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CN102234339B - Catalyst components for olefin polymerization and preparation method thereof - Google Patents

Catalyst components for olefin polymerization and preparation method thereof Download PDF

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CN102234339B
CN102234339B CN 201010152793 CN201010152793A CN102234339B CN 102234339 B CN102234339 B CN 102234339B CN 201010152793 CN201010152793 CN 201010152793 CN 201010152793 A CN201010152793 A CN 201010152793A CN 102234339 B CN102234339 B CN 102234339B
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赵瑾
夏先知
刘月祥
谭扬
乔素珍
彭人琪
李威莅
张纪贵
高平
张天一
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides a preparation method of catalyst components for olefin polymerization and catalyst components obtained thereby. In the preparation method, a spherical catalyst is prepared by using a spherical magnesium halide adduct as the carrier and employing a complex of diol ester compounds and 1,3-diether compounds as the internal electron donor; and the reaction temperature of the internal electron donor and the washing degree of the catalyst are controlled, so that the obtained catalyst presents surprisingly high polymerization activity and high stereoregular directivity when used for olefin polymerization (especially propylene polymerization) and still maintains a high activity even if the concentration of alkyl aluminum is very low; and the obtained polymer has wide molecular weight distribution and relatively low ash content.

Description

Be used for catalyst component of olefinic polymerization and preparation method thereof
Technical field
The present invention relates to a kind of catalyst component for olefinic polyreaction and preparation method thereof, more particularly, relate to a kind of take spherical adduct of magnesium halides as carrier, spherical catalyst component and catalyzer thereof take diol-lipid compound and diether compound as internal electron donor.
Technical background
As everyone knows, solid titanium series catalysts component take magnesium, titanium, halogen and electron donor as basal component, be used for olefinic polyreaction, particularly when propylene polymerization, have higher polymerization activity and vertical structure directional property, wherein the electron donor compound is one of requisite composition in the catalyst component, and along with the development of internal electron donor compound, polyolefin catalyst constantly updates.Adopt the catalyzer of different internal electron donors to have different characteristics, for example, some catalyzer has higher polymerization activity, and some catalyzer has preferably hydrogen response, and the polyolefin resin of some catalyzer preparation has wider molecular weight distribution etc.But in polyolefinic industrial production, need the employed catalyzer of polymerization to have very good over-all properties.
In order to improve the over-all properties of catalyzer, carrying out a large amount of research work always.Adopt the composite deficiency that remedies single internal electron donor performance of two kinds of (or two or more) internal electron donors in some research, improve the over-all properties of catalyzer.As: in the disclosed technology of patent US 6825309B2, the characteristics that the composite wide molecular mass that has not only kept the polymkeric substance of succinate catalyst of succinate and phthalic ester is distributed, and further improve the vertical structure directional property of catalyzer; Chinese patent ZL 200410073623.8 disclosed catalyst component and catalyzer, the catalyzer of the method preparation that employing is composite with 1,3-diol ester and dibutyl phthalate is used for the polymkeric substance that propylene polymerization obtains and has higher degree of isotacticity and wider molecular weight distribution.The disclosed catalyst component of Chinese patent CN1743346 and catalyzer, employing is carried out three kinds of electron donors composite, concrete is with 1,3-diol ester, dibutyl phthalate and ethyl benzoate carry out composite, the catalyst activity that it obtains improves, and molecular weight distribution and the degree of isotacticity of resulting polymkeric substance also are improved simultaneously.
Adopt in some researchs and improve the performance that catalyst preparation process improves catalyzer, its microtexture of ingredient of solid catalyst that adopts different preparation technologies to obtain may differ larger, can cause like this distribution in the quantity in active centre and various active centre different, thereby the performance of catalyzer differ larger.The improvement of catalyst preparation process mainly comprises uses different magnesium chloride supports, different preparation method and the optimization of preparation condition.Disclose the method for Kaolinite Preparation of Catalyst component among the patent WO 02/48208, very high solids concn is used in strong suggestion in this patent, and when pointing out to reduce solids concn, active and isotactic index can descend to some extent.Technology according to patent US4226741 prepares ingredient of solid catalyst, obtains the remarkable improvement aspect active and stereoselectivity two.The method for preparing catalyst that provides a kind of substep to add ester among the patent CN 101472681A, the catalyzer that uses the method to obtain can obviously reduce the fine powder content of polymkeric substance when being used for olefinic polymerization.
