CN102453150B - Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst - Google Patents
Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst Download PDFInfo
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Abstract
The invention relates to a support of an olefinic polymerization catalyst and a preparation method thereof, solid catalyst components for olefinic polymerization and an olefinic polymerization catalyst. The support of the olefinic polymerization catalyst is dialkoxy magnesium. The preparation method of the support of the olefinic polymerization catalyst comprises the following steps: in an inert gas protective atmosphere, reacting magnesium and alcohol, which serve as raw materials, in the presence of a halogenating agent under reflux to prepare the dialkoxy magnesium, wherein the weight ratio of alcohol to magnesium is (4-50):1; the halogenating agent is at least one of halogen simple substances and halides, and the mol ratio of halogen atom to magnesium is (0.0002-0.2):1; and the dialkoxy magnesium is spherical particles of which the average particle size is 10-150 um and the particle size distribution index SPAN is smaller than 1.1. The olefinic polymerization catalyst prepared by the support has high activity, and the polymer has the advantages of high bulk density, good particle shape and uniform distribution; and thus, the olefinic polymerization catalyst is suitable for producing propylene homopolymer and copolymer.
Description
Technical field
The present invention relates to a kind of carrier of catalyst for olefines polymerizing, a kind of spheroidal particle thing dialkoxy magnesium carrier and preparation method thereof particularly, with the solid catalyst component for olefine polymerization that includes examples of such carriers, reaching with this ingredient of solid catalyst is the olefin polymerization catalysis of Primary Catalysts.
Background technology
Generally, olefin polymer carries out polymerization with the compound of titanium and compound formation Z-N (Ziegler-Natta) catalyzer of organoaluminum.Patent such as CN 85100997A, CN 1453298A for example, in polyacrylic preparation, use contain the ingredient of solid catalyst that mainly constituted by titanium, magnesium, chlorine and electron donor compound, as the organo-aluminium compound of cocatalyst component with as the catalyzer of the silicoorganic compound of the alkoxyl group of taxis rising agent, obtain propene polymer.At present, the research of catalyzer mainly concentrates on following several respects: improve the polymerization activity of catalyzer, improve polyolefinic taxis, improve the hydrogen response of catalyzer, improve the particle form of olefin polymer, reduce Cl residual in the polymkeric substance etc.
Be the loaded catalyst component of carrier with dialkoxy magnesium, resulting propene polymer, it is good to have a particle form, and fine powder content is few, premium propertiess such as taxis height.Obtain this good catalyst component for olefin, at first must prepare the dialkoxy magnesium spheroidal particle thing of excellent property.
Originally the making method of the spheroidal particle thing dialkoxy magnesium of Ti Chuing mainly contains following several: the one, make dialkoxy magnesium through pure and mild MAGNESIUM METAL reaction earlier, and adjust the method for size of particles then with mechanical disintegration; The 2nd, in the reaction of MAGNESIUM METAL and ethanol, in 9/1～1/15 scope, ethanol and magnesium adopt the manufacture method (spy opens flat 3-74341) of being interrupted or reacting continuously when alcohol reflux with the final adding proportion control of magnesium/ethanol; The 3rd, the spirituous solution of the carboxylated magnesium after the carboxylation is carried out spraying drying, proceed decarboxylation, obtain the manufacture method (spy opens flat 6-87773) of circular minuteness particle with this; The 4th, the manufacture method (special public clear 63-4815) that MAGNESIUM METAL and ethanol are reacted under the concurrent conditions of saturated hydrocarbon.
In first and second kinds of methods, the shape of particle is pulverized have been destroyed, if want to obtain all complete particles of configuration of surface and particle size distribution, and difficulty relatively, having to output capacity sometimes lowly is cost.In three and four the method, except Mg and ROH, also need other raw material, and operation is also very complicated, so we can say that it is inconsiderable wanting the method for the particulate matter that obtains as manufacturing.In addition, consider the aspects such as diameter of shape and particle, the manufacture method that can not say so.
The research for preparing olefin polymerization catalyst components with dialkoxy magnesium also has a lot.Patent EP0459009 discloses a kind of catalyst component for olefinic polymerization, its preparation method is: form suspension by suspension diethoxy magnesium in alkylbenzene, and between 80～125 ℃, the dichloride of this suspension with titanium tetrachloride and phthalyl contacted, wash with alkylbenzene, obtained the titanium-containing catalyst component at last, though active high, active lasting during the catalyzer polymerization that is obtained by this catalyst component, the tap density of propene polymer is lower.
Patent EP 0811639 discloses a kind of ingredient of solid catalyst for olefinic polymerization, and it is reacted to each other by a kind of halogenated titanium, a kind of aryl dicarboxylic acid's diester and a kind of dialkoxy magnesium and makes.Tap density by control dialkoxy magnesium, indexs such as average particulate size, and the temperature that control begins to contact with dialkoxy magnesium from halogenated titanium rises to the speed (temperature rise rate is controlled between 0.5～20/min) of the temperature that reacts, thereby obtain a kind of ingredient of solid catalyst, can obtain a kind of high isotactic, the close polyolefine of high heap thus, but its fine powder content is higher.
