CN1393479A - Olefine polymerized solid catalyst component containing clay and its preparing process - Google Patents
Olefine polymerized solid catalyst component containing clay and its preparing process Download PDFInfo
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- CN1393479A CN1393479A CN 01119816 CN01119816A CN1393479A CN 1393479 A CN1393479 A CN 1393479A CN 01119816 CN01119816 CN 01119816 CN 01119816 A CN01119816 A CN 01119816A CN 1393479 A CN1393479 A CN 1393479A
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Abstract
A solid catalyst for polymerizing olefines is prepared from kaolin clay, magnesium halide and transition metal compound in a certain proportion through calcining kaolin clay at 400-1000 deg.C, suspending it with magnesium chloride in hydrocarbon solvent, and reaction under existance of small amount of alcohol. The mentioned solid catalyst in match with an alkyl aluminium cocatalyst is used for polymerizing ethylene. Its advantage is high reaction activity.
Description
The present invention is a kind of solid catalyst for olefin polymerization component and preparation method thereof, specifically, be a kind of olefinic polymerization that is used for, particularly gas-phase polymerization process contain spherical solid catalyst component of transistion metal compound and clay and preparation method thereof.
At present, the industrial efficient polyolefin catalyst that generally uses is a Ziegler-Natta type catalyzer of making carrier with the compound of magnesium chloride or other magnesium, as USP4, and 298,718, USP4,526,943 and USP4,495,338 is described.This class catalyzer is applied in the polymer beads that can obtain solid form in typical slurry and the gas-phase polymerization process.For avoiding in polymerization process, particularly form little polymer beads or wide polymer particle size distribution in the gas-phase fluidized bed polymerization process, prevent to cause sticking problem by tiny granules of catalyst.Require solid catalyst that good particle form and uniform size distribution are not only arranged, also will have certain intensity, to adapt to the needs of fluidized bed process.For this reason, people add the intensity height in the catalyzer that with the magnesium chloride is carrier, and wear resistance is made the material of single-size well and easily, waits as silica gel and improves catalyst performance.The particle form that it is advantageous that catalyzer can depend on the indifferent oxide particle form that carries titanium, thereby can control the particle form and the size distribution of solid catalytic ingredient easily, finally can obtain the good polymkeric substance of particle form and size distribution.
EP43220A
1Disclosing a kind of is the catalyzer of carrier with silicon-dioxide, and this catalyzer is made with the precursor components impregnation of silica, and described precursor components is made by titanium, magnesium compound and electron donor compound, and its source is respectively MgCl
2, TiCl
4And tetrahydrofuran (THF).
USP5,278,117 disclose a kind of Ziegler-Natta catalyst and preparation method who is used for the load of vinyl polymerization, and the solid ingredient of this catalyzer contains the silica support of titanium, magnesium, chlorine, alkoxy base and microspheroidal, and its titanium/magnesium mol ratio is 1～6: 1.This solid constituent makes by the following method, the granular porous solid carrier of solution impregnation that in the liquid aliphatic hydrocarbon, forms with magnesium chloride and tetrol titanium, magnesium in the described solution/titanium mol ratio is 0.1～0.5: 1, behind the evaporating solvent, use the solution-treated of magnesium chloride in aliphatic ester again, evaporating solvent handles activating in 10 minutes～24 hours again at 10～100 ℃ with the chlorination aluminum alkyls.
Except that using silicon-dioxide and the carrier of magnesium chloride as Ziegler-Natta catalyst, also wish to adopt other comparatively cheap solids as carrier, as USP5,362,825 disclose a kind of preparation method of polyolefin catalyst, this method is with the reactant of cross-linked clay and metal dihalides and at least a transistion metal compound, and contact generates solids in the presence of liquid diluent, and the weight of used clay is 0.1～30 heavy % of above-mentioned reactant.The gained solids contacts with the halogenation organoaluminum and obtains solid catalyst.Metal dihalides described in this method is a magnesium dichloride, and transistion metal compound is Ti (OR)
4Clay is polynite or wilkinite, used clay need could use through complicated crosslinking Treatment step, and after the reactant contact reacts of itself and above-mentioned metal dihalides and at least a transistion metal compound, the gained solids also needs to handle with organo-aluminium compound and just can be used for polymerization catalyzed reaction.
