CN102399326B - Solid catalyst component for olefin polymerization, and catalyst thereof - Google Patents
Solid catalyst component for olefin polymerization, and catalyst thereof Download PDFInfo
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Abstract
The present invention relates to a solid catalyst component for olefin polymerization, and a catalyst thereof. According to the solid catalyst component, amorphous spherical dialkoxy magnesium is adopted as a carrier, toluene is adopted as a dispersing agent, the amorphous spherical dialkoxy magnesium contacts titanium halide at a certain temperature, and then reacts with a polyol ester compound with a special structure, wherein the polyol ester compound is adopted as an electron donor; then the resulting material is treated by the titanium halide to obtain the solid catalyst component, during the polymerization process, an organic aluminum compound is adopted as an assistant catalyst, and an silicone compound is adopted as a stereo structure directing agent. According to the present invention, the catalyst has high activity during the polymerization process, and the prepared polymer has characteristics of wide molecular weight distribution, good stereoregularity, good particle morphology and low powder content.
Description
Technical field
The present invention relates to a kind of solid catalyst component for olefine polymerization and catalyzer, belong to field of olefin polymerisation.
Background technology
Field of olefin polymerisation generally adopts Z-N (Ziegler-Natta) polymerization catalyst with the compound formation of the compound of titanium and organoaluminum to obtain olefin polymer.For example using in polyacrylic preparation described in the patent such as CN85100997A, CN 1453298A contained mainly the ingredient of solid catalyst that is made of titanium, magnesium, chlorine and electron donor compound and as the organo-aluminium compound of cocatalyst component with as the catalyzer of the silicoorganic compound of taxis rising agent, to 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 carrier of excellent property.
The making method of spherical dialkoxy magnesium mainly contains following several in the prior art: 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, with the final adding proportion control of the magnesium/ethanol scope at 9/1-1/15, ethanol and magnesium adopt the manufacture method (spy opens flat 3-74341) of being interrupted or reacting continuously when alcohol reflux; 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 that MAGNESIUM METAL and ethanol react under the concurrent conditions of stable hydrocarbon (special public clear 63-4815).
In first and second kinds of methods, the shape of particle is pulverized have been destroyed, if want to obtain all complete particle difficulties relatively of configuration of surface and particle size distribution, having to reduce output capacity sometimes is cost.In the 3rd and four the method, except Mg and ROH, also need other raw material, and operation is also very complicated, all there is deficiency separately in above method.
Be that the research that carrier prepares olefin polymerization catalyst components also has much with dialkoxy magnesium.Patent EP0459009 discloses a kind of catalyst component for olefinic polymerization, its preparation method is that diethoxy magnesium is formed suspension 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 EP0811639 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 alkoxyl magnesium and makes.Tap density by the control alkoxyl magnesium, indexs such as average particulate size, and the temperature that control begins to contact with alkoxyl 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.
Among the CN101054424A dialkoxy magnesium for preparing is suspended in the toluene, is cooled to 0 ℃, add titanium tetrachloride then, heat up, add electron donor, fully the reaction back adds toluene wash, and the toluene titanium is handled then, uses hexane wash at last again.The ingredient of solid catalyst polymerization activity is higher, good sphericity, but size distribution is not too concentrated.
The present invention at first reacts the good spherical particle dialkoxy magnesium of manufacturing property with MAGNESIUM METAL and alcohol mixture in the presence of halogen-containing materials.Be carrier with dialkoxy magnesium then, be dispersion agent with toluene, controlling certain temperature contacts with halogenated titanium, react then and as the polyol ester compound with special construction of electron donor, handle through halogenated titanium again, obtaining ingredient of solid catalyst, is promotor with the organo-aluminium compound during polymerization, is upright structure directing agent with organosilyl compound.Active high during this polymerization catalyst, the molecular weight distribution that obtains is wide, tacticity good, particle form is good, fine powder content is few.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of solid catalyst component for olefine polymerization, catalyst for olefines polymerizing and olefin polymer, the present invention is carrier with the spheroidal particle thing dialkoxy magnesium of excellent property, with the polyol ester compound with special construction as electron donor, prepare the high catalyzer of polymerization activity, obtain the olefin polymer that molecular weight distribution is wide, tacticity good, particle form is excellent.