Summary of the invention
Problem to be solved by this invention provides a kind of carrier and preparation method thereof of catalyst for olefines polymerizing of excellent property, and then prepare ingredient of solid catalyst based on this carrier, with be a kind of highly active olefin polymerization catalysis of Primary Catalysts with this ingredient of solid catalyst, finally tap density height, degree of isotacticity height, particle form are good for the preparation of going out, the few olefin polymer of fine powder content.
One of purpose of the present invention is to provide this kind carrier, more precisely a kind of dialkoxy magnesium spheroidal particle thing carrier.Described carrier makes by the following method:
Under protection of inert gas, be raw material with magnesium and alcohol, back flow reaction in the presence of halogenating agent, preparation spherical particle dialkoxy magnesium; The weight ratio of described alcohol and magnesium is (4～50): 1, preferred (6～25): 1; Described halogenating agent is selected from least a in halogen simple substance, the halogenide, and its consumption is that the mole of halogen atom and magnesium is (0.0002～0.2): 1, preferred (0.001～0.05): 1.
The shape of dialkoxy magnesium of the present invention is close to sphere, and size distribution is even.The median size of described dialkoxy magnesium is 10～150um, preferred 10～80 μ m; And size distribution index SPAN＜1.1, preferable particle size dispersion index SPAN＜1.05.
Wherein, the calculation formula of SPAN is as follows:
SPAN＝(D90-D10)/D50
In the formula, D90 represents corresponding to accumulating weight branch rate to be 90% particle diameter, and D10 represents corresponding to accumulating weight branch rate to be 10% particle diameter, and D50 represents that corresponding accumulating weight branch rate is 50% particle diameter.
In the present invention, employed magnesium is MAGNESIUM METAL, under the good situation of its reactivity worth, whatsoever shape can, even can the using of particulate state, silk ribbon shape or shape such as Powdered.For the median size size of the dialkoxy magnesium that impels generation remains in the suitable scope, and particle form is good, the way of comparative optimization is, require MAGNESIUM METAL for median size be the spheroidal particle of 10～360 μ m, 50～300 μ M more preferably can keep the reactivity worth of comparison homogeneous like this.
In addition, the surface of MAGNESIUM METAL is not particularly limited, but forms tunicles such as oxyhydroxide on the surface of MAGNESIUM METAL, can make reaction slack-off, and preferred surface does not generate the MAGNESIUM METAL of tunicles such as magnesium hydroxide.
In the present invention, employed alcohol is monohydroxy-alcohol or the polyvalent alcohol of straight or branched; Preferred at least a in the monohydroxy-alcohol of the straight or branched of C1～C10 or polyvalent alcohol.More preferred examples comprises: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, 2-propyl alcohol, 2-butanols, 2-amylalcohol, 2-hexanol, 2-enanthol, sec-n-octyl alcohol, 2-nonyl alcohol, 2-decyl alcohol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, 4-methyl-2-amylalcohol, 3, at least a in 3,5-trimethylammonium amylalcohol, 4-methyl-3-enanthol, phenylcarbinol, 2-phenylethyl alcohol, 1-phenyl-1-propyl alcohol, ethylene glycol, the glycerine.
The mixture of the special preferred alcohol of the present invention, 2-Ethylhexyl Alcohol, Virahol, three kinds of alcohol can add simultaneously, also can add respectively according to a certain order, there is no special restriction; Wherein ethanol accounts for 80～99wt%, and 2-Ethylhexyl Alcohol accounts for 10～1wt%, and Virahol accounts for 10～1wt%.In addition, the present invention is not particularly limited the water-content of used alcohol, for the dialkoxy magnesium that makes acquisition has better performance, requires moisture content more few more good.Water-content is generally controlled below 1000ppm in the alcohol, and preferably water content is controlled below 200ppm.
In the present invention, employed halogenating agent is selected from least a in halogen simple substance, the halogenide, and preferred examples comprises: at least a in iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, calcium chloride, Calcium Bromide, calcium iodide, mercury chloride, mercuric bromide, red mercury iodide, sodium-chlor, Sodium Bromide, sodium iodide, Repone K, Potassium Bromide, the potassiumiodide.At least a in comparative optimization iodine, magnesium iodide, magnesium chloride, the alkoxyl group magnesium halide.The mixture of preferred especially iodine and magnesium chloride, iodine or magnesium chloride can be applied to the form of pure state or solution also can add reaction system respectively in the reaction, also can partly or entirely mix to add in the reaction system.