CN1262282A discloses a kind of olefin polymerization solid catalyst, and this catalyzer is made up of clay, magnesium halide and transistion metal compound, and clay wherein comprises fiber rod stone kind clay, kaolinite, montmorillonite.This solid catalyst only carries out low-temperature bake to clay in the preparation, and purpose is moisture and other objectionable impurities of removing in the clay.In catalyst preparation process, flood clay again after magnesium chloride dissolved fully with alcohol, and then the carrying transition metal active ingredient.This method preparation process is more with the alcohol amount, is that the catalyst activity of carrier is on the low side with kaolin.
The purpose of this invention is to provide spherical polyolefine ingredient of solid catalyst that a kind of raw material is easy to get, the preparation method is simple and catalytic performance is good and preparation method thereof.
We find, with kaolinite family clay in high-temperature roasting, behind its crystalline structure completely destroy, mix with magnesium chloride again, the catalyzer that the carrier that makes under the effect of a small amount of alcohol obtains behind the carrying transition metal compound has advantages of high catalytic activity and good particle form.
Polyolefine solid catalytic ingredient provided by the invention comprises kaolinite family clay, magnesium halide and the transistion metal compound of no crystalline structure, wherein the content of transition metal is 0.2～10.0 heavy %, preferred 0.4～4.0 heavy %, Mg content are 1.0～10.0 heavy %, preferred 2.0～6.0 heavy %.
The preferred magnesium chloride of described magnesium halide, the kaolinite family clay of no crystalline structure are selected from kaolin, kaolinite, dickite, pearl pottery stone, 10 halloysites or the 7 halloysites of no crystalline structure, preferably do not have kaolin, the kaolinite of crystalline structure.
Described transistion metal compound is selected from halogenide, oxyhalogenation thing, the C of Ti, Zr, Hf, V, Nb, Ta, Ni or Sc
1～C
12Alcoxyl halogenide or hydrohalogen, the halogenide of Ti, oxyhalogenation thing, C
1～C
12Alcoxyl halogenide, more preferably TiCl
4
The preparation method of catalyst solid constituent of the present invention comprises:
(1) with kaolinite family clay in 400～1000 ℃ of roastings, make its crystalline structure completely destroy;
(2) with the clay behind (1) one-step baking and Magnesium Chloride Anhydrous according to 4～40: 1 weight ratio is suspended in the unreactive hydrocarbons solvent, adding the dispersion agent stirring down at 30～200 ℃ carries out pre-dispersed, wherein the mol ratio of dispersion agent and Magnesium Chloride Anhydrous is 0.01～1.0, preferred 0.05～1.0, more preferably 0.1～0.4;
(3) 30～200 ℃, in pre-dispersed system of (2) step, add C under stirring
2～C
8Alcohol, alcohol is 0.05～1.5 with the mol ratio of Magnesium Chloride Anhydrous, and is preferred 0.1～1.0, more preferably 0.1～0.8;
(4) keep (3) Buwen's degree, add transistion metal compound reaction 0.5～6.0 hour, then that solid product is also dry with the unreactive hydrocarbons solvent washing.
Described maturing temperature of (1) step is preferred 500～850 ℃ in the above-mentioned preparation process, and more preferably 620～850 ℃, preferred 4～6 hours of time.The kaolinite family clay that is used for roasting is selected from kaolin, kaolinite, dickite, pearl pottery stone, 10 halloysites or 7 halloysites, is the spheroidal particle of particle diameter less than 100 microns.Spherical clay can adopt spray-drying process to be prepared, and preferred clay particle diameter is 50～70 microns.
The described kaolinite family clay that is used for roasting refers to kandite, and the main component of this kind mineral is a kaolinite, and its molecular formula is Al
4(Si
4O
10) (OH)
8, these mineral are the silicate with 1: 1 type dioctahedron laminate structure.By the crystal chemistry classification, belong to the dioctahedron subtribe in serpentine-kaolinite family.These family's mineral generally include kaolinite (kaolinite), dickite (dickite), pearl pottery stone (nacrite), 10 halloysites (halloysite-10 ) and 7 halloysites (halloysite-7 ).These mineral have same 1: 1 structural unit layer, but the geometric shape difference that characteristics, interlayer and the crystal of layer stacking extend, thereby constituted different mineral species or mutation.