As everyone knows, the polymerization activity that improves catalyzer always is one of important research direction of this area, and in recent years along with to the increasing of ultrapure low ash content acrylic resin demand, to can under low aluminum alkyls (cocatalyst component) concentration, keeping the demand of superelevation polymerization activity catalyzer also become more and more urgent.
The inventor finds by repetition test in research process, employing is take spherical adduct of magnesium halides as carrier, and adopt with diol-lipid compound and 1, the 3-diether compound is composite during as the prepared spherical catalyst of internal electron donor, be used for olefinic polymerization by the temperature of reaction of control internal electron donor and the washing degree gained catalyzer of control catalyzer, especially during propylene polymerization, the polymerization activity (＞180kg PP/g cat) and the higher vertical structure directional property that have shown wonderful superelevation, even and under low aluminum alkyls (cocatalyst component) concentration, still kept very high activity, and the molecular weight distribution of resulting polymers is wider, and ash content is relatively low.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the catalyst component for olefinic polymerization and the catalyst component of acquisition thereof, this catalyst component has the polymerization activity of superelevation and high vertical structure directional property, and the polymkeric substance that obtains has wider molecular weight distribution and lower ash content.
A kind of preparation method of the catalyst component for olefinic polymerization, the method comprises:
(A) will be such as general formula (I) MgX 2.m (the .nE.qH of R ' OH) 2Adducts shown in the O is suspended in general formula (II) Ti (OR) 4-kX kIn shown titanium compound and the mixture of inert solvent, optional keeping for some time; With respect to the adducts shown in 1 mole of general formula (I) (based on MgX 2Meter), the mole number of the titanium compound that uses in step (A) is the 4-50 mole.
(B) under agitation, above-mentioned suspension slowly is heated to 100 ℃～130 ℃, add electron donor compound a and electron donor compound b in temperature-rise period or after temperature, described electron donor compound a and b can add together, also can separate or add step by step; The mol ratio of described electron donor compound a and electron donor compound b is 0.55-50, and preferably, the mol ratio of electron donor a and b is 0.65～10; Adducts shown in relative 1 mole of general formula (I) is (based on MgX 2Meter), the total amount of electron donor a and b is 0.1 to 0.8 mole.
(C) continue to stir 0.5～3h, then liquid is separated with solid;
(D) will process 0.5～3h with the mixture of the titanium compound shown in the general formula (II) or described titanium compound and inert solvent at 100～130 ℃ by the solids that step (C) obtains, then liquid be separated with solid;
(E) titanium compound of optional repeating said steps (D) is processed more than 1 time or 1 time; With
(F) with by step (D) or (E) (if having step (E)) solids of obtaining and dry of inert solvent washing, obtain ingredient of solid catalyst;
Wherein:
In the general formula (I), X is chlorine or bromine; R ' is C 1-C 4Alkyl; E is the o-alkoxyl benzoic acid ester compounds shown at least a general formula (III):
Figure GSA00000075866300031
R in its formula of (III) 1And R 2Be independently selected from C 1-C 12The alkyl of straight or branched, C 3-C 10Cycloalkyl, C 6-C 10Aryl, C 7-C 10Alkaryl and C 7-C 10Aralkyl; M is 1.0-5.0; N is 0-0.5; Q is 0-0.8; Wherein, R 1And R 2Can be identical or different, preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
In the general formula (I), m is 1.0-5.0; N is 0 or 0.001-0.5; Q is 0-0.8.Preferred m is 1.5-3.5, and n is 0 or 0.005-0.2.