The usage quantity that halogen atom of the present invention is total with respect to 1 mole MAGNESIUM METAL, is 0.0002～0.2 mole, is preferably 0.001～0.05 mole.Experiment showed, the quality of the particle form that how much can influence final dialkoxy magnesium that halogen atom adds and the size of particle diameter.When the amount of the halogen atom that uses is very few, the particle form extreme difference of the dialkoxy magnesium of gained; If the usage quantity of halogen atom is too much, the cost that not only prepares dialkoxy magnesium can increase, and the size of the particle of dialkoxy magnesium can be very inhomogeneous, and reaction also is difficult to be controlled.
Two of purpose of the present invention is to provide the preparation method of this kind carrier.Method of the present invention may further comprise the steps:
Under protection of inert gas, be raw material with magnesium and alcohol, back flow reaction in the presence of halogenating agent, preparation spherical particle dialkoxy magnesium, the weight ratio of described alcohol and magnesium is (4～50): 1; Described halogenating agent is selected from least a in halogen simple substance, the halogenide, and its consumption is that the mole of halogen atom and magnesium is (0.0002～0.2): 1.
In the present invention, for the preparation method of this carrier, the addition sequence of each reactant can be determined according to actual needs.Specifically, have no particular limits for halogenating agent adding method, can be dissolved in the alcohol and add, also can directly join in MAGNESIUM METAL and the alcohol with solid or liquid form, also can adopt in the process of heating of metal magnesium and alcoholic solution, splash into the method for the alcoholic solution of halogenating agent, thereby be prepared the reaction of carrier.
In addition, for the adding of magnesium, alcohol, halogenating agent and inert solvent, can also can select gradation to drop at first with the disposable input of reactant.Gradation drops into raw material can prevent the hydrogen that instantaneous generation is a large amount of, and prevents because instantaneous a large amount of hydrogen produces the alcohol that causes or the spittle of halogenating agent, from safety perspective and the inhomogeneity angle consideration of reaction, preferred this feed way.The number of times of cutting apart can be determined according to the scale of reactor and the consumption of various materials.
In the method for the invention, describedly be reflected at 0 ℃ and carry out between the reflux temperature of reaction system.The subtle change of reaction pressure can make reflux temperature change, and it is more high that temperature of reaction is selected, and it is more fast that reaction is carried out.Temperature of reaction also can change between the reaction period, can change particle diameter and particle form by the selective reaction temperature.The preferred temperature of reaction of the present invention is the reflux temperature of reaction system.
In this method, the time of described reaction is 2～30 hours.In actually operating, the discharging of the hydrogen that can also produce by observing response stops to judge that reaction finishes.
After reaction was finished, the final product dialkoxy magnesium that obtains can kept dry, in the time of also can being suspended in the ingredient of solid catalyst for the preparation of step down in the used inert diluent.
Three of purpose of the present invention is to provide a kind of solid catalyst component for olefine polymerization that to include above-mentioned dialkoxy magnesium be carrier, it is characterized in that, makes by the method that may further comprise the steps:
(1) with above-mentioned dialkoxy magnesium compound, in the presence of inert diluent, carries out contact reacts with titanium compound and electron donor compound;
(2) solid that obtains by step (1) obtains ingredient of solid catalyst with the inert solvent washing;
In step (1),
Described inert diluent is selected from least a in the alkane of C6～C10 or the aromatic hydrocarbons; The consumption of described inert diluent is with respect to the mol ratio (0.5～100) of the magnesium in the dialkoxy magnesium compound: 1; Preferably (1～50): 1.The specific examples of described inert diluent can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture; The preferred toluene of the present invention.
Among the present invention, it is Ti (OR) that described titanium compound is selected from general formula
4-nX
nCompound at least a, the R in the formula is selected from aliphatic hydrocarbyl or the aromatic hydrocarbyl of C1～C14, X is halogen atom, n is selected from 0 to 4 integer; When n is 2 when above, a plurality of R of existence can distinguish identical also can be different.The consumption of described titanium compound is (0.5～100) with respect to the mol ratio of the magnesium in the dialkoxy magnesium compound: 1; Preferably (1～50): 1.
More specifically, in the general formula of described titanium compound, X is preferably chlorine atom and bromine atoms, and particularly preferred is the chlorine atom.There is multiple possibility in the structure of R, comprises saturated group or unsaturated group, can also be straight chain shape or the group with side chain, the perhaps group of ring-type; Comparative optimization C1～C14 is alkyl, alkenyl, cycloalkenyl group, aralkyl; The alkyl of the straight or branched of preferred especially C1～C14.When n is more than 2, when having a plurality of R, can be identical between them, also can be different.The specific examples of R is selected from least a in methyl, ethyl, n-propyl, sec.-propyl, allyl group, normal-butyl, sec-butyl, isobutyl-, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, allyl group, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, the styroyl.