(2) step of aforesaid method is the clay after the roasting and magnesium chloride to be carried out pre-dispersed in unreactive hydrocarbons solvent with dispersion agent, and the amount of unreactive hydrocarbons solvent should be 5～100 times of magnesium halide weight.Clay and magnesium chloride can add in the hydrocarbon solvent simultaneously, also can add in the hydrocarbon solvent respectively.It is Ti (OR) that described dispersion agent is selected from general formula
4Alkoxy titanium compound or C
3～C
8Alcohol, wherein R is C
2～C
6Alkyl, preferred C
2～C
4Alkyl, as titanium butoxide, ethanolato-titanium, titanium propanolate.The described preferred propyl alcohol of alcohol, butanols, hexanol, octanol or their mixture that is used for dispersion agent.
Described (3) step is that the material after pre-dispersed is activated with a small amount of alcohol, and the carrier that obtains like this gets final product load active component without dealcoholysis.Carry out activatory alcohol preferred alcohol, propyl alcohol, Virahol, butanols, hexanol, octanol or their mixture.
Carrier loaded transistion metal compound after described (4) step activates (3) step prepares ingredient of solid catalyst.Described transistion metal compound is selected from halogenide, oxyhalogenation thing, the C of Ti, Zr, Hf, V, Nb, Ta, Ni or Sc
1～C
12Alcoxyl halogenide or hydrohalogen, halogenide, oxyhalogenation thing, the C of preferred titanium
1～C
12Alcoxyl halogenide or hydrohalogen, the halogenide of titanium more preferably is as TiCl
4The mol ratio of transistion metal compound and magnesium chloride is 1.0～2.0: 1 in this step.
(4) solid that obtains after the reaction of step and transistion metal compound needs with the unreactive hydrocarbons solvent washing, and the degree of washing should make the content of transition metal in the washings less than 0.2 mg/ml.Drying temperature after the washing is 40～100 ℃, preferred 0.5～4.0 hour of time.
Unreactive hydrocarbons solvent described in the preparation method of catalyst solid constituent provided by the invention is selected from C
5～C
15Alkane or C
6～C
18Aromatic hydrocarbons, preferred C
5～C
10Alkane and C
6～C
8Aromatic hydrocarbons, as pentane, hexane, heptane, octane, decane, benzene or toluene.In addition, answer unanimity for the temperature of easy to operate step (2)～(4), preferred temperature is 40～100 ℃.
For further improving the flowability of catalyst activity and spherical catalyst, can in the product after the above-mentioned unreactive hydrocarbons washing, add aluminum alkyls or alkyl aluminum halide compound treatment, treatment temp is 10～25 ℃, and the time is 1～1.5 hour, and described alkylaluminium cpd is selected from C
8Aluminum alkyls or chlorination aluminum alkyls, preferred triisobutyl aluminium, triethyl aluminum or aluminium diethyl monochloride.The dosage of alkylaluminium cpd should make wherein aluminium and reaction product in the mol ratio of transition metal be 2～20: 1, preferred 2～17: 1.
Solid catalyst of the present invention is applicable to the homopolymerization or the copolyreaction of alpha-olefin, should use alkylaluminium cpd as promotor during polymerization, and preferred alkylaluminium cpd is triethyl aluminum, triisobutyl aluminium or three n-butylaluminum.The mol ratio of aluminium and transition metal should be greater than 1 in the used aluminum alkyls, and the mol ratio of suitable aluminium/transition metal is 20～800: 1, is preferably 20～300: 1.Polyreaction can be carried out in gas phase or liquid phase, can select for use unreactive hydrocarbons as attenuant during liquid polymerization, and unreactive hydrocarbons commonly used are hexane, heptane.Vapour phase polymerization can adopt fluidized bed polymerization process.Temperature of reaction suitable during polymerization is 20～150 ℃, preferred 60～90 ℃.Reaction can be carried out under normal pressure, also can under high pressure carry out, as carrying out under 0.6～3.0MPa pressure.