In the general formula (II), R is C 1～C 20Alkyl, X is F, Cl or Br, k is 1～4 integer;
The electron donor compound a is selected from least a in the diol-lipid compound shown in the general formula (IV):
Figure GSA00000075866300041
In its formula of (IV), R 1-R 6, R 1-R 2Group is independently selected from the C of hydrogen, halogen atom, straight or branched 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Aralkyl;
The electron donor compound b is selected from least a in the diether compound shown in the logical formula V:
R 1R 2C(CH 2OR 3)(CH 2OR 4)
(V)
In its formula of (V), R 1And R 2Be independently selected from the C of hydrogen, straight or branched 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 6-C 20Aryl, C 7-C 20Aralkyl and C 7-C 20A kind of in the alkaryl optionally is keyed to ring, R between group 3And R 4Be independently selected from C 1-C 10Alkyl;
Preparation method at the catalyst component for olefinic polymerization of the present invention, preferably, described step (A) is following carries out: the adducts shown in the general formula (I) is suspended in advance in the mixture of the titanium compound shown in the general formula (II) that is chilled to-40 ℃～0 ℃ or described titanium compound and unreactive hydrocarbons solvent, then keep 5min～2h, the concentration of wherein said adducts solid in this suspension is lower than 200g/L.
Preferably, in the described step (B), after reaching more than 30 ℃, described electron donor compound a or b or the two temperature at suspension just add.
Preferably, the titanium compound that uses in step (A), (D) and the step (E) of choosing wantonly is identical, the total mole number of the titanium compound that uses in the described step is the 20-200 mole, with respect to the adducts shown in 1 mole of general formula (I) (based on MgX 2Meter); And the mole number of the titanium compound that uses in step (A) is the 4-50 mole, with respect to the adducts shown in 1 mole of general formula (I) (based on MgX 2Meter).
Preferably, in the general formula (I), m is 1.5-3.5, and n is 0.The electron donor compound a is selected from the heptanediol ester.
Preferably, in the general formula (I), m is 1.5-3.5, and n is 0.005-0.2, and the electron donor compound a is selected from heptanediol ester or pentadiol ester.
A catalyst component preparation method's of the present invention specific embodiments, it may further comprise the steps:
(A) adducts shown in the general formula (I) is suspended in advance in the mixture of the titanium compound shown in the general formula (II) that is chilled to-40 ℃～0 ℃ or described titanium compound and unreactive hydrocarbons solvent, then keep 5min～2h, the concentration of wherein said adducts solid in this suspension is lower than 200g/L, inert solvent such as hexane, heptane, octane, decane, toluene etc.;
(B) under agitation, above-mentioned suspension slowly is heated to 100 ℃～130 ℃, after the temperature of suspension reaches more than 30 ℃, just adds and state electron donor compound a or b or the two;
(C) continue to stir 0.5～3h, then liquid is separated with solid;
(D) will process 0.5～3h with the mixture of the titanium compound shown in the general formula (II) or described titanium compound and inert solvent at 100～130 ℃ by the solids that step (C) obtains, then liquid be separated with solid;
(E) titanium compound of repeating said steps (D) is processed 1 time to 3 times, and the titanium compound of use is identical in step (A), (D) and step (E), with respect to the adducts shown in 1 mole of general formula (I) (based on MgX 2Meter), the total mole number of the titanium compound that uses is the 20-200 mole; And in step (A) with respect to the adducts shown in 1 mole of general formula (I) (based on MgX 2Meter), the mole number of the titanium compound that uses is the 4-50 mole; With
(F) also dry by the solids that step (E) obtains with the inert solvent washing, obtain ingredient of solid catalyst;
Adducts shown in the above-mentioned general formula (I) is by magnesium halide, Organic Alcohol R 1The spherical adduct particle that OH and o-alkoxyl Benzoyl chloride (or o-alkoxyl benzoate compounds) reaction obtains, the carrier of its conduct in the preparation process of catalyzer uses.The polycomponent carrier that preferably contains the o-alkoxyl benzoic ether.
In the above-mentioned general formula (II), R is C 1～C 20Alkyl, X is F, Cl or Br, k is 1～4 integer.Described titanium compound in the component (2) is specifically selected a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine three titanium butoxide, dichloro dibutoxy titanium, trichlorine one titanium butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, the titanous chloride or their mixture, preferred titanium tetrachloride.