Accordingly, the titanium compound that satisfies the said structure general formula is selected from and comprises: at least a in four titan-alkoxides, titanium tetrahalide, three halogenated alkoxy titaniums, dihalide dialkoxy titanium, the single halogenation tri-alkoxy titanium.
More specifically, described four titan-alkoxides are selected from least a in tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, Fourth Ring hexyloxy titanium, four phenoxide titaniums; Described titanium tetrahalide is selected from least a in titanium tetrachloride, titanium tetrabromide, the titanium tetra iodide; Described three halogenated alkoxy titaniums are selected from least a in trichlorine methoxyl group titanium, trichlorine ethanolato-titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide, the tribromo ethanolato-titanium; Described dihalide dialkoxy titanium is selected from least a in dichloro dimethoxy titanium, dichloro diethoxy titanium, dichloro two positive propoxy titaniums, dichloro diisopropoxy titanium, the dibromo diethoxy titanium; Described single halogenation tri-alkoxy titanium is selected from least a in a chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titaniums, a chlorine three titanium isopropoxides.The preferred titanium tetrahalide compound of the present invention is preferably titanium tetrachloride especially.
Among the present invention, described electron donor compound comprises alkyl ester, aliphatic ether, cyclic aliphatic ether and the aliphatic ketone of aliphatic series and aromatic monocarboxylate's alkyl ester, aliphatic series and aromatic polycarboxylic acid; Preferably from alkyl ester, the alkyl ester of C7～C8 aromatic carboxylic acid, C2～C6 aliphatic ether, C3～C4 cyclic ethers, the C3～C6 saturated fatty ketone of C1～C4 aliphatic saturated monocarboxylic acid.The consumption of described electron donor compound is with respect to the mol ratio (0.005～10) of the magnesium in the dialkoxy magnesium compound: 1; Preferably (0.01～1): 1.
In specific examples, described electron donor compound is selected from methyl-formiate, ethyl acetate, butylacetate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, phthalic acid 1, at least a in 3-diamyl ester, ether, hexyl ether, tetrahydrofuran (THF) (THF), acetone and the methyl iso-butyl ketone (MIBK); The preferred n-butyl phthalate of the present invention, diisobutyl phthalate, phthalic acid 1, at least a in the 3-diamyl ester.Among the present invention, described electron donor compound can use separately or several being used.
Among the present invention, in the preparation process of this solid catalyst component for olefine polymerization, abovementioned alkyl magnesium compound, titanium compound, inert diluent are contacted with the electron donor compound react, preferably make according to following condition and order that it contacts, reaction:
The contact temperature of described each raw material is generally-40～200 ℃, is preferably-20～150 ℃ scope;
Be generally 1 minute the duration of contact of described each raw material～20 hours, be preferably 5 minutes～8 hours scope;
There is no particular limitation for the order that contacts, and for example can make each composition contact in the presence of inert diluent, can also dilute each composition with inert solvent in advance they are contacted.Also there is no particular limitation for the number of times that contacts, and can contact once, also can contact repeatedly.
The ingredient of solid catalyst that obtains by above contact reacts can wash with inert solvent, as: hydrocarbon compound.The concrete example of this inert solvent can select oneself a kind of in alkane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.Be preferably hexane among the present invention.
In the present invention, there is no particular limitation for the method for washing, modes such as preferred decant, filtration.The usage quantity of inert solvent, washing time, washing times are not particularly limited, and use 1～1000 mole with respect to the compound of 1 mole of magnesium is common, are preferably 10～500 moles solvent, wash preferred 10～6 hours usually 1～24 hour.From the homogeneity of washing and the aspect of detersive efficiency, preferably in washing operation, stir in addition.Need to prove that the ingredient of solid catalyst of gained can be preserved or preserve in inert solvent under drying regime.
It is the olefin polymerization catalysis of Primary Catalysts that four of purpose of the present invention is to provide with above-mentioned solid catalyst component for olefine polymerization.
Described catalyst pack contains following component: Primary Catalysts A, cocatalyst B, upright structure directing agent C.
Wherein, described Primary Catalysts A is ingredient of solid catalyst, and it is as above chatted.
Described cocatalyst B is organo-aluminium compound, and being selected from general formula is AlR
nX
3-nCompound at least a, to be selected from hydrogen, carbonatoms be at least a in 1～20 the alkyl to R in the formula; X is halogen, preferably from chlorine and bromine; N is the integer of 0＜n≤3;
Described cocatalyst B, its more specifically example comprise: aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, dichloro one aluminium triethyl, ethyl aluminum dichloride; Wherein preferred triethyl aluminum, triisobutyl aluminium.Ratio between described B and the described A is (5～5000) with aluminium and titanium molar ratio computing: 1; , be preferably 20～500;
Described upright structure directing agent C is silicoorganic compound, is a kind of external electron donor, and being selected from general formula is R
1R
2Si (OR ')
2Compound, R in the formula
1, R
2For identical or different, be alkyl, cycloalkyl or the aryl of C1～C20, R ' is for containing the alkyl of 1～4 carbon atom.Ratio between B component and the component C, count (2～100) with aluminium and silicon mol ratio: 1, preferred (5～50): 1.
