CN1151183C - Spherical catalyst components used for polymerization or copolymerization of olefin and its catalyst - Google Patents
Spherical catalyst components used for polymerization or copolymerization of olefin and its catalyst Download PDFInfo
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Abstract
The present invention relates to a spherical catalyst component, a catalyst thereof and application thereof. The catalyst component comprises at least one titanium compound and at least one electron donor compound which are loaded on a magnesium chloride alcohol compound. The average diameter of a particle of the catalyst component is between 10 mu m and 200 mu m, the surface area of the particle of the catalyst component is greater than 300m<2>/g, and the porosity of the particle of the catalyst component is from 0.3 ml/g to 0.6 ml/g. The pore diameter distribution comprises at least 60% of pores, and the radii of the pores are smaller than 100*, wherein the mol ratio of alcohol to magnesium chloride in the magnesium chloride alcohol compound is from 2.0 to 3.6.
Description
The present invention relates to a kind of spherical catalyst component that is used for olefinic polymerization or copolymerization and reach the catalyzer that obtains thus, and it is at alpha-olefin CH
2Application in the polyreaction of=CHR and composition thereof, wherein R is the alkyl of hydrogen or 1～12 carbon atom.
Introduce in industrial production with the magnesium halide is that the catalyzer of carrier can be simplified polyolefinic production technique greatly.Particularly can obtain the catalyzer of form of spherical particles, this catalyzer can be produced similar to catalyst shape, has good fluidity, higher bulk density, even need not the polymkeric substance of granulation.
Example with catalyzer of this may command polymer morphology once had narration in USP 4399054.Catalyst component is by with MgCl in this patent
2The adducts that forms with about 3 mol of alcohol is the starting raw material preparation, with TiCl
4Before the reaction, the content of alcohol in the adducts is reduced to 2.5～2 moles, it is 0.3～0.4 centimetre that the catalyst component that this method makes presents porosity
3/ gram, mean pore size is between 15～20 .But this catalyst component is when being used for olefinic polymerization, and catalyst efficiency and orientation property are all relatively poor.
Disclose a kind of spherical catalyst component of olefinic polymerization in Chinese patent 90104123, it contains and is stated from Magnesium Chloride Anhydrous (MgCl
2) on titanium compound, also can contain electron donor.The surface-area of this catalyst component is 20～250 centimetres
2/ gram, porosity is 0.25～0.5 centimetre
3/ gram, pore size distribution are that its radius of hole of at least 50% is greater than 100 .This component is with MgCl
2Form adducts with about 3 mol of alcohol, at itself and TiCl
4Before the reaction, the pure content in the adducts is reduced to 0.2～2mol/molMgCl
2
In Chinese patent 930122677, also narrated another anhydrous MgCl
2Load TiCl
4The spherical catalyst component, its surface-area is 30～100m
2/ g, porosity is greater than 1 centimetre
3/ gram, pore size distribution are that at least 30% hole has mean radius greater than 10000 .The preparation method of its ball type carrier is similar to 90104123, has just carried out further ground dealcoholysis operation, the pure content of adducts is reduced to be not more than 1.0mol/molMgCl
2
Also narrated the spherical catalyst of the magnesium-supported titanium compound of a kind of anhydrous chlorides of rase in the Chinese patent 93102795, X-ray spectrum wherein, at 2 θ is that diffraction peak appears in 15 ° of angles, is 35 ° at 2 θ and diffraction peak do not occur, and replaced by the dizzy of maximum strength from 28 °～36 ° of angles.Also point out magnesium chloride alcohol adduct ball type carrier in the specification sheets simultaneously, need not to be directly used in synthetic catalyst through the dealcoholysis operation.But in its embodiment, still can exist the loss of alcohol in the forming process of alcohol adduct, and in the preparation process of catalyst spherical component, used a large amount of titanium tetrachlorides that the alcohol adduct carrier is handled, therefore in industrial production, the cost of catalyzer is improved greatly, and easily brought serious atmospheric pollution.And the catalyzer by its this method preparation is when being applied to propylene polymerization, and activity is lower, is generally less than 40KgPP/gCat (70 ℃, 2 hours, mass polymerization).