The particular compound of the o-alkoxyl benzoates shown in the above-mentioned general formula (III) is such as methyl o-anisate, the o-methoxybenzoic acid ethyl ester, the o-methoxybenzoic acid n-propyl, the o-methoxybenzoic acid isopropyl ester, the positive butyl ester of o-methoxybenzoic acid, the o-methoxybenzoic acid isobutyl ester, the o-ethoxybenzoic acid methyl esters, the o-ethoxybenzoic acid ethyl ester, the o-ethoxybenzoic acid n-propyl, the o-ethoxybenzoic acid isopropyl ester, the positive butyl ester of o-ethoxybenzoic acid, o-methoxybenzoic acid isobutyl ester etc.
Described electron donor compound a diol-lipid compound specifically can adopt: 1, the ammediol dibenzoate, the 2-methyl isophthalic acid, the ammediol dibenzoate, 2-ethyl-1, the ammediol dibenzoate, 2-propyl group-1, the ammediol dibenzoate, 2-butyl-1, the ammediol dibenzoate, 2,2-dimethyl-1, the ammediol dibenzoate, 2-ethyl-2-butyl-1, the ammediol dibenzoate, 2,2-diethyl-1, the ammediol dibenzoate, 2-methyl-2-propyl-1, the ammediol dibenzoate, 2-sec.-propyl-2-isopentyl-1, the ammediol dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl group-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl group-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2,4-trimethylammonium-1,3-pentanediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate, 2,2-dimethyl-1,5-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate etc.Preferred pentadiol ester and heptanediol ester.
Described electron donor compound b diether compound specifically can adopt: 2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-butyl-1, the 3-Propanal dimethyl acetal, 2-sec-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-1, the 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1, the 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-dipropyl-1, the 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1, the 3-Propanal dimethyl acetal, 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, the 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, the 3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1, the 3-Propanal dimethyl acetal, 9,9-dimethoxy-methyl fluorenes etc.Preferred 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal.
Above-mentioned 1 among the present invention, the 3-diether compound is disclosed among Chinese patent CN1020448C, CN100348624C and the CN1141285A.Its disclosed associated viscera is all introduced the present invention as a reference.
Adducts shown in the general formula of the present invention (I) is disclosed among Chinese patent CN1091748A, CN101050245A and the CN101486722A, and its disclosed associated viscera is all introduced the present invention as a reference.The preparation of relevant binary magnesium halide alcohol adduct carrier can be carried out by the following method: be to mix in 1: 2～1: 3 in molar ratio with anhydrous magnesium halide and low-carbon alcohol, temperature reaction generates the magnesium halide alcohol adduct melt, temperature of reaction is 90～140 ℃, in dispersion medium, after high shear forces, put into the inert media of cooling, form the spherical magnesium halide alcohol polymer particle, after washing, drying, obtain ball type carrier.High shear forces can adopt conventional method to obtain, such as high-speed mixing method (such as CN1330086A), high-gravity rotating bed (such as CN1580136A) and mulser method (CN1463990A) etc.Dispersant system adopts the hydro carbons inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, Vaseline wet goods.Heat-eliminating medium is selected from pentane, hexane, heptane, sherwood oil, raffinates oil etc.The ethanol adducts of preferred magnesium chloride.The preparation of relevant ternary magnesium halide carrier can be carried out by the following method: first with magnesium halide, pure and mild o-alkoxyl Benzoyl chloride (or o-alkoxyl benzoate compounds) three components contact reacts under the condition of heating, final temperature of reaction will reach and can make magnesium halide, the fusing of pure and mild o-alkoxyl benzoate compounds form melt, be preferably 100 ℃～140 ℃, then in dispersion medium, after high shear forces, put into the inert media of cooling, form the spherical magnesium halide alcohol polymer particle, after washing, drying, obtain ball type carrier.Described inert media generally adopts liquid aliphatic hydro carbons inert solvent, such as kerosene, paraffin oil, vaseline oil, white oil, hexane, heptane etc., when needing, also optionally adds some silicoorganic compound or tensio-active agent, such as methyl-silicone oil etc.When the contact reacts of magnesium halide, pure and mild o-alkoxyl Benzoyl chloride (or o-alkoxyl benzoate compounds) three components, also optionally add above-mentioned inert liquid medium.High shear forces can adopt conventional method to obtain, such as high-speed mixing method (such as CN1330086), high-gravity rotating bed (such as CN1580136A) and mulser method (CN1463990A) etc.