Described upright structure directing agent C, its more specifically example comprise: the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, the cyclohexyl methyl diethoxy silane, methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, silicoorganic compound such as vinyltrimethoxy silane, preferably cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane.
All things considered, the present invention are at first reacted in the presence of halogenating agent with magnesium and alcohol, have prepared the spherical particle dialkoxy magnesium of excellent property; Be carrier with this dialkoxy magnesium then, in inert diluent, control certain temperature, make itself and titanium compound and electron donor compound contact reacts, obtain a kind of ingredient of solid catalyst; During polymerization, as Primary Catalysts, be promotor with the organo-aluminium compound with this ingredient of solid catalyst, be upright structure directing agent with organosilyl compound.Active high during this polymerization catalyst, homopolymer tap density height, degree of isotacticity height, the particle form that obtains is good, fine powder content is few; The copolymerized product performance that obtains is good, is suitable as the raw material of anti-impact product.
Description of drawings
Fig. 1 is the carrier microphotograph of the embodiment of the invention 1
Fig. 2 is the carrier microphotograph of comparative example 1 of the present invention
Embodiment
The present invention will be further described below in conjunction with specific embodiment.But the present invention is not limited in following embodiment.
Need to prove, for magnesium compound and the polyolefinic evaluation of preparation in embodiment etc., carry out in order to method down.
(1) with the titanium content in the 721 spectrophotometer detecting catalysts;
(2) use the boiling n-heptane extraction process to measure the isotactic index (II) of polymkeric substance;
(3) press the melting index (MI) that testing standard GB/T3682-2000 measures polymkeric substance;
(4) Malvern Mastersizer TM 2000 normal hexane dispersion agent laser diffractometries are measured grain size, size-grade distribution (wherein, the SPAN=(D90-D10)/D50) of dialkoxy magnesium and catalyzer;
(5) measure tap density (BD) with the method for bulk solids weight in the unit volume.
(6) pass through
13C-NMR measures ethylene content.
(7) press the content (XS%) of the standard test normal temperature xylene soluble composition of ISO 16152-2005.
Embodiment 1
(1) preparation of dialkoxy magnesium carrier
After displacement has the 16L voltage-resistant reactor of agitator fully with nitrogen, in reactor, add ethanol 10000mL, 2-Ethylhexyl Alcohol 300mL and Virahol 200mL, add iodine 12g and magnesium chloride 8g and make it dissolving.Heat up after opening stirring, until the reflux temperature that reaches reaction system.Add magnesium powder 640g then one by one.Reaction is carried out until finishing, no longer existed till the hydrogen discharge.Wash then, separate and drying.The dialkoxy magnesium carrier 1# that obtains.
(2) preparation of catalyst component
Get above-mentioned dialkoxy magnesium carrier 1#650g and toluene 3250mL, n-butyl phthalate (DNBP) 65mL is mixed with suspension; In the withstand voltage reactor of 16L that repeats to replace through high pure nitrogen, add toluene 2600mL and titanium tetrachloride 3900mL, be cooled to-5 ℃, then the suspension for preparing is added in the still, behind the constant temperature 1 hour, slowly be warming up to 110 ℃, add DNBP 65mL when rising to 80 ℃, constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 5070mL and titanium tetrachloride 3380mL then was warming up to 110 ℃ of stir process 1 hour, so handles 3 times, and elimination liquid, the solid of gained washs 4 times with hexane 150ml, and elimination liquid is also dry, namely gets ingredient of solid catalyst 1#.
(3) olefinic polymerization
Use propylene as alkene, follow these steps to carry out polymerization:
In one the 5 liters stainless steel autoclaves that have an agitator, behind nitrogen replacement, at room temperature introduce hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) 5mL, hexane solution (concentration of CHMMS is 0.10mmol/mL) 1mL, anhydrous hexane 10mL and the ingredient of solid catalyst 10mg of cyclohexyl methyl dimethoxy silane (CHMMS) of triethyl aluminum in the stream of nitrogen gas.Close autoclave, introduce hydrogen 4.5L (under the standard state) and liquid propene 2.0L; In under agitation 10 minutes temperature is risen to 70 ℃., stop stirring after 1 hour 70 ℃ of following polyreactions, remove unpolymerized propylene monomer, collected polymer.
Embodiment 2
Except in the preparation of dialkoxy magnesium carrier, except adding ethanol 10200mL, do not add outside the Virahol, other is with embodiment 1.
Embodiment 3
Except in the preparation of dialkoxy magnesium carrier, except adding ethanol 10300mL, do not add outside the 2-Ethylhexyl Alcohol, other is with embodiment 1.