The present invention is used for the ingredient of solid catalyst of olefinic polymerization, this catalyst component is carrier with spherical dialkoxy magnesium, be dispersion agent with the inert solvent, contact with titanium compound at a certain temperature, react with electron donor polyol ester compound then, handle through titanium compound again, obtain ingredient of solid catalyst;
Described spherical dialkoxy magnesium is prepared by following method: under protection of inert gas, be raw material with magnesium powder and alcohol mixture, be halogenating agent with halogen simple substance and/or inorganic halides, be that dispersion medium reaction obtains with one or more inert organic solvents, described alcohol mixture is monohydroxy-alcohol or the polyvalent alcohol of straight or branched, and wherein the mol ratio of halogenating agent and magnesium powder is 0.0002-0.2; The mol ratio of alcohol mixture and magnesium is 2-50;
The general formula of described titanium compound is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is halogen atom, n is 0 to 4 integer;
Described electron donor compound is selected from the binary alcohol esters compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is the C of identical or different hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or ester group, R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more choosing wantonly in the group is in ring, and n is 0～10 integer;
Described inert solvent can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.
Prepare the MAGNESIUM METAL that spherical dialkoxy magnesium uses, under the good situation of its reactivity worth, whatsoever the MAGNESIUM METAL of shape can, even can using of particulate state, silk ribbon shape or shape such as Powdered, for the median size size of the alkoxyl magnesium that guarantees to generate remains on 10-80 μ M, and particle form is good, and the median size that requires MAGNESIUM METAL is the spheroidal particle below 360 μ M preferably, preferably in the scope of 300-50 μ M, can keep the reactivity worth of comparison homogeneous like this.
The surface of MAGNESIUM METAL forms tunicles such as oxyhydroxide, can make reaction slack-off, and preferred surface does not generate the MAGNESIUM METAL of tunicles such as magnesium hydroxide.
Prepare alcohol mixture that spherical non-crystalline state dialkoxy magnesium uses and be monohydroxy-alcohol or the polyvalent alcohol of straight or branched.Preferred carbonatoms is at the mixture of the alcohol of 1-10.Concrete example has: 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,
3,3,5-trimethylammonium amylalcohol, 4-methyl-3-enanthol.Phenylcarbinol, 2-phenylethyl alcohol, 1-phenyl-1-propyl alcohol, ethylene glycol, glycerine etc.
Particularly preferred alcohol mixture is the mixture of ethanol and Virahol, and wherein ethanol accounts for 90-99 weight %, and Virahol accounts for 10-1 weight %.The present invention is not particularly limited the water-content of alcohol, in order to obtain the performance of good alkoxyl magnesium, 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.
The mol ratio control of alcohol mixture and magnesium is preferably controlled at 2.5-18 in the 2-50 scope.
The non-limiting selection for preparing the halogenating agent of spherical dialkoxy magnesium use is: 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 etc., preferred iodine, magnesium iodide, magnesium chloride and 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 in the reaction.Iodine and magnesium chloride can add reaction system respectively, also can partly or entirely mix to add in the reaction system.
Prepare the total usage quantity of spherical dialkoxy magnesium halogen atom, with respect to 1 mole MAGNESIUM METAL, should be at the 0.0002-0.2 mole, preferably in the scope of 0.0025-0.05 mole.The contriver finds, the quality of the particle form that how much can influence final alkoxyl magnesium that halogen atom adds and the size of particle diameter.When the amount of the halogen atom that uses was very few, the particle form of the alkoxyl magnesium of gained was relatively poor; If the usage quantity of halogen atom is too much, the cost that not only prepares alkoxyl magnesium can increase, and the size of the particle of alkoxyl magnesium can be very inhomogeneous, and reaction also is difficult to be controlled.