Another object of the present invention provides a kind of catalyzer for olefinic polymerization, comprises the reaction product of following component;
(1) catalyst component for preparing by aforesaid method of the present invention;
(2) alkylaluminium cpd.
(3) a kind of external donor compound of choosing wantonly is component wherein.
(2) alkylaluminium cpd wherein, its general formula is AlR ' " 3, R ' " is identical or not identical C 1-8Alkyl, wherein one or two alkyl can be replaced by chlorine, can select one or more aluminum alkyls mix to use, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C 6H 13) 3, Al (n-C 8H 17) 3Deng, preferred 10～500 generally take the Al/Ti mol ratio as 1～2000, more preferably 20～300 use the abovementioned alkyl aluminum compounds;
Component (3) a kind of external donor compound randomly wherein, for example list or polyfunctional carboxylic acids, carboxylic acid anhydride and carboxylicesters, ketone, ether, alcohol, lactone, and organophosphorus and silicoorganic compound.Preferably have organic silicon compound, its consumption is that Al/ED (mol/mol) is 2-200, preferred 2.5-100.
Described external electron donor preferably contains at least one Si-OR key, general formula is R 1 aR 2 bSi (OR 3) cSilicon compound, wherein a and b are 0 to 2 integer, c be the integer of 1-3 and (a+b+c) and be 4; R 1, R 2And R 3C 1-C 18Alkyl, randomly contain heteroatoms.Particularly preferred silicon compound, wherein a is that 1, b is that 1, c is 2, R 1And R 2In have at least one to be to be selected from branched-alkyl, alkenyl, alkylidene group, cycloalkyl or the aromatic yl group with 3-10 carbon atom, optional heteroatoms and the R of containing 3Be C 1-C 10Alkyl group, particularly methyl.The example of preferred silicon compound has Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-, three fluoro-2-propyl group)-methyl dimethoxysilane.In addition, preferred silicon compound also has, and wherein a is that 0, c is 3, R 2Be branched-alkyl or group of naphthene base, optional heteroatoms and the R of containing 3Be methyl.The example of optional silicon compound has cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and uncle's hexyl Trimethoxy silane like this.
Alkylaluminium cpd and optional external donor compound can be separately or as mixture and the active ingredient contact reacts of two kinds of compositions.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or contain in the inert solvent of polymerization single polymerization monomer, or in gas phase, or operates by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～90 ℃.Polymerization pressure is normal pressure or higher.In polymerization process, hydrogen can be used as molecular weight and the melting index that the polymericular weight conditioning agent joins telomerized polymer in the polymerization reactor.
Catalyst component, aluminum alkyls and external donor compound can add respectively polymerization reactor, also can mix rear adding polymerization reactor, join polymerization reactor after also can adopting the known prepolymerization method of the industry with the propylene pre-polymerization.
Another object of the present invention provides the directly low polyacrylic method of ash content of preparation from polymeric kettle of the above-mentioned catalyzer of a kind of the present invention of use.Particularly, the method is in the presence of catalyzer of the present invention, carries out the polyreaction of propylene, and resulting polymers directly obtains low ash content polypropylene without the washing last handling process.In this polyreaction, preferably use alkylaluminium cpd take the Al/Ti mol ratio as 10～300, more preferably 20-200; When adding external electron donor, its consumption is that Al/ED (mol/mol) is 5-200, preferred 10-100.
The polymerization of propylene is carried out according to currently known methods, in liquid monomer or contain in the inert solvent of polymerization single polymerization monomer, or in gas phase, or operates by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 ℃～120 ℃, preferably 60 ℃～80 ℃.Polymerization pressure is normal pressure or higher.In polymerization process, hydrogen can be used as molecular weight and the melting index that the polymericular weight conditioning agent joins telomerized polymer in the polymerization reactor.
Catalyst component, aluminum alkyls and external donor compound can add respectively polymerization reactor, also can mix rear adding polymerization reactor, join polymerization reactor after also can adopting the known prepolymerization method of the industry with the propylene pre-polymerization.
