CN101173015B - Catalyst component for polymerization of ethylene or combined polymerization, producing method and catalyst thereof - Google Patents
Catalyst component for polymerization of ethylene or combined polymerization, producing method and catalyst thereof Download PDFInfo
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- CN101173015B CN101173015B CN2007101633213A CN200710163321A CN101173015B CN 101173015 B CN101173015 B CN 101173015B CN 2007101633213 A CN2007101633213 A CN 2007101633213A CN 200710163321 A CN200710163321 A CN 200710163321A CN 101173015 B CN101173015 B CN 101173015B
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Abstract
The invention relates to a catalyst component used for the polymerization or the copolymerization of ethylene, and the component is of a solid with titanium and gets carried with the compound of at least a transition metal titanium and at least one electron donor compound. The invention also provides a preparation method for the catalyst component and a catalyst containing the catalyst component. The polymer powder lot obtained by the polymerization of the catalyst component of the invention has rather centralized granularity distribution, small fine powder content and high bulk density. The invention is applicable for the homopolymerization of various ethylenes or the copolymerization of ethylene and other alpha-alkenes, and more suitable for gas phase fluidization bed polymerization and slurry polymerization, and in particular suitable for the condensation technique of the gas phase fluidization bed.
Description
Technical field
The present invention relates to a kind of catalyst component, its preparation method and catalyzer thereof that is used for vinyl polymerization or copolymerization, belong to the polyalcohol catalyst field.
Background technology
As everyone knows, in the copolymerization of the polymerization of the polyreaction of alkene, particularly ethene or ethene and alpha-olefin, the catalyzer that is adopted is as its basal component with magnesium, titanium, halogen and electron donor.When this class catalyzer is used for gas-phase fluidized bed polymerization process, be to guarantee the form of granules of catalyst and the operation that size-grade distribution is more suitable for fluidized state, normally above-mentioned catalyst component is carried on the carrier such as silica gel.For example: US4,302,565, US4,379,759 and CN1064870A in disclosedly be used for gas-phase fluidized-bed catalyst for reaction, be that precursor components with titanium compound, magnesium compound and electron donor compound is immersed on the carrier substance such as silica gel, handle impregnated precursor components with active compound again and prepare.At US4, the median size of employed silica gel is the 50-150 micron in 302,565, US4,379,759, and surface-area is greater than 50 meters
2/ gram, mean pore size is greater than 80 dusts.
In above-mentioned disclosed patent, in order to make catalyzer applicable to gas-phase fluidized bed polymerization process, all there is strict requirement in median size, surface-area, aperture to employed carrier-silicon-dioxide, and the costing an arm and a leg of this silica supports, the catalyst activity component is to be carried on the carrier by the impregnating method, because the people is dissatisfied in addition yet for factors such as load quantitative limitation, its activity of such catalysts.In addition, use in the polyethylene powder of this Catalyst Production fine powder amount bigger, common particle below 150 microns accounts for about the 15Wt% of whole powders, is unfavorable for the fluidized-bed reactor long-term operation.Simultaneously, this catalyzer is when being applied to ethene gas fluidised bed polymerisation full scale plant, and catalyzer with the charging of solid form, advances the charging process poor stability mostly, easily produces static, and is prone to phenomenons such as plugging, bridge formation.
Among the Chinese patent publication number CN85100997, a kind of olefin polymerization catalysis that is used for is disclosed, it is to be dissolved in organic epoxy compounds by magnesium halide, organo phosphorous compounds forms homogeneous solution, again with at least a precipitation additive, the halogenide and the derivative effect thereof of a kind of multi-carboxylate's electron donor and transition metals Ti prepare, when this catalyzer is used for propylene polymerization, high polymerization activity and stereospecificity have preferably been shown, but activity is lower when being used for vinyl polymerization, the broad particle distribution of polymkeric substance, segment morely, the hydrogen response of this catalyzer is not ideal enough.