The addition sequence of reactive material can be determined as required.Specifically, have no particular limits for halogenating agent adding method, can be dissolved in the ethanol 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, the method that splashes into the alcoholic solution of halogenating agent is prepared.
Prepare spherical dialkoxy magnesium and use inert organic solvents to come dispersed material as dispersion medium, inert organic solvents not only can diluted material, and feed liquid is being carried out under the whipped state preferably; But also can eliminate partial electrostatic, this has certain effect to the particle form preferably that keeps product.Dispersion medium can be selected hexane, heptane, octane, decane, benzene,toluene,xylene, or derivatives thereof etc.The present invention preferably uses toluene.
In addition, for the adding of MAGNESIUM METAL, alcohol mixture, halogen-containing materials 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 halogen, from safety perspective consideration, preferred this feed way.The number of times of cutting apart can be determined according to the scale of reactive tank and the consumption of various materials.
Temperature of reaction of the present invention can be carried out under the reflux temperature of 0 ℃-reaction system, and 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.Preferred temperature of reaction is the reflux temperature of reaction system.
The discharging of the hydrogen that produces by observing response stops to judge that reaction finishes normally 2-30 hour reaction times.
The shape of dialkoxy magnesium of the present invention is close to sphere, and size distribution is even.Preferred median size D50 is 10～80um, and size distribution index SPAN＜1.1.
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.)
The present invention is used for the ingredient of solid catalyst of olefinic polymerization, this catalyst component is carrier with spherical dialkoxy magnesium, be dispersion agent with the inert solvent, contact with titanium compound at a certain temperature, react with electron donor polyol ester compound then, handle through titanium compound again, obtain ingredient of solid catalyst;
Described spherical non-crystalline state dialkoxy magnesium is prepared by following method: under protection of inert gas, be raw material with magnesium powder and alcohol mixture, be halogenating agent with halogen simple substance and/or inorganic halides, be that dispersion medium reaction obtains with one or more inert organic solvents, described alcohol mixture is monohydroxy-alcohol or the polyvalent alcohol of straight or branched, and wherein the mol ratio of halogenating agent and magnesium powder is 0.0002-0.2; The mol ratio of alcohol mixture and magnesium is 2-50;
The general formula of described titanium compound is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is halogen atom, n is 0 to 4 integer; N is 2 when following, and a plurality of R can be identical or different.X is preferably chlorine atom and bromine atoms, and particularly preferred is the chlorine atom.R can be saturated group or unsaturated group, can also be straight chain shape or the group with side chain, the perhaps group of ring-type, particularly preferred for alkyl, alkenyl, cycloalkenyl group and aralkyl, particularly preferably be the alkyl of straight or branched.When having a plurality of R, can be identical between them, also can be different.Object lesson as R can be 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, styroyl etc.
Specifically can select four titan-alkoxides such as 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 for use; Titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide; Three halogenated alkoxy titaniums such as trichlorine methoxyl group titanium, trichlorine ethanolato-titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide, tribromo ethanolato-titanium; Dihalide dialkoxy titaniums such as dichloro dimethoxy titanium, dichloro diethoxy titanium, dichloro two positive propoxy titaniums, dichloro diisopropoxy titanium, dibromo diethoxy titanium; Single halogenation tri-alkoxy titaniums such as one chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titaniums, a chlorine three titanium isopropoxides.Preferred titanium tetrahalide wherein, particularly preferred is titanium tetrachloride.The usage quantity of titanium compound is generally 0.5～100 mole with respect to the magnesium of 1 mole of spherical dialkoxy magnesium compound, is preferably 1～50 mole.