Embodiment 4
Except in the preparation of dialkoxy magnesium carrier, except adding ethanol 10400mL and 2-Ethylhexyl Alcohol 100mL, other is with embodiment 2.
Embodiment 5
Except in the preparation of dialkoxy magnesium carrier, except adding ethanol 10000mL and 2-Ethylhexyl Alcohol 500mL, other is with embodiment 2.
Embodiment 6
Except in the preparation of dialkoxy magnesium carrier, except adding iodine 6g, magnesium chloride adding 4g, other is with embodiment 2.
Embodiment 7
(1) preparation of dialkoxy magnesium carrier
With embodiment 1.
(2) preparation of catalyst component
Get above-mentioned dialkoxy magnesium 1#650g and toluene 3250mL; In the withstand voltage reactor of 16L that repeats to replace through high pure nitrogen, add toluene 2600mL and titanium tetrachloride 3900mL, be cooled to-5 ℃, then the suspension for preparing is added in the still, behind the constant temperature 1 hour, slowly be warming up to 110 ℃, add DNBP 130mL when rising to 80 ℃, constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 5070mL and titanium tetrachloride 3380mL then was warming up to 110 ℃ of stir process 1 hour, so handles 3 times, and elimination liquid, the solid of gained washs 4 times with hexane 150mL, and elimination liquid is also dry, namely gets ingredient of solid catalyst.
(3) olefinic polymerization
With embodiment 1.
Embodiment 8
(1) preparation of dialkoxy magnesium carrier
With embodiment 1.
(2) preparation of catalyst component
Get above-mentioned dialkoxy magnesium 650g and toluene 3250ml, n-butyl phthalate (DNBP) 182mL is mixed with suspension; In the withstand voltage reactor of the 16L that repeats to replace through high pure nitrogen, add toluene 2800mL and titanium tetrachloride 3900mL, be warming up to 80 ℃, then the suspension for preparing is slowly added in the still, constant temperature continued to be warming up to 110 ℃ after 1 hour, constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 5070mL and titanium tetrachloride 3380mL then was warming up to 110 ℃ of stir process 1 hour, so handles 3 times, and elimination liquid, the solid of gained washs 4 times with hexane 150mL, and elimination liquid is also dry, namely gets ingredient of solid catalyst.
(3) olefinic polymerization
With embodiment 1.
Comparative Examples 1
(1) preparation of dialkoxy magnesium carrier
After displacement has the 16L voltage-resistant reactor of agitator fully with nitrogen, in reactor, add ethanol 13300ml, add iodine 23g.Heat up after opening stirring, until the reflux temperature that reaches reaction system.Add magnesium powder 640g then one by one.Reaction is carried out until finishing, no longer existed till the hydrogen discharge.Wash then, separate and drying.The dialkoxy magnesium that obtains.
(2) preparation of catalyst component
Except with the dialkoxy magnesium in above-mentioned (1), other is with embodiment 1.
(3) olefinic polymerization
With embodiment 1.
From table 1 and Fig. 1 data as can be seen, use preparation method of the present invention to make catalyst component polymerization activity height, polymer bulk density height, fine powder are few, and degree of isotacticity, the performance of melting index molecular weight distribution are better.Relatively be suitable for using at gas phase process.
[embodiment of propylene-ethylene block copolymer]
Embodiment 9
(1) preparation of dialkoxy magnesium carrier
With embodiment 1.
(2) preparation of catalyst component
With embodiment 1.
(3) olefinic polymerization
Use propylene and ethene as alkene, follow these steps to carry out polymerization:
Have in the stainless steel autoclave of agitator at a 5L, with fully displacement displacement in the nitrogen, with after the propylene gas ventilation, at room temperature introduce hexane solution (concentration of triethyl aluminum the is 0.5mmol/ml) 5mL of triethyl aluminum, hexane solution (concentration of DIPDMS is 0.10mmol/mL) 0.5mL, anhydrous hexane 10mL and the ingredient of solid catalyst 10mg of diisopropyl dimethoxy silane (DIPDMS) again.To 1.2MPa, add liquid propene 2.0L with pressurized with hydrogen again; Under agitation temperature is risen to 70 ℃.70 ℃ of following polyreactions 1 hour.
Then, stop stirring, slowly emptying, the logical hot water of chuck, is opened and is stirred when dropping to 1.0Mpa to the still internal pressure to 80 ℃ of intensification simultaneously, continues slow emptying and warming temperature; 80 ℃ after temperature, emptying to still internal pressure is 0Mpa (gauge pressure); Ratio with 3.2: 6.8 mol ratios feeds 1.0Mpa (gauge pressure) ethylene gas/propylene gas again, under 80 ℃, 1.0Mpa, carries out the propylene-ethylene copolyreaction 1 hour.Then, unload and be depressed into outer air pressure, and be cooled to normal temperature, open reactor, reclaim the polymer beads that generates.The results are shown in table 2.