The present invention also provides the propene polymer by above-mentioned preparation method's preparation, and the ash oontent of this propene polymer can be lower than 100ppm, further can be lower than 50ppm, further can be lower than 30ppm; Isotactic index (II),, can be regulated according to the purposes of polymkeric substance further greater than 98.0% further greater than 97.5% greater than 96.7%; Melting index (MI) is greater than 0.1g/10min, and is preferred: 1.0-100g/10min; Molecular weight distributing index (Mw/Mn) is greater than 5.5, preferred 6-8.
It is low that propene polymer of the present invention has an ash oontent, and degree of isotacticity is high and can regulate, and the characteristics that molecular weight distribution is wider can be used for masking, such as capacitor films, fiber and non-woven fabrics, such as the staple fibre of spinning usefulness, spinning non-woven fabrics etc.; Also can be used for preparing medical treatment product etc.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
1. polymkeric substance isotactic index: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours).The dry polymer samples of two grams was placed in the extractor with the extracting of boiling heptane after 6 hours, and the polymer weight (g) that residuum is dried to the constant weight gained is isotactic index with 2 ratio.
2. the mensuration of melt index: measure according to ASTM D1238-99.
3. polymericular weight and molecular weight distribution MWD (MWD=Mw/Mn): adopt PL-220 type gel permeation chromatography, under 150 ℃, measure (standard specimens: polystyrene take trichlorobenzene as solvent, flow velocity: 1.0ml/min, pillar: 3xPlgel 10um M1xED-B 300x7.5nm).
4. the mensuration of polymkeric substance ash content: measure according to GB/T 9345-1988.
Embodiment 1
The preparation of spherical catalyst component
(A) in the glass reaction bottle that the 300ml band of fully replacing through high pure nitrogen stirs, add the titanium tetrachloride of 90ml and the hexane of 10ml, be cooled to-20 ℃, add spherical magnesium chloride alcohol adduct carrier 8g (preparation method is referring to Chinese patent CN1330086A)
(B) under agitation, slowly heat up stage by stage, when temperature reaches 40 ℃, add 2,4-pentanediol dibenzoate 1.5ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.5ml,
(C) continue to be warming up to 110 ℃, behind the rear constant temperature 0.5h of temperature, suction filtration is removed liquid,
(D) add titanium tetrachloride 100ml, be warming up to 110 ℃, to the rear constant temperature 1h of temperature, suction filtration is removed liquid.Altogether add titanium and process three times,
(E) then with hexane washing five times, obtain spherical catalyst after the vacuum-drying.
Propylene polymerization
In the autoclave of a 5L, adopt stream of nitrogen gas to purge, then in stream of nitrogen gas, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of triethyl aluminum, the hexane solution (the concentration 0.1mmol/ml of CHMMS) of Cyclohexyl Methyl Dimethoxysilane (CHMMS), anhydrous hexane and a certain amount of spherical catalyst component of 10ml.The add-on of triethyl aluminum and Cyclohexyl Methyl Dimethoxysilane represents with Al/Ti and Al/Si, sees Table 1.Close autoclave, the liquid propene of hydrogenation 2NL and 2.3L.Be warmed up to 70 ℃, polymerization 1.5 hours.Test result sees Table 1.
Embodiment 2
The preparation of spherical catalyst component: except 2,4-pentanediol dibenzoate 1.0ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.3ml is outer with embodiment 1.
Propylene polymerization is with embodiment 1.
Embodiment 3
The preparation of spherical catalyst component: except 2,4-pentanediol dibenzoate 1.5ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.3ml is outer with embodiment 1.
Propylene polymerization is with embodiment 1.
Comparative Examples 1
The preparation of spherical catalyst component
(A) in the glass reaction bottle that the 300ml band of fully replacing through high pure nitrogen stirs, add the titanium tetrachloride of 90ml and the hexane of 10ml, be cooled to-20 ℃, add spherical magnesium chloride alcohol adduct carrier 8g (preparation method is referring to Chinese patent CN1330086A)
(B) under agitation, slowly heat up stage by stage, when temperature reaches 20 ℃, add 2,4-pentanediol dibenzoate 1.5ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.5ml,
(C) continue to be warming up to 110 ℃, behind the rear constant temperature 0.5h of temperature, suction filtration is removed liquid,
(D) add titanium tetrachloride 80ml, be warming up to 110 ℃, to the rear constant temperature 0.5h of temperature, suction filtration is removed liquid.Altogether add titanium and process 2 times,
(E) then with hexane washing five times, obtain spherical catalyst after the vacuum-drying.