Described electron donor compound is selected from the binary alcohol esters compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is the C of identical or different hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C2-C10 alkylene, C
10-C
20Fused ring aryl or ester group, R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more choosing wantonly in the group is in ring, and n is 0～10 integer;
Described electron donor compound is disclosed among Chinese patent CN1436766 and the CN1436796A, and the associated viscera of this patent disclosure is all introduced the present invention as a reference.
In the binary alcohol esters compounds shown in the above-mentioned general formula (I), preferably comprise the compound shown in the general formula (II).
R wherein
1-R
6, R
1-R
2C for hydrogen identical or inequality, 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 usage quantity of electron donor compound is generally 0.005～10 mole with respect to the magnesium of 1 mole of spherical dialkoxy magnesium compound, is preferably 0.01～1 mole.
Described inert diluent can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.Be preferably toluene.
The usage quantity of inert diluent is generally 0.5～100 mole with respect to the magnesium of 1 mole of spherical dialkoxy magnesium compound, is preferably 1～50 mole scope.
The contact temperature of each composition is generally-40～200 ℃, is preferably-20～150 ℃ scope; Be generally 1 minute duration of contact～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 can wash with inert solvent.This inert solvent can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.The present invention is preferably hexane.As the method for washing, there is no particular limitation, 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 usually, be preferably 10～500 moles solvent with respect to the compound of 1 mole of magnesium, wash usually 1～24 hour, preferred 10～6 hours.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.
The invention still further relates to a kind of solid catalyst for olefinic polymerization, comprise the reaction product of following component:
The ingredient of solid catalyst of A, olefinic polymerization of the present invention;
B, organo-aluminium compound component; Its general formula is AlR
nX
3-n, in the formula R be hydrogen, and carbonatoms be 1～20 alkyl; X is halogen, and n is the integer of 0＜n≤3;
The silicoorganic compound component of C, a kind of optional adding; Its general formula is R
1R
2Si (OR ')
2, R in the formula
1, R
2Identical or different, be C
1～C
20Alkyl, cycloalkyl or aryl, R ' is for containing the alkyl of 1～4 carbon atom.
The organo-aluminium compound particular compound is as 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 dichlorides, wherein with triethyl aluminum, triisobutyl aluminium for well.Ratio between B component and the component A is 5～5000 with aluminium and titanium molar ratio computing, is preferably 20～500;
Silicoorganic compound concrete as: 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, vinyltrimethoxy silane etc.Ratio between B component and the component C counts 5～30 with aluminium and silicon mol ratio.
It is carrier that the present invention adopts the alkoxyl magnesium of excellent property, and the olefin polymerization catalysis prepared is active high, and bulk specific gravity is higher, and particle form keeps, and is evenly distributed, and is applicable to that gas phase process produces polyacrylic device.
Embodiment
Specifically describe the present invention by embodiment, the present invention is not limited to following embodiment.
Polyolefinic evaluation method is as follows:
Titanium content in (1) the 721 spectrophotometer detecting catalyst;
(2) the boiling n-heptane extraction process is measured 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
TM2000 normal hexane dispersion agent laser diffractometries are measured grain size, the size-grade distribution of dialkoxy magnesium and catalyzer;
(5) measure tap density with the method for bulk solids weight in the unit volume.
Embodiment 1
(1) preparation of dialkoxy magnesium carrier
In having the 1L reactor of agitator, reflux condensing tube, thermometer and drop-burette are installed.After nitrogen displacement fully, in reactor, add ethanol 550ml and Virahol 10ml, add iodine 0.68g and magnesium chloride 0.42g and make it dissolving.Heat up after opening stirring, until the reflux temperature that reaches reaction system.Add magnesium powder 32g then one by one, and introduce toluene 90ml.Reaction is carried out until finishing, no longer existed till the hydrogen discharge.Wash then, separate and drying.The tap density of the dialkoxy magnesium that obtains is 0.40g/cm
3, median size (D50) is 43.0 μ m, SPAN=(D90-D10)/D50=(60.8-29.5)/43.0=0.73.