Chinese patent publication number CN1229092A discloses a kind of catalyzer that is used for vinyl polymerization or copolymerization, it is to be dissolved in organic epoxy compounds by magnesium halide, organo phosphorous compounds adds the electron donor stimulator again and forms homogeneous solution, halogenide and derivative effect thereof with at least a precipitation additive and transition metals Ti prepares again, this catalyzer has shown very high activity when being used for the slurry polymerization of ethene, the particle form of resulting polymers is better simultaneously, apparent density is also higher, but polymer beads is thinner, the coating of particles systematicness is bad, and the people is dissatisfied in addition for the result.
A kind of catalyzer that is used for vinyl polymerization or copolymerization is disclosed in the Chinese patent application number 02120861, it is to be dissolved in organic epoxy compounds by magnesium halide, in the homogeneous solution of organo phosphorous compounds and inert solvent, the solids that obtains titaniferous magnesium with the halogenide and the derivative effect thereof of at least a precipitation additive and transition metals Ti again, at least a electron donor of load and at least a activator on the solids of this titaniferous magnesium again, this catalyzer has shown higher activity when being used for the slurry polymerization of ethene, the particle form of resulting polymers is good, apparent density is higher, but this catalyzer hydrogen response is poor, and the polymer powders size-grade distribution is not ideal enough.
A kind of catalyst component that is used for vinyl polymerization or copolymerization is disclosed in the Chinese patent application numbers 200410078279, it is to be dissolved in organic epoxy compounds by magnesium halide, in the homogeneous solution of organo phosphorous compounds and inert solvent, obtain containing the solids of magnesium titanium again with the halogenide or derivatives thereof effect of at least a precipitation additive and transition metals Ti, at least a transition metal titanium compound of load on this solids, at least a suitable electron donor, at least a hydrogen regulation performance improving agent, activity was higher when this catalyzer was used for the slurry polymerization of ethene, hydrogen response is good, but also has problems such as the polymer powders size-grade distribution is undesirable.
Summary of the invention
The object of the present invention is to provide the high ingredient of solid catalyst that is used for vinyl polymerization or copolymerization of a kind of activity.
Another object of the present invention is to provide a kind of preparation method of catalyst component.
A further object of the present invention is to provide a kind of catalyzer.
The catalyst component that is used for vinyl polymerization or copolymerization of the present invention, it is a kind of titaniferous solids, and at least a transition metal titanium compound of load and at least a electron donor.
The general formula of the compound of wherein said transition metals Ti is Ti (OR)
aX
b, R is aliphatic hydrocarbyl or the aromatic hydrocarbyl of C1～C14 in the formula, and X is a halogen, and a is 0 to 2 integer, and b is 1 to 4 integer, a+b=3 or 4.Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine ethanolato-titanium, the titanous chloride or their mixture for use, preferred titanium tetrachloride, trichlorine ethanolato-titanium or titanous chloride.
Described electron donor compound is selected from aliphatic ether, cyclic aliphatic ether and aliphatic ketone; Be preferably C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers, C
3～C
6Aliphatic ketone.Be specially ether, n-butyl ether, ethyl isobutyl ether, hexyl ether, phenyl ethyl ether, tetrahydrofuran (THF) (THF), acetone and methyl iso-butyl ketone (MIBK).This class electron donor can use separately or several being used.
Titaniferous solids of the present invention is that dialkoxy magnesium and transition metals Ti compound effects are obtained.It can have inert diluent, also can carry out under the situation that the inertialess thinner exists.
Described dialkoxy magnesium is a kind of in magnesium methylate, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, oxyethyl group methoxy base magnesium, oxyethyl group propoxy-magnesium, the butoxy magnesium ethylate or their mixture.Be preferably diethoxy magnesium or dipropoxy magnesium.
Described inert diluent is pentane, hexane, heptane, octane, decane, benzene,toluene,xylene and derivative thereof; Be preferably toluene, heptane or hexane.