Propylene polymerization is with embodiment 1.
Comparative Examples 2
The preparation of spherical catalyst component: outer with embodiment 1 except only adding 2,4-pentanediol dibenzoate 1.5ml.
Propylene polymerization is with embodiment 1.
Comparative Examples 3
The preparation of spherical catalyst component: except only adding 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.5ml is outer with embodiment 1.
Propylene polymerization is with embodiment 1.
Comparative Examples 4
The preparation of spherical catalyst component: outer with embodiment 1 except only adding 9,9-dimethoxy-methyl fluorenes.
Propylene polymerization is with embodiment 1.
Table 1
Annotate: represent not add external electron donor
Relatively can find out from the data of table 1 embodiment and Comparative Examples, two kinds of electron donor compounds have been used in the present invention, simultaneously two kinds of electron donor compound mol ratios within the specific limits, the polymerization activity superelevation of its catalyzer, and apparently higher than the catalyzer that only contains single internal electron donor; When not adding external electron donor, the polymkeric substance that obtains also has higher degree of isotacticity, and the polymkeric substance that obtains has wider molecular weight distribution.Be it can also be seen that by embodiment 3 and Comparative Examples 1, when adopting the composite and compound proportion of identical internal electron donor identical, the preparation process condition of optimization of catalysts can further improve the polymerization activity of catalyzer significantly.

Claims (14)

1. preparation method who is used for the catalyst component of olefinic polymerization, the method comprises:
(A) will be such as logical formula I MgX 2.m (the .nE.qH of R ' OH) 2Adducts shown in the O is suspended in logical formula II Ti (OR) 4-kX kIn shown titanium compound and the mixture of inert solvent, optional keeping for some time;
(B) under agitation, above-mentioned suspension slowly is heated to 100 ℃～130 ℃, in temperature-rise period or after temperature, add electron donor compound a and electron donor compound b, after reaching more than 30 ℃, described electron donor compound a or b or the two temperature at suspension just add, described electron donor compound a and b randomly add together, or separately or step by step add;
(C) continue to stir 0.5～3h, then liquid is separated with solid;
(D) will process 0.5～3h with the mixture of the titanium compound shown in the logical formula II or described titanium compound and inert solvent at 100～130 ℃ by the solids that step (C) obtains, then liquid be separated with solid;
(E) titanium compound of repeating said steps (D) is processed more than 1 time or 1 time; With
(F) also dry by the solids that step (E) obtains with the inert solvent washing, obtain ingredient of solid catalyst;
Wherein:
In the logical formula I, X is chlorine or bromine; R ' is C 1-C 4Alkyl; E is the o-alkoxyl benzoic acid ester compounds shown at least a logical formula III:
Figure FDA00001993072500011
R wherein 1And R 2Be independently selected from C 1-C 12The alkyl of straight or branched, C 3-C 10Cycloalkyl, C 6-C 10Aryl and C 7-C 10Aralkyl; M is 1.0-5.0; N is 0-0.5; Q is 0-0.8;
In the logical formula II, R is C 1～C 20Alkyl, X is F, Cl or Br, k is 1～4 integer;
The electron donor compound a is selected from least a in the diol-lipid compound shown in the logical formula IV:
Figure FDA00001993072500021
In its formula of (IV), R 1-R 6, R 1-R 2Group is independently selected from the C of hydrogen, halogen atom, straight or branched 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 6-C 20Aryl or C 7-C 20Aralkyl;
The electron donor compound b is selected from least a in the diether compound shown in the general formula (V):
R 1R 2C（CH 2OR 3）（CH 2OR 4）
（Ⅴ）
In its formula of (V), R 1And R 2Be independently selected from the C of hydrogen, straight or branched 1-C 20Alkyl, C 3-C 20Cycloalkyl, C 6-C 20Aryl, C 7-C 20A kind of in the aralkyl optionally is keyed to ring, R between group 3And R 4Be independently selected from C 1-C 10Alkyl;
The mol ratio of described electron donor compound a and electron donor compound b is 0.55-50;
With respect to the adducts shown in 1 mole of logical formula I based on MgX 2Meter, the mole number of the titanium compound that uses in step (A) is the 4-50 mole;
Adducts shown in relative 1 mole of logical formula I is based on MgX 2Meter, the total amount of electron donor a and b is 0.1 to 0.8 mole.