(2) preparation of catalyst component
Get above-mentioned alkoxyl magnesium 10g and toluene 50ml, 4-ethyl-3,5-heptanediol dibenzoate 2.0ml is mixed with suspension; In the reactor of the 300ml that repeats to replace through high pure nitrogen, add toluene 10ml and titanium tetrachloride 90ml, be warming up to 80 ℃, then the suspension for preparing is added in the still, constant temperature continued to be warming up to 115 ℃ after 1 hour, constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 120ml and titanium tetrachloride 30ml 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
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 catalyst component, with 4-ethyl-3,5-heptanediol dibenzoate is changed to outside 3, the 5-heptanediol dibenzoate, and other is with embodiment 1.
Embodiment 3
Except in the preparation of catalyst component, with 4-ethyl-3,5-heptanediol dibenzoate is changed to outside 2, the 4-pentanediol dibenzoate, and other is with embodiment 1.
Embodiment 4
(1) preparation of dialkoxy magnesium carrier
With embodiment 1.
(2) preparation of catalyst component
In the reactor of the 300ml that repeats to replace through high pure nitrogen, add toluene 10ml and titanium tetrachloride 90ml, be cooled to-5 ℃, the suspension of the alkoxyl magnesium 10g that adding is obtained by embodiment 1 and toluene 50ml preparation slowly is warming up to 80 ℃ then, adds 4-ethyl-3,5-heptanediol dibenzoate 1.8ml, continue to be warming up to 115 ℃, constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds titanium tetrachloride 120ml and toluene 30ml then was warming up to 110 ℃ of stir process 1 hour, so handled 3 times, and washing 4 times, elimination liquid is also dry with hexane 150ml for elimination liquid, the solid of gained.
(3) olefinic polymerization
With embodiment 1.
Embodiment 5
Except in the preparation of catalyst component, with 4-ethyl-3,5-heptanediol dibenzoate is changed to outside 3, the 5-heptanediol dibenzoate, and other is with embodiment 4.
Embodiment 6
Except in the preparation of catalyst component, with 4-ethyl-3,5-heptanediol dibenzoate is changed to outside 2, the 4-pentanediol dibenzoate, and other is with embodiment 4.
Comparative example 1
(1) preparation of dialkoxy magnesium carrier
With embodiment 1.
(2) preparation of catalyst component
Get above-mentioned alkoxyl magnesium 10g and toluene 50ml, n-butyl phthalate (DNBP) 2.5ml is mixed with suspension; In the reactor of the 300ml that repeats to replace through high pure nitrogen, add toluene 10ml and titanium tetrachloride 90ml, be warming up to 80 ℃, then the suspension for preparing is added in the still, constant temperature continued to be warming up to 115 ℃ after 1 hour, constant temperature 2 hours is clean with the liquid press filtration then.The mixed solution that adds toluene 120ml and titanium tetrachloride 30ml 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 example 2
(1) preparation of catalyst component
In the reactor that repeats to replace through high pure nitrogen, add 4.8g Magnesium Chloride Anhydrous, 100ml toluene, 4.0ml epoxy chloropropane, 12.5ml tributyl phosphate successively.Be under 60 ℃ the condition, to allow reaction mixture reaction 2 hours in mixing speed 450rpm, temperature.Add the 1.4g Tetra hydro Phthalic anhydride, and allow reaction mixture to continue reaction one hour, be cooled to-28 ℃ then.Drip titanium tetrachloride 56ml, be warming up to 85 ℃ gradually, in the time of 80 ℃, add 2.0ml2,4-pentanediol dibenzoate, 85 ℃ are arrived temperature back constant temperature one hour.Elimination mother liquor, residual solid thing be with 0.95 mole of toluene wash twice, handled 2 hours at 110 ℃ with 0.36 mole of 0.57 mole of toluene and titanium tetrachloride then.Repeat this processing more once after the filtration.With solids hexane wash 5 times that obtain, dry then, obtain solid titanium-containing catalyst component.