Now have been found that by controlledly directly acting on of adopting that alcohol and magnesium chloride form with an amount of titanium compound without the alcohol adduct of dealcoholysis, can obtain having spherical catalyst component high activity and stereospecificity, that be used for alpha-olefine polymerizing, and when the copolymerization that is used for alpha-olefin, make comonomer distribution even, produce the good spherical polymer of particle form.
Catalyst component of the present invention is a spheroidal particle, and it comprises at least a titanium compound and at least a electron donor compound that is carried on the magnesium chloride alcohol adduct, and the average diameter of particles of this catalyst component is between 10～200 μ m, and surface-area is greater than 300m
2/ g, porosity is 0.3～0.6ml/g, pore size distribution is that its pore radius of hole of at least 60% is less than 100 , its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and be occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ, the alcohol in the wherein said magnesium chloride alcohol adduct and the mol ratio of magnesium chloride are 2.0～3.6.
Titanium content is 1～4wt% in this catalyst component, is preferably 1.5～3wt%; The content of electron donor is 5～16wt%, is preferably 6～12wt%.
Surface-area of the present invention and porosity adopt the B.E.T. method to measure; Pure content in the alcohol adduct is measured with thermogravimetry (TGA); Measure the X-ray spectrum of spherical catalyst component, adopt copper anticathode and K alpha-ray to write down its spectrogram.
It is worthy of note that spherical catalyst component of the present invention has higher surface area, all greater than 300m
2/ g is preferably 300～400m
2/ g, the best is 300～360m
2/ g, therefore resulting catalyzer is used for olefinic polymerization and has very high activity, the pore radius of this spherical catalyst grain fraction is less simultaneously, wherein pore size distribution is that its pore radius of hole of at least 60% is less than 100 , make the catalyzer of its preparation have very high intensity, be difficult for broken at polymerization process.
Described magnesium chloride alcohol adduct is with C
1～C
4Low-carbon alcohol and magnesium chloride, be to mix in 2.0: 1～3.6: 1 in molar ratio, can in inert solvent medium, carry out, quick cooling after fusion under the heating, melt temperature is preferably 100～135 ℃, obtains containing a kind of alcohol adduct spheroidal particle that contains 2.0～3.6 moles of alcohol per mole magnesium chlorides.The magnesium alkoxide mol ratio of carrier is 2.0～3.6, is preferably 2.4～3.0.Unlike the prior art be this spherical magnesium chloride alcohol adduct carrier, in preparation process, do not adopt any dealcoholation treatment, thus alcohol content can be higher.In actual use, do not need sometimes above-mentioned alcohol adduct is carried out drying, and directly use the preparation catalyzer, thereby simplified preparation technology greatly with the form of suspension.
Described C
1～C
4Low-carbon alcohol comprise methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
The general formula of described titanium compound is: TiX
n(OR)
4-n, R is C in the formula
1～C
20Alkyl, be preferably normal-butyl, isobutyl-, 2-ethylhexyl, n-octyl and phenyl; X is a halogen, and n is 1～4.Concrete titanium compound can be selected titanium tetrahalide, particularly titanium tetrachloride for use; Trichlorine titanium alkoxides, particularly trichlorine butoxy and Trichlorophenoxy titanium; Four titan-alkoxides, particularly four titanium butoxide, purity titanium tetraethoxide.
Described electron donor compound is selected from alkyl, cycloalkyl or the aryl ester of phthalic acid.For example: diethyl phthalate, dipropyl phthalate, diisobutyl phthalate (DIBP), n-butyl phthalate (DNBP), diamyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate (DOP); Be preferably diisobutyl phthalate (DIBP) or n-butyl phthalate (DNBP).
