CN102558398B - Method for preparing spherical magnesium chloride carrier - Google Patents
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- CN102558398B CN102558398B CN 201010613980 CN201010613980A CN102558398B CN 102558398 B CN102558398 B CN 102558398B CN 201010613980 CN201010613980 CN 201010613980 CN 201010613980 A CN201010613980 A CN 201010613980A CN 102558398 B CN102558398 B CN 102558398B
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Abstract
The invention discloses a method for preparing a spherical magnesium chloride carrier. The method comprises the following steps of: performing alcohol combination reaction on magnesium chloride and fatty alcohol (ROH), dispersing, quenching, solidifying and drying to obtain a carrier precursor, performing primary alcohol removal on the carrier precursor in inert airflow at the temperature of between 30 and 40 DEG C, heating to the temperature of between 41 and 55 EG C, performing secondary alcohol removal, and thus obtaining the spherical magnesium chloride and alcohol carrier. An olefin polymerization catalyst prepared from the carrier obtained after alcohol removal by the method has high catalytic activity, the granular size of the olefin polymerization catalyst is increased, and the fine powder quantity of the olefin polymerization catalyst is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of polyolefine solid catalyst carrier, specifically, is a kind of preparation method of spherical magnesium chloride carrier.
Background technology
With the magnesium chloride alcohol adducts as ball type carrier, itself and halogenated titanium and electron donor compound are carried out contact reacts can prepare the high-effective spherical olefins polymerizing solid catalyst component, relevant preparation method and condition all have description in CN85100997A, CN1039234, CN1358773A, CN1141303A, CN1552742A, CN1490340A.
When preparation magnesium chloride alcohol adducts, its alcohol/magnesium mol ratio is 2～4.But vigorous reaction occurs during for fear of the load halogenated titanium, cause that carrier ball breaks, affect the form of catalyzer, cause in polymerization process fine polymer powder more, the alcohol of magnesium chloride alcohol adducts solid/magnesium mol ratio should be controlled to be 1～3.Therefore, before Kaolinite Preparation of Catalyst, generally to carry out dealcoholation treatment to magnesium chloride alcohol adducts carrier.Has specific X-diffractogram through the carrier after dealcoholation treatment.
USP4,421,674 disclose a kind of preparation method of olefin polymerization catalysis.The method is dissolved in Magnesium Chloride Anhydrous and forms solution in alcohol, and then spraying drying in the nitrogen that flows, slough part alcohol, obtains containing the carrier of 1.5～20 quality % alcohol.In the X-diffraction spectrogram of carrier, locate to exist diffraction peak 8.15 ° of diffraction angle, 9.65 ° and 13.15 °.
EP0700936A discloses a kind of method for preparing olefin polymerization solid catalyst, wherein MgCl
2The preparation of EtOH adducts comprises the following steps: (1) preparation MgCl
2The mROH mixture, wherein R is C
1～C
10Alkyl, m is 3.0～6.0; (2) spraying-cooling mixture obtains a kind of solid adduct; (3) (2) are obtained adducts 35～50 ℃ of continuous dealcoholysis 4～20 hours under reduced pressure, making alcohol in adducts/magnesium mol ratio is 0.4～2.8: 1.This patent Fig. 3 demonstration, after dealcoholysis, the X-diffractogram of adducts is located without diffraction peak at 7～8 °, and highest peak is positioned at 8.8 ° to be located, and locates two weak peaks at 9.5～10 ° and 11～11.5 °.
It is that carrier prepares solid catalyst that CN1089622A adopts magnesium chloride and the adducts of alcohol.The method for preparing adducts is under the existence of inert solvent, adds in the magnesium chloride alcohol to form solution, obtains alcohol/magnesium mol ratio greater than 3 adducts, then 50～150 ℃ of nitrogen dealcoholysis, obtains alcohol/magnesium mol ratio and be 1.1 adducts carrier.
CN1037609C discloses a kind of catalyst component for olefinic polymerization and catalyzer, carries out dealcoholysis by magnesium chloride alcohol adducts solid is heated to 130 ℃ from 50 ℃, and obtaining alcohol/magnesium mol ratio is 0.2～2.0 carrier.
CN1038593C discloses a kind of method for preparing ethene (being total to) polymerization solid catalyst component.Form after the ethanolic soln impregnation of silica particle drying of carrier wherein with magnesium chloride, heating evaporation below 150 ℃ is deviate from the ethanol of part absorption, and the mol ratio that makes ethanol and magnesium chloride is 1.5～4.0.
CN1109067A discloses the preparation of a kind of spheric polypropylene catalyst and carrier thereof, uses water content to prepare adducts up to magnesium chloride and the ethanol synthesis of 5 quality %, then prepares the spherical solid catalyst component through dispersion, chilling curing and Separation and Recovery.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of spherical magnesium chloride carrier, the method for dealcoholized that this method is used can improve the active of catalyzer and reduce the fine powder content of polymkeric substance.
The preparation method of spherical magnesium chloride carrier provided by the invention, comprise that magnesium chloride and fatty alcohol roh are carried out alcohol closes reaction, the dry precursor carrier that gets after dispersion, chilling solidify, precursor carrier is carried out one section dealcoholysis at 30～40 ℃ in noble gas stream, then be warming up to 41～55 ℃ and carry out two sections dealcoholysis and obtain spherical magnesium chloride alcohol carrier.