(2) olefinic polymerization
With embodiment 1.
The contrast of data from table 1 as can be seen, the polymerization catalyst that the present invention obtains is active high, fine polymer powder is few, molecular weight distribution is wide, isotactic index, melting index performance better.Has good processing properties.
Claims (9)
1. ingredient of solid catalyst that is used for olefinic polymerization, it is characterized in that, this catalyst component is carrier with spherical dialkoxy magnesium, be dispersion agent with the inert solvent, contact with titanium compound at a certain temperature, react with electron donor polyol ester compound then, handle through titanium compound again, obtain ingredient of solid catalyst;
Described spherical non-crystalline state dialkoxy magnesium is prepared by following method: under protection of inert gas, be raw material with magnesium powder and alcohol mixture, be halogenating agent with halogen simple substance and/or inorganic halides, be that dispersion medium reaction obtains with one or more inert organic solvents, described alcohol mixture is monohydroxy-alcohol or the polyvalent alcohol of straight or branched, and wherein the mol ratio of halogenating agent and magnesium powder is 0.0002-0.2; The mol ratio of alcohol mixture and magnesium is 2-50;
The general formula of described titanium compound is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is halogen atom, n is 0 to 4 integer;
Described electron donor compound is selected from the binary alcohol esters compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is the C of identical or different hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or ester group, R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more choosing wantonly in the group is in ring, and n is 0～10 integer;
Described inert solvent can adopt a kind of in hexane, heptane, octane, decane, the benzene,toluene,xylene or their mixture.
2. the ingredient of solid catalyst of olefinic polymerization according to claim 1 is characterized in that, in the preparation of described spherical dialkoxy magnesium, described alcohol mixture is that carbonatoms is at the mixture of the alcohol of 1-10; Halogenating agent is a kind of of iodine, magnesium iodide, magnesium chloride, alkoxyl group magnesium halide or their mixture; Dispersion medium is hexane, heptane, octane, decane, benzene,toluene,xylene, or derivatives thereof, and the mol ratio control of alcohol mixture and magnesium is at 2.5-18, and the mol ratio of halogenating agent and magnesium powder is 0.0025-0.05.
3. the ingredient of solid catalyst of olefinic polymerization according to claim 1, it is characterized in that in the preparation of described spherical dialkoxy magnesium, described alcohol mixture is the mixture of ethanol and Virahol, wherein ethanol accounts for 90-99 weight %, and Virahol accounts for 10-1 weight %; Halogenating agent is the mixture of iodine and magnesium chloride; Dispersion medium is toluene.
4. the ingredient of solid catalyst of olefinic polymerization according to claim 1 is characterized in that, dialkoxy magnesium median size D50 is 10～80um, and size distribution index SPAN＜1.1; Wherein:
SPAN=(D90-D10)/D50
D90 is for being 90% particle diameter corresponding to accumulating weight branch rate in the following formula;
D10 is for being 10% particle diameter corresponding to accumulating weight branch rate in the following formula.
5. the ingredient of solid catalyst of olefinic polymerization according to claim 1 is characterized in that, described electron donor compound is selected from the binary alcohol esters compounds shown in the logical formula II:
R wherein
1-R
6, R
1-R
2C for hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl or C
7-C
20Aralkyl.
6. the ingredient of solid catalyst of olefinic polymerization according to claim 1, it is characterized in that, the usage quantity of described each component, magnesium in every mole of dialkoxy magnesium, the usage quantity of titanium compound is 0.5～100 mole, electron donor is 0.005～10 mole, and inert diluent is 0.5～100 mole.