Embodiment 10
Except the ratio of the mol ratio of the ethylene-propylene of subordinate phase changes 5.3: 4.7 into, carry out similarly to Example 7.The results are shown in table 2.
Comparative example 2
(1) preparation of dialkoxy magnesium carrier
After displacement has the 16L voltage-resistant reactor of agitator fully with nitrogen, in reactor, add ethanol 13300mL, add iodine 6g.Heat up after opening stirring, until the reflux temperature that reaches reaction system.Add magnesium powder 640g then one by one.Reaction is carried out until finishing, no longer existed till the hydrogen discharge.Wash then, separate and drying.The dialkoxy magnesium that obtains.D50 is 26.3 μ m, and SPAN is that 1.05, BD is 0.22g/cm
3
(2) preparation of catalyst component
Except with the dialkoxy magnesium in above-mentioned (1), other is with embodiment 1.The Ti content that obtains catalyzer is 2.42wt%, and median size (D50) is 25.1 μ m, and SPAN is 1.01.
(3) olefinic polymerization
With embodiment 10.
The aggregated data of table 2 embodiment 9～10, Comparative Examples 2 relatively
As can be seen from Table 2, catalyzer provided by the invention under the lower condition of ethylene raw gas content, can obtain the multipolymer of high ethylene content, and this catalyzer copolymerization performance is good, and application prospect is good.
On the whole, carrier provided by the present invention, catalyst component for olefin and catalyzer, can make tacticity and the good olefin polymer of particle form at its polymerization activity height.Use the present invention can prepare the high ethylene-propylene copolymer of ethylene content, tacticity is good during in view of the homopolymerization of this catalyzer propylene, and its multipolymer of preparing is suitable as the raw material of the anti-impact product of rerum natura equilibriums such as rigidity, shock-resistance.
Claims (13)
1. the carrier of a catalyst for olefines polymerizing is characterized in that:
Described carrier is dialkoxy magnesium, makes by the following method:
Under protection of inert gas, be raw material with magnesium and alcohol, back flow reaction in the presence of halogenating agent, preparation dialkoxy magnesium; The weight ratio of described alcohol and magnesium is (4～50): 1; Described halogenating agent is selected from least a in halogen simple substance, the halogenide, and its consumption is that the mole of halogen atom and magnesium is (0.0002～0.2): 1;
Described dialkoxy magnesium is spherical particle, and median size is 10～150 μ m, size distribution index SPAN＜1.1;
Described alcohol is selected from ethanol, 2-Ethylhexyl Alcohol, Virahol three's mixture, and wherein ethanol accounts for 80～99wt%, and 2-Ethylhexyl Alcohol accounts for 10～1wt%, and Virahol accounts for 10～1wt%, and three's weight percentage sum is 100wt%;
The water-content of described alcohol is below 1000ppm.
2. the carrier of catalyst for olefines polymerizing as claimed in claim 1 is characterized in that:
The weight ratio of described alcohol and magnesium is (6～25): 1; The mole of halogen atom and magnesium is (0.001～0.05) in the described halogenating agent: 1;
The median size of described dialkoxy magnesium is 10～80 μ m, and size distribution index SPAN＜1.05.
3. the carrier of catalyst for olefines polymerizing as claimed in claim 1 is characterized in that:
Described magnesium is that median size is the spheroidal particle of 10～360 μ m;
Described halogenating agent is selected from least a in iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, calcium chloride, Calcium Bromide, calcium iodide, mercury chloride, mercuric bromide, red mercury iodide, sodium-chlor, Sodium Bromide, sodium iodide, Repone K, Potassium Bromide, potassiumiodide, the alkoxyl group magnesium halide.
4. the carrier of catalyst for olefines polymerizing as claimed in claim 3 is characterized in that:
Described magnesium is that median size is the spheroidal particle of 50～300 μ m;
Described halogenating agent is selected from iodine, magnesium iodide, magnesium chloride, the alkoxyl group magnesium halide at least a.
5. preparation method who prepares as the carrier of the described catalyst for olefines polymerizing of one of claim 1～4 is characterized in that:
Under protection of inert gas, be raw material with magnesium and alcohol, in the presence of halogenating agent, by the weight of described alcohol and magnesium when the mol ratio of described halogen atom and magnesium carry out back flow reaction, preparation dialkoxy magnesium.
6. the preparation method of the carrier of catalyst for olefines polymerizing as claimed in claim 5 is characterized in that:
Describedly be reflected at 0 ℃ and carry out between the reflux temperature of reaction system; The time of described reaction is 2～30 hours.