According in the actual application to the requirement of activity of such catalysts, also adopt at least a activator that catalyst component of the present invention is handled.
It is AlR that described activator adopts general formula
cX
dH
eCompound, R is C in the formula
1～C
14Saturated hydrocarbyl, X is a halogen, d is 0,1 or 2, e is 1 or 0, c+d+e=3 specifically can select AlEt for use
3, Al (n-Bu)
3, Al (i-Bu)
3, Al (n-C
6H
13)
3, AlEt
2Cl, Al (n-C
8H
17)
3Deng.
The catalyst component that is used for vinyl polymerization or copolymerization of the present invention, adopt the following step preparation:
1) preparation of titaniferous solids: dialkoxy magnesium under the situation that has inert diluent or inertialess thinner to exist, is obtained with the transition metals Ti compound effects;
2) in the presence of described electron donor compound, titaniferous solids and the reaction of transition metal titanium compound are formed.
Further comprise step 2) reaction after, be AlR with general formula again
cX
dH
eActivator compound carry out activation treatment.
The ratio of each component in the step 1) wherein, in every mole of dialkoxy magnesium, inert diluent is 0～100 mole, the transition metal titanium compound is 2～20 moles.
Step 2) in the presence of described electron donor compound, after titaniferous solids and the reaction of transition metal titanium compound, be AlR with general formula again
cX
dH
eActivator compound carry out activation treatment, in every mole of dialkoxy magnesium compound, titanium compound is 0.3～20 mole, is preferably 0.5～10 mole; Electron donor is 0.01～10 mole, is preferably 0.01～1mol; 0.1～10 mole in activator is preferably 0.1～5 mole.
In the resulting catalyst component of the present invention, magnesium: 6～30%, titanium: 0.5～10%, electron donor: 1～50%, be weight percentage.
The catalyzer that is used for vinyl polymerization or copolymerization of the present invention, it is made up of catalyst component of the present invention and alkylaluminium cpd.
The general formula of wherein used alkylaluminium cpd is AlR
3, R is C identical or inequality
1-8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls to mix use, particular compound such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter aluminium triethyl etc. are preferably triethyl aluminum, triisobutyl aluminium etc.
Ratio between catalyst component and the alkylaluminium cpd with the molar ratio computing of titanium and aluminium is: 1: 5～100, be preferably 1: 8～and 30.
Researchist of the present invention selects suitable titaniferous solids, transition metal titanium compound and electron donor, and find out suitable proportioning between each component, obtain highly active ethylene polymerization catalysts component thus, and the size-grade distribution of the polymer powders that the active high solid catalyst polymerization of employing the present invention obtains is very concentrated, and fine powder content is few, the tap density height.
Catalyzer of the present invention is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts C
3～C
8Alpha-olefin; Concrete as propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation and slurry polymerization particularly gas-phase fluidized-bed condensation technology.
Because activity of such catalysts of the present invention is very high, can adopt inert diluent with catalyst dilution during the suggestion industrial application, for example the mineral wet goods is realized catalyst slurry charging equably by the pumping feeding manner, and is very favourable to the fluidized-bed stable operation.
Embodiment
Further describe the present invention with embodiment below, help understanding, but described embodiment only is used to illustrate the present invention rather than restriction the present invention the present invention and advantage thereof, better effects if.
Testing method:
1. melting index (MI) is to measure according to ASTM D1238-99;
2. flow index (FI) is to measure according to ASTM D1238-99;
3. melt flow ratio (MFR) is a melting index and the ratio of flow index;
4. density polymer is to measure according to GB-1033;
5. size-grade distribution-basis is based on the method for the optical diffraction principle of one-wavelength laser, with " MalvernInstr.2600 " tester.