Spherical catalyst component of the present invention can prepare as follows:
1, the preparation of spherical alcohol adduct carrier:
(1) generation of alcohol adduct and fusion: with inert solvent, for example white oil is a medium, makes Magnesium Chloride Anhydrous and C
1～C
4Low-carbon alcohol according to the proportioning of 2.0～3.6mol alcohol/1.0m0l magnesium chloride, 100 ℃～135 ℃ following frit reactions;
(2) dispersion of alcohol adduct: with the reactant transfer of above-mentioned reaction gained to being preheated in 110 ℃～135 ℃ the methyl-silicone oil medium; Stirred 5～15 minutes with 2000～5000 rev/mins rotating speeds; Wherein selecting viscosity preferably for use is the methyl-silicone oil of 200～500 centipoises (20 ℃), and consumption is 8～15ml/gMgCl
2
(3) chilling solidifying formation: be 30～60 pipe flow with length-to-diameter ratio with 100～500ml/min, above-mentioned height is stirred scattered mixed solution transfer in advance in the diluent medium that is cooled to-25 ℃～35 ℃, stirred 15～30 minutes with 200～500 rev/mins rotating speeds; Thinner can adopt alkane solvent, for example hexane, heptane etc., and the volume ratio of thinner and mixed solution is 3～6: 1;
(4) filter, wash dry: behind chilling, filter out particulate solid the suspension of gained; At room temperature wash this particulate matter with thinner, vacuumize under 30 ℃～50 ℃ and be drying to obtain ball type carrier.Also can add a certain amount of thinner after having washed, (concentration of carrier is 0.6～2.5g/10ml) in the suspension, makes carrier be directly used in the synthetic of catalyst component with the form of suspension to be made into carrier suspension.
2, the preparation of spherical catalyst component:
Spherical alcohol adduct carrier is added thinner formulated suspension (dilution dosage is 8～15ml/g carrier), or directly get a certain amount of above-mentioned carrier suspension that stirs for preparing, (10 ℃～-30 ℃) drip an amount of titanium compound through the inert solvent dilution at low temperatures, and maintain low-temp reaction after for some time, progressively be warming up to 80～130 ℃ then, adding electron donor compound and titanium compound again is further processed the solids of gained, also can be after titanium compound be handled, handle with electron donor again, at last after filtration, washing, obtain spherical catalyst after the drying.
It is worthy of note when spherical alcohol adduct carrier and titanium compound and electron donor reaction, preferably adopt with excessive spherical alcohol adduct carrier and react with the form that a spot of titanium compound contacts gradually, titanium compound can be evenly distributed on the alcohol adduct carrier, and also outbalance of the consumption of titanium compound, be generally 2～6ml titanium compound/g carrier, the minimizing of titanium compound consumption not only can reduce the cost of catalyzer and improve environmental pollution, and the more important thing is that to make the particle form of gained catalyst component better, activity of such catalysts is higher when being used for olefinic polymerization.
A kind of catalyzer that is used for olefinic polymerization comprises: the reaction product of spherical catalyst component of the present invention and aluminum alkyls.Alkylaluminium cpd is preferably the employing trialkyl aluminium compound, and for example: triethyl aluminum, three n-butylaluminum or triisobutyl aluminium, its consumption are 50～1000 to be advisable with the Al/Ti mol ratio generally.When being used for the tactic polymerization of alkene, can also add that to be selected from general formula be R
1R
2Si (OR)
2Silicoorganic compound, R wherein
1And R
2Be same to each other or different to each other, be C
1～C
20Alkyl, cycloalkyl or aryl, R is the alkyl that contains 1～4 carbon atom.Particular compound as: cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane or dicyclopentyl dimethoxyl silane, its consumption generally is advisable with Al/Si mol ratio 5～30.
Catalyzer of the present invention is applicable to that preparation has good flowability, high apparent density and form of spherical particles alkene (being total to) polymkeric substance of anti-mechanical property.The mean diameter of polymer beads is 50～3000 μ m.
Surprisingly, catalyzer of the present invention has high activity when being used for olefinic polymerization, during especially for preparation crystalline alfon and propylene-ethylene copolymers, its activity can reach above (70 ℃ of 60～100KgPP/gCat, 2 hours, mass polymerization).And when being used for the tactic polymerization of alkene, the degree of isotacticity of polymkeric substance is higher, and for example polyacrylic degree of isotacticity can be greater than 97.5%.Simultaneously, the hydrogen response of this catalyzer is also fine.