7. solid catalyst component for olefine polymerization that includes as the carrier of the described catalyst for olefines polymerizing of one of claim 1～4 is characterized in that described ingredient of solid catalyst makes by following steps:
(1) with described dialkoxy magnesium compound, in the presence of inert diluent, carries out contact reacts with titanium compound and electron donor compound;
(2) solid that obtains by step (1) obtains ingredient of solid catalyst with the inert solvent washing;
In step (1),
Described inert diluent is selected from least a in the alkane of C6～C10 or the aromatic hydrocarbons;
It is Ti (OR) that described titanium compound is selected from general formula
4-nX
nCompound at least a, the R in the formula is selected from aliphatic hydrocarbyl or the aromatic hydrocarbyl of C1～C14, X is halogen atom, n is selected from 0 to 4 integer; When n is 2 when following, a plurality of R of existence can distinguish identical also can be different;
Described electron donor compound is selected from alkyl ester, the alkyl ester of C7～C8 aromatic carboxylic acid, C2～C6 aliphatic ether, C3～C4 cyclic ethers, the C3～C6 saturated fatty ketone of C1～C4 aliphatic saturated monocarboxylic acid.
8. ingredient of solid catalyst as claimed in claim 7 is characterized in that:
The consumption of described titanium compound is (0.5～100) with respect to the mol ratio of the magnesium in the dialkoxy magnesium compound: 1;
The consumption of described inert diluent is with respect to the mol ratio (0.5～100) of the magnesium in the dialkoxy magnesium compound: 1;
The consumption of described electron donor compound is with respect to the mol ratio (0.005～10) of the magnesium in the dialkoxy magnesium compound: 1.
9. ingredient of solid catalyst as claimed in claim 8 is characterized in that:
The consumption of described titanium compound is (1～50) with respect to the mol ratio of the magnesium in the dialkoxy magnesium compound: 1;
The consumption of described inert diluent is (1～50) with respect to the mol ratio of the magnesium in the dialkoxy magnesium compound: 1;
The consumption of described electron donor compound is (0.01～1) with respect to the mol ratio of the magnesium in the dialkoxy magnesium compound: 1.
10. ingredient of solid catalyst as claimed in claim 7 is characterized in that,
Described inert diluent is selected from least a in hexane, heptane, octane, decane, the benzene,toluene,xylene;
Described titanium compound is selected from least a in four titan-alkoxides, titanium tetrahalide, three halogenated alkoxy titaniums, dihalide dialkoxy titanium, the single halogenation tri-alkoxy titanium compound.
11. one kind is the olefin polymerization catalysis of Primary Catalysts with the described solid catalyst component for olefine polymerization of one of claim 7～10, it is characterized in that:
Include described Primary Catalysts A, cocatalyst B, upright structure directing agent C;
Described Primary Catalysts A is ingredient of solid catalyst;
Described cocatalyst B is organo-aluminium compound, and being selected from general formula is AlR
nX
3-nCompound at least a, R is selected from least a in the alkyl of C1～C20 in the formula; X is halogen; N is the integer of 0＜n≤3;
Described upright structure directing agent C is silicoorganic compound, and being selected from general formula is R
lR
2Si (OR')
2Compound and trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, phenyl triethoxysilane, phenyltrimethoxysila,e, at least a in the vinyltrimethoxy silane, R in the described general formula
l, R
2Be alkyl, cycloalkyl or the aryl of identical or different C1～C20, R' is the alkyl that contains 1～4 carbon atom;
Ratio between described B and the described A is (5～5000) with aluminium and titanium molar ratio computing: 1; Ratio between described B and the described C is counted (2～100) with aluminium and silicon mol ratio: 1.
12. olefin polymerization catalysis as claimed in claim 11 is characterized in that:
Ratio between described B and the described A is (20～500) with aluminium and titanium molar ratio computing: 1; Ratio between described B and the described C is counted (5～50) with aluminium and silicon mol ratio: 1.
13. olefin polymerization catalysis as claimed in claim 11 is characterized in that:
Described cocatalyst B is selected from least a in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, the ethyl aluminum dichloride;
Described upright structure directing agent C is selected from the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, the methylcyclohexyl diethoxy silane, methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, at least a in the vinyltrimethoxy silane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010522125 CN102453150B (en) | 2010-10-25 | 2010-10-25 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
| ES11824428T ES2804259T3 (en) | 2010-09-16 | 2011-09-09 | Catalyst support for olefin polymerization, solid catalyst component and catalyst |
| RU2013116751/04A RU2586684C2 (en) | 2010-09-16 | 2011-09-09 | Olefin polymerisation catalyst support, solid catalyst component and catalyst |
| KR1020137009647A KR20130100155A (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst |
| US13/824,127 US20130196847A1 (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst |
| PCT/CN2011/001536 WO2012034357A1 (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst |
| KR1020187018668A KR102127722B1 (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst |
| EP11824428.4A EP2617739B1 (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst |
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| CN114149524B (en) * | 2020-09-05 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof |
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