Clay in the ingredient of solid catalyst provided by the invention is cheap and easy to get, be easy to make be evenly distributed, the particle of good fluidity.Described catalyst component preparation method is simple, will the magnesium chloride fusion not flood clay again, only needs with a small amount of alcohol the magnesium chloride activation to be got final product load active component, thereby has saved dealcoholysis step of the prior art, has simplified operation, has also saved pure consumption simultaneously.The gained catalyzer has high polymerization activity and good particle form.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare ingredient of solid catalyst of the present invention.
(1) particle diameter of getting spray shaping is 40～74 microns a spherical kaolin (group company of CNPC Lanzhou refinery head factory is produced), 620 ℃ of roastings 6 hours, and X-ray diffraction spectrogram shown in Figure 1 shows after the roasting kaolinic crystalline texture completely destroy.
(2) under nitrogen protection, get 0.5 clay that restrains after Magnesium Chloride Anhydrous (5.25mmol) powder (Fushun No.3 Petroleum Factory's production) and 4.0 restrains above-mentioned roasting; add and have in the vial of reflux exchanger and mechanical stirrer; add 40 milliliters of hexanes; be warming up to reflux temperature, drip 0.05 milliliter of (0.147mmol) titanium butoxide [Ti (OBu)
4] (production of Great Wall, Beijing chemical reagent factory), under 60 ℃, 300 rev/mins condition, stirred pre-dispersed 1 hour.
(3) in above-mentioned predispersion is, drip 0.15 milliliter of (1.64mmol) butanols reaction at 60 ℃ and activated in 1 hour,
(4) add 0.75 milliliter of TiCl in the system in (3) while stirring
4, 60 ℃ of reactions 2.0 hours, the gained solid is with 30 milliliters of hexane wash 4 times, and the content of Ti is less than 0.2 mg/ml in the washings.60 ℃ of dryings 1 hour obtain spherical solid catalyst component A4.8 gram, and wherein Mg content is 3.12 heavy %, and titanium content is 0.93 heavy %.Opticmicroscope is observed this catalyst component down and has been reappeared spherical clay carrier particulate form.
Example 2
Method according to example 1 prepares ingredient of solid catalyst, and different was with the kaolin microsphere in (1) step 800 ℃ of following roastings 6 hours, the microspheroidal ingredient of solid catalyst B4.4 gram that makes at last, and wherein Mg content is 2.6 heavy %, titanium content is 1.05 heavy %.Kaolinic x-ray diffraction pattern figure shows its crystalline texture completely destroy after the roasting shown in Figure 2.
Example 3
Method according to example 1 prepares ingredient of solid catalyst C, and different is to add 0.40 milliliter of TiCl in (4) step
4, the gained solid obtains spherical solid 4.3 grams after with hexane wash, drying, and opticmicroscope is observed this catalyst component down and has been reappeared spherical clay carrier particulate form.Wherein Mg content is 3.61 heavy %, and titanium content is 1.17 heavy %.
Example 4
Method by example 1 prepares ingredient of solid catalyst D, and different is 3.2 grams of the kaolin microsphere after the adding roasting in (2) step, and anhydrous magnesium chloride 0.27 gram (2.8mmol) is at 0.05 milliliter of (0.15mmol) titanium butoxide [Ti (OBu) of 80 ℃ of droppings
4] carry out pre-dispersedly, under same temperature, drip 0.16 milliliter of (1.7mmol) butanols and activate, add TiCl then while stirring
40.35 milliliter, 80 ℃ of reactions 2.0 hours, the gained solid obtains spherical solid granules of catalyst 3.4 grams with 30 milliliters of hexane wash 4 times after 60 ℃ of dryings, and wherein Mg content is 1.86 heavy %, and titanium content is 0.79 to weigh %.Opticmicroscope is observed this catalyst component down and has been reappeared spherical clay carrier particulate form.