Embodiment 1
1, the preparation of catalyst component
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml, add 10g magnesium ethylate (tap density 0.27g/cm
3) and the prepare suspension of 80ml toluene, maintain 0 ℃ then and drip titanium tetrachloride 20ml.After dropwising system was warming up to 110 ℃ of constant temperature 2 hours, then that the liquid press filtration is clean, elimination liquid, the solid of gained obtains titaniferous solids A with toluene and twice washing of hexane after drying.
10 gram solids A are joined in another reactor, add 100ml iso-pentane, 0.4 gram titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, normal temperature reacted 1 hour down, filter solution, add the 100ml iso-pentane again, the aluminium diethyl monochloride solution reaction of 4 ml volumes concentration 26.43% 1 hour, evaporation drying obtain particulate solid thing B component 12.6 grams, wherein contain Ti1.98% (weight), Mg13.51% (weight), tetrahydrofuran (THF) 46.8% (weight).
2, ethene slurry polymerization (polymerization appreciation condition)
Volume is 2 liters a stainless steel cauldron, after hydrogen gas is fully replaced, add through about 0.5 liter of refining exsiccant hexane, adding concentration is 1mmol/ml triethyl aluminum one hexane solution 2ml, stir the above-mentioned solid ingredient B that adds 10 milligrams down again, replenish the hexane total amount and be about 1 liter.
Heat up and successively feed hydrogen and ethene, 2.8 * 10 in the reinforced back that finishes
5Pa H
2, 7.5 * 10
5Pa ethene, polymerization temperature are 85 ℃, react two hours, and overbottom pressure in the still of lowering the temperature, drain is emitted the polymer slurries material, with the polymkeric substance oven dry, obtain polyethylene powder, the results are shown in Table 1.Measure the granularity of catalyzer and polymkeric substance respectively, the results are shown in Table 2 and 3.
Embodiment 2
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml, add the 80ml titanium tetrachloride and be cooled to 0 ℃, slowly add 10g magnesium ethylate (tap density 0.27g/cm
3), then, system was warming up to 110 ℃ of constant temperature 2 hours, the liquid press filtration is clean, elimination liquid, the solid of gained obtains titaniferous solids A with toluene and twice washing of hexane after drying.
In reactor, the solids A10 gram that adds preparation among the embodiment 2, add 100 milliliters of hexanes, normal temperature drips 5 milliliters of 0.6 milliliter of titanium tetrachloride and tetrahydrofuran (THF)s down, reacted 2 hours, the aluminium diethyl monochloride that adds 3 ml volumes concentration 26.43% again reacted 2 hours, and evaporation drying obtains solid ingredient B12.5 gram, contains Ti3.2% (weight), Mg12.78% (weight), tetrahydrofuran (THF) 18.5% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
Solid ingredient A 10 grams that in reactor, add preparation among the embodiment 1, add 80 milliliters of toluene, 50 milliliters of titanium tetrachlorides, normal temperature drips 10 milliliters of tetrahydrofuran (THF)s down, be warming up to 100 ℃, reacted 2 hours, filter solution, 100ml toluene wash 1 time, 100ml hexane wash 2 times, drying obtain solid ingredient B11.2 gram, contain Ti 2.53% (weight), Mg14.6% (weight), tetrahydrofuran (THF) 22.9% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 4
Under the normal temperature, 2.5 liter of four titanium butoxide and 8 liters of tetrahydrofuran (THF)s joined in 15 liters the reactor, mix the back and add 600 gram titanous chlorides, stirs the even compound titanium solution of generation after 6 hours.
