can be identical or not identical, be selected from hydrogen, C
1-C
14the alkyl of straight or branched, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl or aralkyl; R
3and R
4can be identical or not identical, be selected from C
1-C
10straight or branched alkyl, C
3-C
10cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl or C
7-C
20aralkyl;
In formula III, radicals R
5and R
6be same to each other or different to each other, be selected from C
1-C
20line style or the alkyl of side chain, alkylene, cycloalkyl, aryl, aralkyl and alkaryl; Radicals R
7-R
10being same to each other or different to each other, is hydrogen or C
1-C
20line style or the alkyl of side chain, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl; Described R
5and R
6optionally can contain heteroatoms;
TiX
n(OR
13)
4-n（IV）
In formula IV, X is halogen; R
13for C
1-C
20alkyl, n is the integer of 0-4.
2. catalyst component according to claim 1, is characterized in that, R
7-R
9be all hydrogen, R
10be selected from and there is C
3-C
20primary, secondary or tertiary alkyl group, cycloalkyl, aryl, aralkyl and alkaryl.
3. according to catalyst component described in any one in claim 1 or 2, it is characterized in that, the mol ratio of described internal electron donor compound a and b consumption is 2:3-3:2.
4. according to the catalyst component in claim 1-3 described in any one, it is characterized in that, internal electron donor compound a shown in described formula I is selected from following compound: 2, 3-di-isopropyl-2-cyano group dimethyl succinate, 2, 3-di-isopropyl-2-cyano group diethyl succinate, 2, 3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2, 3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2, 3-di-isopropyl-2-cyano group succinic acid di-n-butyl, 2, 3-di-isopropyl-2-cyano group succinic acid diisobutyl ester, 2, 3-di-isopropyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-isopropyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=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 di-n-propyl ester, 2,3-diisobutyl-2-cyano group diisopropyl ester amber acid, 2,3-diisobutyl-2-cyano group succinic acid di-n-butyl, 2,3-diisobutyl-2-cyano group succinic acid diisobutyl esters, 2,3-diisobutyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-diisobutyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=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 diisopropyl ester amber acid, 2,3-di-sec-butyl-2-cyano group succinic acid di-n-butyl, 2,3-di-sec-butyl-2-cyano group succinic acid diisobutyl esters, 2,3-di-sec-butyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-sec-butyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-bicyclopentyl-2-cyano group dimethyl succinate, 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 esters, 2,3-bicyclopentyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-bicyclopentyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-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 diisopropyl ester amber acid, 2,3-dicyclohexyl-2-cyano group succinic acid di-n-butyl, 2,3-dicyclohexyl-2-cyano group succinic acid diisobutyl esters, 2,3-dicyclohexyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-dicyclohexyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), be preferably selected from 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl and 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester.
5. according to the catalyst component in claim 1-4 described in any one, it is characterized in that, the internal electron donor compound b shown in described formula II is selected from following compound: two (2-ethyl-butyl) the succsinic acid diethyl ester of 2,3-, 2,3-diethyl-2-sec.-propyl succsinic acid diethyl ester, 2,3-di-isopropyl succsinic acid diethyl ester, 2,3-di-t-butyl succsinic acid diethyl ester, 2,3-diisobutyl succsinic acid diethyl ester, the two trimethyl silyl of 2,3-() succsinic acid diethyl ester, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid diethyl ester, 2,3-di neo-pentyl succsinic acid diethyl ester, 2,3-diisoamyl succsinic acid diethyl ester, 2,3-(1-trifluoromethyl-ethyl) succsinic acid diethyl ester, 2-sec.-propyl-3-isobutyl-succsinic acid diethyl ester, the 2-tertiary butyl-3-sec.-propyl succsinic acid diethyl ester, 2-sec.-propyl-3-cyclohexyl succsinic acid diethyl ester, 2-isopentyl-3-cyclohexyl succsinic acid diethyl ester, 2,2,3,3-tetramethyl-succsinic acid diethyl ester, 2,2,3,3-tetraethyl-succsinic acid diethyl ester, 2,2,3,3-tetrapropyl succsinic acid diethyl ester, 2,3-diethyl-2,3-di-isopropyl disuccinic acid diethyl ester, two (2-ethyl-butyl) the succsinic acid diisobutyl ester of 2,3-, 2,3-diethyl-2-sec.-propyl di-iso-octyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-t-butyl succsinic acid diisobutyl ester, 2,3-diisobutyl succsinic acid diisobutyl ester, the two trimethyl silyl of 2,3-() succsinic acid diisobutyl ester, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid diisobutyl ester, 2,3-di neo-pentyl succsinic acid diisobutyl ester, 2,3-diisoamyl succsinic acid diisobutyl ester, 2,3-(1-trifluoromethyl-ethyl) succsinic acid diisobutyl ester, 2-sec.-propyl-3-isobutyl-succsinic acid diisobutyl ester, the 2-tertiary butyl-3-sec.-propyl succsinic acid diisobutyl ester, 2-sec.-propyl-3-cyclohexyl succsinic acid diisobutyl ester, 2-isopentyl-3-cyclohexyl succsinic acid diisobutyl ester, 2,2,3,3-tetramethyl-succsinic acid diisobutyl ester, 2,2,3,3-tetraethyl-succsinic acid diisobutyl ester, 2,2,3,3-tetrapropyl succsinic acid diisobutyl ester, 2,3-diethyl-2,3-di-isopropyl disuccinic acid diisobutyl ester, be preferably selected from 2,3-di-isopropyl succsinic acid diethyl ester, 2,3-di-t-butyl succsinic acid diethyl ester, 2,3-diisobutyl succsinic acid diethyl ester and 2,3-di-isopropyl di-iso-octyl succinate.