Because this catalyzer has high activity, thereby reduces greatly with the residual quantity of catalyzer and promotor in the polymkeric substance of its preparation, makes every performance of polymeric articles better.
It is worthy of note the multipolymer of catalyzer particularly suitable of the present invention and preparation propylene and other alkene.
Embodiment 1:
1, the preparation of spherical alcohol adduct carrier, step is as follows:
(1) generation of alcohol adduct and fusion: with the white oil is medium, adds 47.6g magnesium chloride and 59.8g ethanol (mol ratio of ethanol and magnesium chloride is 2.6/1), and the white oil consumption is 286ml, and the viscosity of white oil is 30 centipoises (20 ℃), reacts 2 hours down at 125 ℃.
(2) dispersion of alcohol adduct: the molten polyol of above-mentioned reaction gained and the mixed solution of thing and white oil are transferred in the methyl-silicone oil medium that is preheated to 125 ℃; The viscosity of methyl-silicone oil is 300 centipoises (20 ℃), and the consumption of methyl-silicone oil is 572ml; Stirred 12 minutes with 2400 rev/mins rotating speeds.
(3) chilling solidifying formation: be 45 pipe flow with length-to-diameter ratio, above-mentioned height stirred scattered mixed solution transfer in advance in the hexane medium that is cooled to-30 ℃, stirred 15 minutes with 300 rev/mins rotating speeds with 300ml/min; The volume ratio of hexane and mixed solution is 4: 1.
(4) filter, wash dry: behind chilling, filter out particulate solid the suspension of gained; At room temperature wash this particulate matter with hexane, the hexane consumption is 5～10ml/g particulate matter, washs altogether five times; Vacuumize drying under 30 ℃～50 ℃, obtained the 105g ball type carrier, record with the TGA thermogravimetry that the mol ratio of ethanol and magnesium chloride is 2.6 in the prepared ball type carrier.
2, the preparation of spherical catalyst component: with the alcohol adduct carrier 7g of above-mentioned preparation add join in the 80ml hexane suspension, be cooled to-20 ℃; Add 20ml hexane and 20ml TiCl
4Mixed solution, be warming up to 20 ℃, 20 ℃ keep 30min after, filter liquid; Add 100ml TiCl
4, be warming up to 100 ℃, when rising to 40 ℃, temperature adds 1.4ml DNBP, filter liquid at 100 ℃ while hot after keeping 2 hours; Add 100ml TiCl again
4, be warming up to 120 ℃, filter liquid at 120 ℃ after keeping 2 hours; With hexane solids is washed 3 times down at 50 ℃～60 ℃, at room temperature wash 2 times, each hexane consumption is 60ml.Under 40 ℃, vacuumize dry spherical solids 2 hours then, obtain 4.35g spherical catalyst component.
The specific surface that records the spherical catalyst component with the B.E.T. method is 330m
2/ g, porosity is 0.35ml/g, pore size distribution is that its pore radius of hole of 63% is less than 100 ; Catalyst Ti content is 2.8% (weight), and DNBP content is 9.6% (weight); Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ.
3, propylene polymerization:
At 5 liters of autoclaves, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and 8.5mg such as the above-mentioned prepared solid spherical catalyst component of 1ml cyclohexyl methyl dimethoxy silane (CHMMS) under the room temperature in the stream of nitrogen gas.Introduce the hydrogen of 1.7NL (standard liter) and the liquid propene of 1.5Kg, be warming up to 70 ℃ of polyreactions after 2 hours, stop stirring, remove unpolymerized propylene monomer, with the still internal cooling to room temperature.
From autoclave, draw off the 540g polypropylene, this polyacrylic degree of isotacticity (I.I.)=98.6%, melt index (MFR)=3.0g/10min.Activity of such catalysts is 63.5Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.46g/ml.Wherein the polymkeric substance degree of isotacticity is measured with boiling n-heptane extraction process (GB-2412-80).