The solid ingredient A10 gram that in reactor, adds preparation among the embodiment 1, add 100 milliliters of hexanes, 10 milliliters of the compound titanium solutions that dropping generates above, normal temperature reacted 2 hours down, evaporation drying obtains solid ingredient B13.8 gram, contains Ti3.5% (weight), Mg11.65% (weight), tetrahydrofuran (THF) 23.6% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 5
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml, add 10g magnesium ethylate (tap density 0.27g/cm
3) and the prepare suspension of 80ml toluene, maintain 0 ℃ then and drip titanium tetrachloride 20ml.After dropwising system was warming up to 110 ℃ of constant temperature 2 hours, then that the liquid press filtration is clean, elimination liquid, the solid of gained obtains titaniferous solids A with toluene and twice washing of hexane after drying.In the reactor that fills solids A, add the 100ml hexane, under agitation add 10mlTiCl
4Normal temperature reacted 0.5 hour down, add the 100ml hexane behind the suction filtration, under agitation add 2ml THF, normal-temperature reaction 2 hours, obtain particulate solid thing B component 10.53 grams through twice hexane wash and vacuum-drying, wherein contain Ti7.56% (weight), Mg19.78% (weight), tetrahydrofuran (THF) 13.82% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Comparative example 1
4.8 gram magnesium chlorides, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition, to react two hours in mixing speed 450rpm, temperature, add 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction 1 hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature 1 hour, the elimination mother liquor through toluene and twice washing of hexane after drying, obtains containing the solids A of magnesium and titanium.
10 gram solids A are joined in another reactor, add 90ml iso-pentane, 0.3 gram titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, normal temperature reacted 1 hour down, filter solution, add the 90ml iso-pentane again, 3.5 the aluminium diethyl monochloride solution reaction of ml volumes concentration 26.43% 1 hour obtains particulate solid thing B component 12.1 grams through evaporation drying, wherein contains Ti1.66% (weight), Mg10.98% (weight), tetrahydrofuran (THF) 46.77% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.Measure the granularity of catalyzer and polymkeric substance respectively, the results are shown in Table 2 and 3.
Comparative example 2
4.8 gram magnesium chlorides, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition, to react two hours in mixing speed 450rpm, temperature, add 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction 1 hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature 1 hour, the elimination mother liquor through toluene and twice washing of hexane after drying, obtains containing the solids A of magnesium and titanium.
10 gram solids A are joined in another reactor, add 90ml iso-pentane, 0.3 gram titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, normal temperature reacted 1 hour down, filter solution, add the 90ml iso-pentane again, 10 milliliters of silicon tetrachlorides reacted 1 hour at normal temperatures, obtained particulate solid thing B component 10.5 grams through evaporation drying, wherein contained Ti1.72% (weight), Mg12.03% (weight), tetrahydrofuran (THF) 42.87% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.Measure the granularity of catalyzer and polymkeric substance respectively, the results are shown in Table 2 and 3.
The polymerization result of table 1 embodiment and comparative example
| Embodiment | Active (gPE/gcat) | BD(g/cm 3) | The content (Wt%) of the following fine powder of 150 μ m | MI (g/10min) |
| Embodiment 1 | 9218 | 0.381 | 3.2 | 1.56 |
| Embodiment | Active (gPE/gcat) | BD(g/cm 3) | The content (Wt%) of the following fine powder of 150 μ m | MI (g/10min) |
| Embodiment 2 | 15361 | 0.373 | 2.5 | 0.48 |
| Embodiment 3 | 13476 | 0.423 | 3.8 | 0.65 |
| Embodiment 4 | 14359 | 0.416 | 0.9 | 1.88 |
| Embodiment 5 | 12644 | 0.387 | 2.0 | 0.82 |
| Comparative example 1 | 7526 | 0.352 | 5.3 | 1.73 |
| Comparative example 2 | 6869 | 0.362 | 7.5 | 2.56 |
Table 2 embodiment 1 distributes relatively with the polymer particle size of comparative example 1 and comparative example 2
| ＞800μm | ～350μm | ～150μm | ～75μm | ＜75μm | |
| Embodiment 1 | 88.3 | 9.4 | 1.2 | 2.4 | 0.8 |
| Comparative example 1 | 6.5 | 60.7 | 27.5 | 3.2 | 2.1 |
| Comparative example 2 | 7.8 | 55.6 | 29.1 | 5.2 | 2.3 |