7. the ingredient of solid catalyst of olefinic polymerization according to claim 1 is characterized in that, the usage quantity of described each component, magnesium in every mole of dialkoxy magnesium, the usage quantity of titanium compound is 1～50 mole, and electron donor is 0.01～1 mole, and inert diluent is 1～50 mole.
8. a solid catalyst that is used for olefinic polymerization is characterized in that, comprises the reaction product of following component:
The ingredient of solid catalyst of the described olefinic polymerization of one of A, claim 1～7;
B, organo-aluminium compound component; Its general formula is AlR
nX
3-n, in the formula R be hydrogen, and carbonatoms be 1～20 alkyl; X is halogen, and n is the integer of 0＜n≤3;
The silicoorganic compound component of C, a kind of optional adding; Its general formula is R
lR
2Si (OR')
2, R in the formula
l, R
2Identical or different, be C
1～C
20Alkyl, cycloalkyl or aryl, R' is the alkyl that contains 1～4 carbon atom.
9. the described solid catalyst for olefinic polymerization of claim 8 is in the application of olefinic polymerization.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010283034 CN102399326B (en) | 2010-09-16 | 2010-09-16 | Solid catalyst component for olefin polymerization, and catalyst thereof |
| KR1020137009647A KR20130100155A (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier 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 |
| 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 |
| ES11824428T ES2804259T3 (en) | 2010-09-16 | 2011-09-09 | Catalyst support 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 |
| EP11824428.4A EP2617739B1 (en) | 2010-09-16 | 2011-09-09 | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst |
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| CN 201010283034 CN102399326B (en) | 2010-09-16 | 2010-09-16 | Solid catalyst component for olefin polymerization, and catalyst thereof |
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| 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 |
| CN103788274B (en) * | 2012-10-30 | 2017-02-15 | 中国石油化工股份有限公司 | Propylene copolymer and preparation method thereof |
| SG2014001325A (en) * | 2013-05-21 | 2014-12-30 | China Petroleum & Chemical | A supported nonmetallocene catalyst, preparation and use thereof |
| WO2016086836A1 (en) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | Disulfonic acid ester compound, olefin polymerization catalyst component and olefin polymerization catalyst |
| BR112018015611A2 (en) * | 2016-02-15 | 2018-12-26 | Basell Polyolefine Gmbh | pre-activated catalyst component for olefin polymerization |
| CN106832069B (en) * | 2017-02-22 | 2019-03-08 | 营口风光新材料股份有限公司 | A kind of catalyst and preparation method thereof for olefinic polymerization |
| CN106632752B (en) * | 2017-02-22 | 2019-04-02 | 营口风光新材料股份有限公司 | A kind of olefine polymerizing process |
| CN106608941B (en) * | 2017-02-22 | 2019-03-29 | 营口风光新材料股份有限公司 | A kind of carrier and preparation method thereof for olefin polymerization catalysis |
| EP3489244A1 (en) * | 2017-11-28 | 2019-05-29 | Scg Chemicals Co. Ltd. | Magnesium compound, method for producing the same and use thereof |
| CN108912253A (en) * | 2018-06-12 | 2018-11-30 | 朴蓝聚烯烃科技发展（上海）有限公司 | A kind of solid polypropylene catalytic component |
| CN109503740B (en) * | 2018-11-09 | 2021-07-30 | 上海葛蓝化工科技有限公司 | Solid catalyst component for olefin polymerization |
| CN110483247A (en) * | 2019-07-16 | 2019-11-22 | 北京国达恒泰科贸有限责任公司 | Metal alkoxides powder and preparation method and application |
| WO2021018042A1 (en) | 2019-07-26 | 2021-02-04 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and use thereof |
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| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN101802024A (en) * | 2007-12-28 | 2010-08-11 | 三星Total株式会社 | Method of preparation of spherical support for olefin polymerization catalyst |
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| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN101802024A (en) * | 2007-12-28 | 2010-08-11 | 三星Total株式会社 | Method of preparation of spherical support for olefin polymerization catalyst |
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