The comparative example 1:
The preparation of l, spherical alcohol adduct carrier: carry out the preparation of spherical alcohol adduct carrier according to the method for embodiment 1, obtain the 102g ball type carrier, record with the TGA thermogravimetry that the mol ratio of ethanol and magnesium chloride is 2.62 in this ball type carrier.
2, the preparation of spherical catalyst component: in reaction flask, add 100mlTiCl
4, be cooled to-20 ℃, at-20 ℃ of alcohol adduct carriers that add the above-mentioned preparation of 7g down; Slowly be warming up to 100 ℃ afterwards, and in the time of 40 ℃, add 1.4mlDIBP, filter liquid while hot after keeping 2 hours at 100 ℃; Add 100mlTiCl again
4, be warming up to 120 ℃, filter liquid at 120 ℃ while hot after keeping 2 hours; According to the method for embodiment 1 with solids wash, drying, obtain 4.2g spherical catalyst component.
3, propylene polymerization: identical with embodiment 1, just the add-on of catalyzer is 9.2mg.Obtain the 382g polypropylene, this polyacrylic degree of isotacticity (I.I)=97.1%, melt index (MFR)=5.9g/10min.Activity of such catalysts is 41.5Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.47g/ml, and polymer beads is rough, and fragmentation is arranged.
Embodiment 2:
1, the preparation of alcohol adduct carrier is with embodiment 1, just after carrier wash, no longer vacuumizes drying, but adding 1100ml anhydrous hexane is made into carrier suspension, suspension concentration be the 0.95g carrier/
10ml suspensionSampling records that the mol ratio of ethanol and magnesium chloride is 2.6 in the solid carrier after the drying.
2, get above-mentioned carrier suspension 80ml, stirring is cooled to-20 ℃, and the preparation of remaining spherical catalyst component obtains 4.5g solid spherical catalyst component with embodiment 1.
The specific surface that records spherical catalyst with the B.E.T. method is 316m
2/ g, porosity is 0.38ml/g, pore size distribution is that its pore radius of hole of 80% is less than 100 ; Catalyst Ti content is 2.6% (weight), and DNBP content is 8.0% (weight).Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ.
3, propylene polymerization: identical with embodiment 1, just the add-on of solid spherical catalyst component is 8.6mg.Obtain the 594g polypropylene, this polyacrylic degree of isotacticity (I.I.)=98.5%, melt index (MFR)=5.4g/10min.Activity of such catalysts is 69.0Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.46g/ml.
Embodiment 3:
With embodiment 2, when difference spherical catalyst component prepares, just carry titanium and finish back TiCl
4Further treating processes change, promptly filter liquid while hot after keeping 2 hours at 100 ℃, add 50mlTiCl
4With the mixed solution of 50ml anhydrous hexane, rather than add pure TiCl
4, be warming up to 80 ℃ in 10 minutes, keep filtering liquid in 0.5 hour at 80 ℃; And then adding 100ml TiCl
4, be warming up to 120 ℃ in 0.5 hour, filter liquid at 120 ℃ after keeping 2 hours; Thereafter operation is identical with embodiment 2.Obtain 4.2g solid spherical catalyzer.
The specific surface that records spherical catalyst with the B.E.T. method is 332m
2/ g, porosity is 0.36ml/g, pore size distribution is that its pore radius of hole of 90% is less than 100 ; Catalyst Ti content is 2.45% (weight), and DNBP content is 8.8% (weight).Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ.
Propylene polymerization: identical with embodiment 1, just the add-on of solid spherical catalyst component is 7.6mg.Obtain the 564g polypropylene, this polyacrylic degree of isotacticity (I.I.)=97.8%, melt index (MFR)=6.4g/10min.Activity of such catalysts is 74.2Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.46g/ml.
Embodiment 4:
The preparation of alcohol adduct carrier, the preparation of ingredient of solid catalyst are all with embodiment 1, and difference is at the hexane that the alcohol adduct carrier of gained is adopted 50ml, rather than the 80ml formulated suspension, and this suspension is cooled to-20 ℃, add 50ml TiCl
4, but not 20ml hexane and 20m1 TiCl
4Mixed solution, all the other are operated with embodiment 1, obtain 4.3g solid spherical catalyst component.