Example 5
Method by example 1 prepares ingredient of solid catalyst E, and different is 8.0 grams of the kaolin microsphere after the adding roasting in (2) step, and anhydrous magnesium chloride 0.25 gram (2.6mmol) drips 0.1 milliliter of (0.29mmol) titanium butoxide [Ti (OBu) then
4], under 60 ℃, 300 rev/mins condition, stirred pre-dispersed 1 hour, under similarity condition, drip 0.30 milliliter of (3.3mmol) butanols activation then, again with 0.8 milliliter of TiCl
4Reaction.Reacted solid is with 30 milliliters of hexane wash 4 times, and 60 ℃ of dryings obtain spherical solid 8.4 grams, and wherein Mg content is 1.2 heavy %, and titanium content is 1.11 heavy %.Opticmicroscope is observed this catalyst component down and has been reappeared spherical clay carrier particulate form.
Example 6
Method by example 1 prepares ingredient of solid catalyst F, and different is 3.3 grams of the kaolin microsphere after the adding roasting in (2) step, and anhydrous magnesium chloride 0.60 gram (6.3mmol) drips 0.1 milliliter of (0.29mmol) titanium butoxide [Ti (OBu) then
4] pre-dispersed, drip 0.30 milliliter of (3.3mmol) butanols activation again, (4) add TiCl in the step
40.74 milliliter reacts, reaction gained solid is with 30 milliliters of hexane wash 4 times, and 60 ℃ of dryings obtain spherical solid granules of catalyst 4.1 grams, and wherein Mg content is 3.51 heavy %, and titanium content is 1.77 to weigh %.This catalyst component has reappeared spherical clay carrier particulate form under opticmicroscope.
Example 7
Method by example 5 prepares solid catalytic ingredient F, and different is to add TiCl
4Reaction back solid with hexane wash after, with the diethylaluminum chloride (AlEt of 2.0M
2Cl) hexane solution was handled 1 hour under 20 ℃ for 9.3 milliliters, obtained spherical catalyst 1.0 grams after 60 ℃ of dryings, and wherein Mg content is 1.2 heavy %, and titanium content is 1.74 heavy %.
Example 8
Method by example 6 prepares solid catalytic ingredient H, and different is that (2) go on foot with 0.26 milliliter of ethanolato-titanium Ti (OEt)
4(1.25mmol) replace Ti (OBu)
4, drip 0.2 milliliter of (0.59mmol) butanols activation, obtain solid catalyst 2.93 grams, wherein Mg content is 3.51 heavy %, titanium content is 1.06 heavy %.
Comparative Examples 1
Method according to example 1 prepares ingredient of solid catalyst M, and different was with the kaolin in (1) step 200 ℃ of roastings 6 hours, and X-ray diffraction spectrogram shown in Figure 3 shows that its crystalline texture still exists.Therefore low-temperature bake has only been removed the moisture content in the kaolin.Mg content is 4.05 heavy % among the catalyzer M, and titanium content is 1.94 heavy %.
Comparative Examples 2
This example is with magnesium chloride dissolving back preparation ingredient of solid catalyst.Get 0.45 gram Magnesium Chloride Anhydrous (4.7mmol) powder under nitrogen protection, adding has in the vial of reflux exchanger and mechanical stirrer, adds 40 milliliters of hexanes, is warming up to reflux temperature, drips 0.09 milliliter of (0.26mmol) titanium butoxide [Ti (OBu)
4] and 2.16 milliliters of butanols (23.6mmol), under 60 ℃, 300 rev/mins condition, solid is dissolved fully.Add 2.61 grams again by the reaction of the kaolin after example 1 (1) the one step process roasting 0.5 hour, add 4.6 milliliters of TiCl afterwards while stirring
4Reacted 1 hour, solid is with 30 milliliters of hexane wash 4 times, and 60 ℃ of dryings 1.5 hours obtain spherical solid catalyst component N3.11 gram, and wherein Mg content is 3.57 heavy %, and titanium content is 2.79 heavy %.