6. according to the catalyst component in claim 1-5 described in any one, it is characterized in that, the median size 25 ~ 80um of described alkoxyl magnesium or its alcohol adduct; Size distribution index SPAN<1.05; 0.001≤m≤0.25, preferably 0.001≤m≤0.1.
7. according to the catalyst component in claim 1-6 described in any one, it is characterized in that, in the general formula of described titanium compound, X is preferably chlorine, bromine or iodine; R
13for C
1-C
5alkyl, n is the integer of 0-4; Described titanium compound is preferably selected from four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-dialkoxy titanium and single halogen tri-alkoxy titanium; More preferably titanium tetrahalide compound.
8. according to the catalyst component in claim 1-7 described in any one, it is characterized in that, with the gross weight of described catalyst solid constituent for benchmark, the content of titanium elements is 1-8%, the content of magnesium elements is 10-70%, the content of halogen is 20-90%, the content of the total amount of described internal electron donor a and internal electron donor b is 2-30%, and wherein the mol ratio of internal electron donor a and internal electron donor b content is 1:4-4:1; Preferably, 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 is 3-20 % by weight, and wherein the mol ratio of internal electron donor a and internal electron donor b is 1:4-3:1.
9. a catalyst for olefines polymerizing, it comprises the reaction product of following component:
A. the catalyst component in claim 1-8 described in any one;
B. organo-aluminium compound, is preferably general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3;
C. optionally, dispatch from foreign news agency donor compound, is preferably general formula R
1 " m "r
2 " n "si (OR
3 ")
4-m "-n "shown silicoorganic compound, wherein, R
1 "and R
2 "identical or different, be selected from halogen, hydrogen atom, C independently of one another
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3 "be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M'' and n'' is respectively the integer of 0-3, and m''+n''<4.
10. catalyzer according to claim 9, is characterized in that, the mol ratio of described organo-aluminium compound and catalyst solid constituent counts 5:1-5000:1 with aluminium/titanium, is preferably 20:1-1000:1, is more preferably 50:1-500:1; Aluminium in described organo-aluminium compound and the mol ratio of external electron donor are 0.1:1-500:1, preferred 1:1-300:1, more preferably 3:1-100:1.
11. 1 kinds of olefine polymerizing process, are polymerized under the existence of described alkene catalyzer described in catalyst component described in any one or claim 9 or 10 in claim 1-8.
12. methods according to claim 11, is characterized in that, the temperature of described polymerization is 85-130 DEG C, preferred 95-110 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585642A (en) * | 2014-10-23 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing catalyst component, catalyst and application thereof |
| CN106608935A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst components used for olefin polymerization, catalyst and application of catalyst |
| CN108290974A (en) * | 2015-11-24 | 2018-07-17 | 东邦钛株式会社 | The manufacturing method of polymerization of olefines catalyst |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE335014T1 (en) * | 1999-04-15 | 2006-08-15 | Basell Poliolefine Srl | COMPONENTS AND CATALYSTS FOR OLEFIN POLYMERIZATION |
| CN102453150B (en) * | 2010-10-25 | 2013-08-14 | 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 |
| CN102603931B (en) * | 2011-01-19 | 2014-03-12 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
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2013
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585642A (en) * | 2014-10-23 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing catalyst component, catalyst and application thereof |
| CN106608935A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst components used for olefin polymerization, catalyst and application of catalyst |
| 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 |
| CN108290974A (en) * | 2015-11-24 | 2018-07-17 | 东邦钛株式会社 | The manufacturing method of polymerization of olefines catalyst |
| EP3381952A4 (en) * | 2015-11-24 | 2019-07-31 | Toho Titanium Co., Ltd. | Method for producing catalyst for polymerization of olefins |
| 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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