The specific surface that records the spherical catalyst component with the B.E.T method is 343m
2/ g, porosity is 0.56ml/g, pore size distribution is that its pore radius of hole of 90% is less than 100 ; Titanium content is 2.7% (weight) in the catalyzer, and DNBP content is 10.1% (weight).Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ.
Propylene polymerization is identical with embodiment 1, and just the add-on of solid spherical catalyst component is 8.4mg.Obtain the 586g polypropylene, this polyacrylic degree of isotacticity (I.I.)=97.8%, melt index (MFR)=5.1g/10min.Activity of such catalysts is 69.8Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.45g/ml.
Embodiment 5:
The preparation of spherical alcohol adduct carrier, the preparation of ingredient of solid catalyst be all with embodiment 1, difference be 100 ℃ keep filtered liquid in 2 hours after, the 100mlTiCl of adding
4Change into and add 20mlTiCl
4With the mixed solution of 80ml toluene, holding temperature thereafter changes 110 ℃ into by 120 ℃, and all the other operations are identical with embodiment 1, obtain 4.0g solid spherical catalyst component.
The specific surface that records spherical catalyst with the B.E.T. method is 312m
2/ g, porosity is 0.43ml/g, pore size distribution is that its pore radius of hole of 78% is less than 100 ; Catalyst Ti content is 1.9% (weight), and DNBP content is 6.8% (weight).Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ.
Propylene polymerization is identical with embodiment 1, and just the add-on of solid spherical catalyst component is 8.0mg.Obtain the 556g polypropylene, this polyacrylic degree of isotacticity (I.I.)=98.0%, melt index (MFR)=4.3g/10min.Activity of such catalysts is 69.5Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.48g/ml.
Embodiment 6:
The preparation of spherical alcohol adduct carrier, the preparation of ingredient of solid catalyst are all with embodiment 1, and difference is that DNBP is changed DIBP, and all the other operations are identical, obtain 4.2g solid spherical catalyst component.
The specific surface that records the spherical catalyst component with the B.E.T. method is 308m
2/ g, porosity is 0.42ml/g, pore size distribution is that its pore radius of hole of 75% is less than 100 ; Catalyst Ti content is 2.1% (weight), and DIBP content is 7.8% (weight).Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ.
Propylene polymerization is identical with embodiment 1, and just the add-on of solid spherical catalyst component is 8.7mg.Obtain the 520g polypropylene, this polyacrylic degree of isotacticity (I.I.)=97.6%, melt index (MFR)=5.3g/10min.Activity of such catalysts is 59.8Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.45g/ml.
Embodiment 7:
Propylene polymerization: the ingredient of solid catalyst that adopts embodiment 1 gained, add-on is 8.4mg, other polymerizing conditions are with embodiment 1, only cyclohexyl methyl dimethoxy silane is changed into the dicyclopentyl dimethoxyl silane (DCPMS) of identical mole number, obtain the 563g polypropylene, this polyacrylic degree of isotacticity (I.I.)=99.4%, melt index (MFR)=0.8g/10min.Activity of such catalysts is 67.0Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.46g/ml.
Embodiment 8:
Propylene polymerization: adopt the prepared spherical solid catalyst component of embodiment 1, polymerizing condition is with embodiment 1, difference is that the add-on of cyclohexyl methyl dimethoxy silane (CHMMS) is 0.5mmol, the add-on of spherical solid catalyst component is 7.6mg, introduces the hydrogen of 22NL and the liquid propene of 1.3Kg.Polymerization obtains the 382g polypropylene, this polyacrylic degree of isotacticity (I.I.)=96.3%, melt index (MFR)=136g/10min.Activity of such catalysts is 50.2Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.45g/ml.
Embodiment 9:
The preparation of propylene-based block copolymer: use the prepared spherical solid catalyst component of embodiment 1, and carry out the propylene homopolymerization earlier according to the method for embodiment 1, the add-on of ingredient of solid catalyst is 8.9mg., open breather valve and reduce to normal pressure after 2 hours 70 ℃ of following polyreactions, carry out the copolyreaction of ethene and propylene after the step-down as follows.