2. the preparation method of catalyst component according to claim 1, it is characterized in that, described step (A) is following carries out: will lead in the mixture that the adducts shown in the formula I is suspended in advance the titanium compound shown in the logical formula II that is chilled to-40 ℃～0 ℃ and unreactive hydrocarbons solvent, then keep 5min～2h, the concentration of wherein said adducts solid in this suspension is lower than 200g/L.
3. the preparation method of catalyst component according to claim 1 is characterized in that, the titanium compound that uses in step (A), (D) and step (E) is identical, with respect to the adducts shown in 1 mole of logical formula I based on MgX 2Meter, the total mole number of the titanium compound that uses in the described step is the 20-200 mole.
4. the preparation method of catalyst component according to claim 1 is characterized in that, the mol ratio of electron donor a and b is 0.65～10.
5. the preparation method of catalyst component according to claim 1, in its formula of (I), m is 1.5-3.5, n is 0.
6. the preparation method of catalyst component according to claim 1, in its formula of (I), m is 1.5-3.5, n is 0.005-0.2.
7. the preparation method of catalyst component according to claim 1 is characterized in that, n is 0 o'clock in the general formula (I), and the electron donor compound a is selected from the ester of heptanediol.
8. the preparation method of catalyst component according to claim 1 is characterized in that, when n was 0.005-0.2 in the general formula (I), the electron donor compound a was selected from the ester of heptanediol or the ester of pentanediol.
9. the preparation method of catalyst component according to claim 1, the method comprises:
(A) will lead in the mixture that the adducts shown in the formula I is suspended in advance the titanium compound shown in the logical formula II that is chilled to-40 ℃～0 ℃ and unreactive hydrocarbons solvent, then keep 5min～2h, the concentration of wherein said adducts solid in this suspension is lower than 200g/L;
(B) under agitation, above-mentioned suspension slowly is heated to 100 ℃～130 ℃, after the temperature of suspension reaches more than 30 ℃, just adds described electron donor compound a or b or the two;
(C) continue to stir 0.5～3h, then liquid is separated with solid;
(D) will process 0.5～3h with the mixture of the titanium compound shown in the logical formula II or described titanium compound and inert solvent at 100～130 ℃ by the solids that step (C) obtains, then liquid be separated with solid;
(E) titanium compound of repeating said steps (D) is processed 1 time to 3 times, and the titanium compound of use is identical in step (A), (D) and step (E), with respect to the adducts shown in 1 mole of logical formula I based on MgX 2Meter, the total mole number of the titanium compound that uses is the 20-200 mole; And count based on MgX2 with respect to the adducts shown in 1 mole of logical formula I in step (A), the mole number of the titanium compound that uses is the 4-50 mole; With
(F) also dry by the solids that step (E) obtains with the inert solvent washing, obtain ingredient of solid catalyst.
10. the catalyst component that is obtained by the preparation method of one of claim 1-9 described catalyst component is characterized in that, described catalyst component is spherical.
11. a catalyzer that is used for olefinic polymerization comprises the reaction product of following component;
(1) catalyst component of claim 10;
(2) alkylaluminium cpd;
(3) optional a kind of external donor compound.
12. the described catalyzer for olefinic polymerization of claim 11 is used for directly preparing the polypropylene that ash content is lower than 100ppm at polymeric kettle.
13. the catalyzer for olefinic polymerization according to claim 12 is characterized in that, the mol ratio of the Ti in the Al in the component (2) and the component (1) is 10～300.
14. the catalyzer for olefinic polymerization according to claim 13 is characterized in that, the mol ratio of the Ti in the Al in the component (2) and the component (1) is 20～200.
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