Comparative Examples 3
This example is preparing carriers ingredient of solid catalyst K with silica gel.With trade names is the Davison 955 (U.S., Grace company produces) silica gel 600 ℃ of roastings 6 hours; get silica gel 2.69 grams after the roasting and 0.45 gram (4.7mmol) magnesium chloride and prepare ingredient of solid catalyst; different is (2) goes on foot 0.09 milliliter of (0.26mmol) titanium butoxide of dropping and carry out pre-dispersed; drip 0.27 milliliter of butanols (2.95mmol) again and activate, add 0.6 milliliter of TiCl afterwards by the method in example 1 (2)～(4) step
4, after the hexane wash drying, obtain 3.24 gram catalyst component K, wherein Mg content is 6.63 heavy %, titanium content is 3.10 heavy %.
Example 9～19
Following example carries out the normal pressure ethylene polymerization, investigates the reactive behavior of solid catalyst.
500 milliliters of there-necked flasks that have agitator and constant temperature system are replaced three times with the nitrogen pump drainage, again once with the ethene displacement, add 100 milliliters of hexanes successively, 30 milligrams of the hexane solution of the triethyl aluminum of 4 milliliter of 1.5 mol and solid catalysts start stirring, feed ethylene gas, reaction is 2 hours under 40 ℃, 0.1MPa condition, with 2 milliliters of ethanol termination reactions, obtain the spherical polyethylene particle that easily flows, catalyst activity sees Table 1.
Example 20～21
This example carries out gas-phase fluidized-bed vinyl polymerization experiment to catalyst component of the present invention.
It with 40 gram ingredients of solid catalyst of the present invention and the good particle diameter of 100 gram screenings 175～147 microns polyethylene base-material, with 10 ml concns be that the hexane solution thorough mixing of triethyl aluminum of 2.0 mol is even, add diameter then and be in 100 millimeters the gas-phase fluidized-bed reactor, feed ethene and hydrogen, Controlling System pressure is 1.0MPa, hydrogen partial pressure is 0.28MPa, and temperature is 80 ℃, polyreaction 2 hours.Unreacting ethylene is discharged from the fluidized-bed reactor top in the reaction process, enter the reactor cycles reaction by recycle compressor compression back from fluidized-bed reactor, simultaneously fresh ethylene and hydrogen are injected the recycle stream of discharging from reactor head with the ethene of postreaction with keep the hydrogen dividing potential drop.Gas phase polymerization catalytic activity and polymer particle size distribute and see Table 2.Table 1
Table 2
| Instance number | The catalyzer numbering | Catalytic activity, gram PE/ gram catalyzer | Polymer particle size distributes, heavy % | |||
| ??＞3.2mm | ??3.2～1.4mm | ??1.4～0.83mm | ??0.83～0.18mm | |||
| ??19 | ??E | ????2500 | ????5.0 | ????50.0 | ????30.0 | ????15.0 |
| ??20 | ??F | ????7000 | ????8.0 | ????60.0 | ????20.0 | ????10.0 |
Claims (18)
1, a kind of polyolefine solid catalytic ingredient comprises kaolinite family clay, magnesium halide and the transistion metal compound of no crystalline structure, and wherein the content of transition metal is 0.2～10.0 heavy %, and Mg content is 1.0～10.0 heavy %.
2,, it is characterized in that the kaolinite family clay of described no crystalline structure is selected from the kaolin of no crystalline structure, kaolinite, dickite, pearl pottery stone, 10 halloysites or 7 halloysites according to the described catalyst component of claim 1.
3,, it is characterized in that described magnesium halide is a magnesium chloride according to the described catalyst component of claim 1.
4,, it is characterized in that described transistion metal compound is selected from the halogenide of Ti, Zr, Hf, V, Nb, Ta, Ni or Sc, oxyhalogenation thing, C according to the described catalyst component of claim 1
1～C
12Alcoxyl halogenide or hydrohalogen.
5,, it is characterized in that titanium content is 0.4～4.0 heavy % in this component according to the described catalyst component of claim 1.