(mol ratio of each component is C in the gas mixture the gas mixture that is made into ethene, propylene and hydrogen in advance
= 2/ C
= 3/ H
2=1/1/0.1), feed in the reactor, by regulating the aperture of intake valve, make the pressure in the reactor remain on 0.1Mpa, 75 ℃ are reacted 30min, cooling afterwards, step-down, discharging down.
Obtain the 628g polymkeric substance, activity of such catalysts is 70.5Kg polypropylene/g ingredient of solid catalyst; Polymer stacks density is 0.47g/ml, polymer melt index (MFR)=3.0g/10min, and ethylene content is 8.9% (wt) in the polymkeric substance.
Claims (10)
1, a kind of spherical catalyst component that is used for olefinic polymerization, it contains at least a titanium compound and at least a electron donor compound that is carried on the magnesium chloride alcohol adduct, the average diameter of particles of this spherical catalyst component is between 10～200 μ m, and surface-area is greater than 300m
2/ g, porosity is 0.3～0.6ml/g, pore size distribution is that its pore radius of hole of at least 60% is less than 100 ; Its X-ray spectrum is that diffraction peak does not appear in 14.95 ° of angles and 35 ° of angles at 2 θ, and is occur maximum strength between 30 ° to the 36 ° angles dizzy at 2 θ, and the alcohol in the wherein said magnesium chloride alcohol adduct and the mol ratio of magnesium chloride are 2.0～3.6.
2, spherical catalyst component according to claim 1 is characterized in that, described magnesium chloride alcohol adduct is with C
1～C
4Low-carbon alcohol and magnesium chloride be to mix in 2.0: 1～3.6: 1 in molar ratio, quick cooling behind heating and melting obtains containing the spheroidal particle of 2.0～3.6 moles of alcohol per mole magnesium chlorides.
3, spherical catalyst component according to claim 1, it is characterized in that, described magnesium chloride alcohol adduct is to be to mix in 2.4: 1～3.0: 1 in molar ratio with alcohol and magnesium chloride, and quick cooling behind heating and melting obtains containing the spheroidal particle of 2.4～3.0 moles of alcohol per mole magnesium chlorides.
4, spherical catalyst component according to claim 1 is characterized in that, described C
1～C
4Low-carbon alcohol be methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
5, spherical catalyst component according to claim 1 is characterized in that, the general formula of described titanium compound is: TiX
n(OR)
4-n, R is C in the formula
1～C
20Alkyl, X is a halogen, n is 1～4.
6, spherical catalyst component according to claim 1 is characterized in that, described titanium compound is titanium tetrachloride, trichlorine titanium butoxide, Trichlorophenoxy titanium, four titanium butoxide or purity titanium tetraethoxide.
7, spherical catalyst component according to claim 1 is characterized in that, described electron donor compound is selected from alkyl, cycloalkyl or the aryl ester of phthalic acid.
8, spherical catalyst component according to claim 1, it is characterized in that described electron donor compound is diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, n-butyl phthalate, diamyl phthalate, dihexyl phthalate, diheptyl phthalate or dioctyl phthalate (DOP).
9, a kind of olefin polymerization catalysis, contain following component:
(1) the described spherical catalyst component of claim 1;
(2) aluminum alkyls; With
(3) being selected from general formula is R
1R
2Si (OR)
2Silicon compound, R wherein
1And R
2Be same to each other or different to each other, be C
1～C
20Alkyl, cycloalkyl or aryl, R is the alkyl that contains 1～4 carbon atom;
Wherein the Al/Ti mol ratio is 50～1000, Al/Si mol ratio 5～30.
10, the application of the described catalyzer of claim 9 in olefinic polymerization or copolymerization.