Table 3 embodiment 1 distributes relatively with the catalyst grain size of comparative example 1 and comparative example 2
| D10μ | d50μ | d90μ | |
| Embodiment 1 | 14.82 | 28.67 | 45.22 |
| Comparative example 1 | 4.67 | 20.56 | 32.43 |
| Comparative example 2 | 5.24 | 19.41 | 33.15 |
The size-grade distribution of the polymer powders that is obtained by highly active ingredient of solid catalyst of the present invention is very concentrated, and fine powder content is few, the tap density height.Be suitable for the slurry polymerization or the vapour phase polymerization of ethene, be specially adapted to the gas fluidized-bed process of catalyzer with the charging of slurries form.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a catalyst component that is used for vinyl polymerization or copolymerization is characterized in that, it is a kind of titaniferous solids, and the compound and at least a electron donor compound of at least a transition metals Ti in the load; Described titaniferous solids by using dialkoxy magnesium and transition metal titanium compound react in the presence of inert diluent, and described inert diluent is hexane, heptane or toluene, and in every mole of dialkoxy magnesium, the transition metal titanium compound is 2～20 moles; The compound of described transition metals Ti is titanium tetrachloride, trichlorine ethanolato-titanium or titanous chloride; Described electron donor compound is selected from aliphatic ether, cyclic aliphatic ether or aliphatic ketone.
2. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that described dialkoxy magnesium is a kind of in magnesium methylate, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, oxyethyl group methoxy base magnesium, oxyethyl group propoxy-magnesium, the butoxy magnesium ethylate or their mixture.
3. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 2 is characterized in that, described dialkoxy magnesium is diethoxy magnesium or dipropoxy magnesium.
4. according to any described catalyst component that is used for vinyl polymerization or copolymerization of claim 1-3, it is characterized in that also contain at least a activator, the general formula of described activator compound is AlR
cX
dH
e, R is C in the formula
1～C
14Saturated hydrocarbyl, X is a halogen, d is 0,1 or 2, e is 1 or 0, c+d+e=3.
5. any described method that is used for the catalyst component of vinyl polymerization or copolymerization of preparation claim 1-4 is characterized in that, comprises the steps:
1) preparation of titaniferous solids: dialkoxy magnesium under the situation that has inert diluent to exist, is obtained with the transition metals Ti compound effects;
2) in the presence of described electron donor compound, after titaniferous solids and the reaction of transition metal titanium compound.
6. according to the described preparation method who is used for the catalyst component of vinyl polymerization or copolymerization of claim 5, it is characterized in that step 2) reaction after, be AlR with general formula again
cX
dH
eActivator compound carry out activation treatment.
7. according to claim 5 or the 6 described preparation methods that are used for the catalyst component of vinyl polymerization or copolymerization, it is characterized in that in every mole of dialkoxy magnesium, inert diluent is 0～100 mole in the step 1), the transition metal titanium compound is 2～20 moles; Step 2) in every mole of dialkoxy magnesium compound, titanium compound is 0.3～20 mole in; Electron donor is 0.01～10 mole; 0.1～10 mole in activator.
8. according to the described preparation method who is used for the catalyst component of vinyl polymerization or copolymerization of claim 7, it is characterized in that step 2) in every mole of dialkoxy magnesium compound, titanium compound is 0.5～10 mole; Electron donor is 0.01～1mol; Activator is 0.1～5 mole.
9. catalyzer that contains any described catalyst component of claim 1-4, it is characterized in that, it is formed by the reaction of described catalyst component and alkylaluminium cpd, and the ratio between catalyst component and the alkylaluminium cpd with the molar ratio computing of titanium and aluminium is: 1: 5～100.
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|---|---|---|---|
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|---|---|---|---|
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| TWI735673B (en) * | 2016-10-03 | 2021-08-11 | 日商東邦鈦股份有限公司 | Solid catalyst component for olefin polymerization, method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene copolymer, and propylene copolymer |
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