6, the preparation method of the described catalyst component of a kind of claim 1 comprises:
(1) with kaolinite family clay in 400～1000 ℃ of roastings, make its crystalline structure completely destroy;
(2) with the clay behind (1) one-step baking and Magnesium Chloride Anhydrous according to 4～40: 1 weight ratio is suspended in the unreactive hydrocarbons solvent, adds dispersion agents down at 30～200 ℃ and stirs and carry out pre-dispersedly, and wherein the mol ratio of dispersion agent and Magnesium Chloride Anhydrous is 0.01～1.0;
(3) 30～200 ℃, in pre-dispersed system of (2) step, add C under stirring
2～C
8Alcohol, alcohol is 0.05～1.5 with the mol ratio of Magnesium Chloride Anhydrous;
(4) keep (3) Buwen's degree, add transistion metal compound reaction 0.5～6.0 hour, then that solid product is also dry with the unreactive hydrocarbons solvent washing.
7, in accordance with the method for claim 6, it is characterized in that described maturing temperature of (1) step is 500～850 ℃, the time is 4～6 hours.
8, in accordance with the method for claim 6, it is characterized in that (1) step described kaolinite family clay is selected from kaolin, kaolinite, dickite, pearl pottery stone, 10 halloysites or 7 halloysites, is the spheroidal particle of particle diameter less than 100 microns.
9, in accordance with the method for claim 6, it is characterized in that it is Ti (OR) that described dispersion agent of (2) step is selected from general formula
4Alkoxy titanium compound or C
3～C
8Alcohol, wherein R is C
2～C
6Alkyl.
10, in accordance with the method for claim 9, it is characterized in that described alkoxy titanium compound is selected from titanium butoxide, ethanolato-titanium, titanium propanolate.
11, in accordance with the method for claim 9, it is characterized in that the alcohol of selecting for use as dispersion agent is propyl alcohol, butanols, hexanol, octanol or their mixture.
12, in accordance with the method for claim 6, it is characterized in that described alcohol of (3) step is selected from ethanol, propyl alcohol, Virahol, butanols, hexanol, octanol or their mixture.
13, in accordance with the method for claim 6, it is characterized in that described transistion metal compound of (4) step is selected from halogenide, oxyhalogenation thing, the C of Ti, Zr, Hf, V, Nb, Ta, Ni or Sc
1～C
12Alcoxyl halogenide or hydrohalogen.
14, in accordance with the method for claim 13, it is characterized in that described transistion metal compound is halogenide, oxyhalogenation thing, the C of titanium
1～C
12Alcoxyl halogenide or hydrohalogen.
15, in accordance with the method for claim 6, it is characterized in that described unreactive hydrocarbons solvent is selected from C
5～C
12Alkane or C
6～C
8Aromatic hydrocarbons.
16, in accordance with the method for claim 6, it is characterized in that the temperature that (2)～(4) go on foot is 40～100 ℃.
17, in accordance with the method for claim 6, it is characterized in that adding in the product after (4) step washing aluminum alkyls or halogenated alkyl aluminum compound, it is 2～20: 1 that its dosage makes the mol ratio of Ti in aluminium in the alkylaluminium cpd and the reaction product.
18, in accordance with the method for claim 17, it is characterized in that described aluminum alkyls or halogenated alkyl aluminum compound are selected from triisobutyl aluminium, triethyl aluminum or aluminium diethyl monochloride.
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| WO2016074242A1 (en) * | 2014-11-14 | 2016-05-19 | 中国科学院化学研究所 | Olefin polymerisation catalyst component, preparation method therefor, olefin polymerisation catalyst and application thereof |
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2001
- 2001-06-29 CN CN 01119816 patent/CN1132857C/en not_active Expired - Lifetime
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| CN104448064A (en) * | 2014-11-14 | 2015-03-25 | 中国科学院化学研究所 | Polyolefin resin composition and preparation method thereof |
| WO2016074242A1 (en) * | 2014-11-14 | 2016-05-19 | 中国科学院化学研究所 | Olefin polymerisation catalyst component, preparation method therefor, olefin polymerisation catalyst and application thereof |
| WO2016074243A1 (en) * | 2014-11-14 | 2016-05-19 | 中国科学院化学研究所 | Polyolefin resin composition and preparation method therefor |
| CN105732854A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing polyethylene/kaolin composite material |
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