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|---|---|---|---|
| CNB001092162A CN1151183C (en) | 2000-06-15 | 2000-06-15 | Spherical catalyst components used for polymerization or copolymerization of olefin and its catalyst |
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| CNB001092162A CN1151183C (en) | 2000-06-15 | 2000-06-15 | Spherical catalyst components used for polymerization or copolymerization of olefin and its catalyst |
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| CN1330086A CN1330086A (en) | 2002-01-09 |
| CN1151183C true CN1151183C (en) | 2004-05-26 |
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| US20100099833A1 (en) | 2006-04-06 | 2010-04-22 | Xianzhi Xia | Magnesium halide complexes, catalyst components and catalysts for olefin polymerization prepared therefrom |
| CN100491458C (en) | 2006-04-20 | 2009-05-27 | 中国石油化工股份有限公司 | Method of preparing high-performance polypropylene composition |
| US9499569B2 (en) | 2009-07-15 | 2016-11-22 | China Petroleum & Chemical Corporation | Spherical magnesium halide adduct, a catalyst component and a catalyst for olefin polymerization prepared therefrom |
| ATE557044T1 (en) | 2009-08-13 | 2012-05-15 | China Petroleum & Chemical | CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND CATALYST THEREFOR |
| CN102020731B (en) * | 2009-09-10 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization and catalyst thereof |
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| CN102040692A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | High-isotacticity polybutylene-1 polymer and preparation method thereof |
| SG10201500468RA (en) | 2010-01-22 | 2015-03-30 | China Petroleum & Chemical | Propylene homopolymer having high melt strength and preparation method thereof |
| CN103059173B (en) * | 2011-10-18 | 2015-07-22 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN103772551B (en) * | 2012-10-23 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of ethylene polymerization catalytic component and catalyst thereof |
| CN104341543B (en) * | 2013-08-02 | 2017-01-25 | 中国石油天然气股份有限公司 | Preparation method of propylene copolymer with low ethylene content and wide molecular weight distribution |
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| CN104610478B (en) * | 2013-11-05 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of catalyst for olefinic polyreaction |
| CN104610474B (en) * | 2013-11-05 | 2017-03-22 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization reaction |
| CN103936903B (en) * | 2014-03-07 | 2016-10-26 | 中石化上海工程有限公司 | The method producing high-performance polypropylene |
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| US10988553B2 (en) | 2016-06-23 | 2021-04-27 | China Petroleum & Chemical Corporation | Catalyst pre-contact device for continuous polymerization of olefins and method for catalyst pre-contact |
| KR102185631B1 (en) | 2016-08-19 | 2020-12-04 | 인스티튜트 오브 케미스트리, 차이니즈 아카데미 오브 사이언시즈 | Polyethylene with ultra high molecular weight and ultra fine particle diameter and its manufacturing method and application |
| ES2969670T3 (en) | 2016-09-23 | 2024-05-21 | China Petroleum & Chem Corp | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| WO2018054362A1 (en) | 2016-09-23 | 2018-03-29 | 中国石油化工股份有限公司 | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| BR112020001201B1 (en) | 2017-07-19 | 2023-03-21 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | ZIEGLER-NATTA CATALYST SYSTEM FOR OLEFIN POLYMERIZATION, SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND OLEFIN POLYMERIZATION PROCESS |
| EP3868796A4 (en) | 2018-10-19 | 2022-07-13 | China Petroleum & Chemical Corporation | Catalyst component and catalyst for olefin polymerization, and application thereof |
| EP4006061A4 (en) | 2019-07-26 | 2023-08-09 | China Petroleum & Chemical Corporation | Catalyst system for olefin polymerization and use thereof |
| AU2021332812A1 (en) | 2020-08-27 | 2023-03-09 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | Polypropylene composition, preparation method therefor, and article made therefrom |
| CN114149523B (en) | 2020-09-05 | 2022-11-18 | 中国石油化工股份有限公司 | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof |
| TW202225217A (en) | 2020-10-15 | 2022-07-01 | 大陸商中國石油化工科技開發有限公司 | Propylene-butene copolymer, preparation method therefor and use thereof |
| CN114437263B (en) * | 2020-10-20 | 2023-12-08 | 中国石油化工股份有限公司 | Low-VOC low-odor polypropylene resin and preparation method and application thereof |
-
2000
- 2000-06-15 CN CNB001092162A patent/CN1151183C/en not_active Expired - Lifetime
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