The inventive method prepares adducts with alcohol and magnesium chloride, be solidified into ball through over-quenching, again the magnesium chloride alcohol adducts that obtains is carried out two sections dealcoholysis of fluidisation, olefin polymerization catalysis by gained carrier preparation after dealcoholysis, has higher catalyst activity, and the particle size of polymkeric substance increases, and the fine polymer powder amount reduces.
Description of drawings
Fig. 1 is the XRD figure of not carrying out the magnesium chloride alcohol carrier of nitrogen fluidisation dealcoholation treatment.
Fig. 2～Fig. 5 is the XRD figure with the magnesium chloride alcohol carrier of the inventive method dealcoholation treatment.
Embodiment
We are surprised to find that, for magnesium chloride alcohol adducts ball type carrier, through two sections dealcoholation treatment of fluidisation of the present invention, after dealcoholysis, the X-diffraction spectra of gained carrier is to have four diffracted rays between 5～10 ° at 2 θ, laying respectively at 6.1 ± 0.1 °, 7.5 ± 0.1 °, 9.0 ± 0.4 ° and 9.8 ± 0.1 ° locates, wherein, 7.5 ± 0.1 ° of diffracted intensities of locating increase along with the increase of dealcoholysis degree.
Fluidisation dealcoholysis of the present invention refers to and will treat the magnesium chloride alcohol adducts carrier of dealcoholysis, be that precursor carrier is placed in the dealcoholysis of noble gas stream, through high and low temperature two sections fluidisation dealcoholysis, obtain alcohol/magnesium mol ratio and be 2～3, preferred 2～2.8, more preferably 2.4～2.6 magnesium chloride alcohol adducts carrier.The specific surface area of described carrier is 10～30 meters
2/ gram, pore volume are 0.05～0.5 ml/g, and bulk density is 0.6～0.9 grams per milliliter.
The described one section dealcoholysis of the inventive method is carried out under the lesser temps of 30～40 ℃, and preferred 0.5～3.0 hour of time, two sections dealcoholysis are carried out under the comparatively high temps of 41～55 ℃, preferred 1～5 hour of time.The rare gas element preferred nitrogen that dealcoholysis is used, during dealcoholysis, nitrogen is 2.5～25 hours by the mass space velocity of precursor carrier
-1, preferred 5～15 hours
-1
The present invention uses alcohol and magnesium chloride to prepare the magnesium chloride alcohol adducts, and the R in described fatty alcohol roh is C
2～C
6Alkyl, preferred alcohol is ethanol.Described magnesium chloride and Fatty Alcohol(C12-C14 and C12-C18) carry out alcohol and close reaction in the blending agent that methyl-silicone oil and whiteruss form, alcohol closes magnesium chloride that reaction adds and the mol ratio of Fatty Alcohol(C12-C14 and C12-C18) is 1～6, and temperature of reaction is 110～130 ℃, preferred 2～4 hours of time.Preparation adducts magnesium chloride used can be Magnesium Chloride Anhydrous, can be also that water-content is lower than the magnesium chloride of 5 quality %.
Alcohol will further disperse the adducts that generates after closing reaction, described dispersion is alcohol to be closed reaction gained magnesium chloride alcohol adducts solution move in the blending agent that is comprised of methyl-silicone oil and whiteruss that is preheated to 110～130 ℃ and disperse, the volume ratio of blending agent and adduct solution preferred 1.2～2.0.
It is that after disperseing, the adduct solution of gained goes to balling-up in the unreactive hydrocarbons solvent of-30～-15 ℃ that chilling of the present invention solidifies, and the volume ratio of unreactive hydrocarbons solvent and adduct solution is 2.0～2.5.The preferred C of described unreactive hydrocarbons solvent
6～C
12Alkane.
Filter after the mixture that chilling obtains after solidifying is warmed up to room temperature naturally, the solids that leaches is used nitrogen drying with the inert solvent washing is rear under 50～150 ℃ of normal pressures or decompression, obtain spherical magnesium chloride support precursor.
In aforesaid method, alcohol closes reaction and disperses in blending agent used preferred 1: 1 of the volume ratio of methyl-silicone oil and whiteruss, preferred 50～600 centipoises of the viscosity that methyl-silicone oil is 20 ℃, preferred 30～50 centipoises of 20 ℃ of viscosity of whiteruss.
The carrier that chilling solidifies dry rear gained namely gets spherical magnesium chloride alcohol adducts carrier with fluidisation method for dealcoholized of the present invention dealcoholysis.
Method with magnesium chloride alcohol adducts carrier Kaolinite Preparation of Catalyst provided by the invention comprises the steps:
(1) ball type carrier is mixed by the amount of 3.0～6.0 liters of solvents of every kilogram of carrier with inert solvent, gained suspension is 30～60 by the Ti/Mg mol ratio, preferred 35～45 amount joins in advance and is chilled in the compound titanium solution with a Ti-halogen key at least of-20～0 ℃
(2) system slowly is warming up to 40～80 ℃, presses Mg/ internal electron donor mol ratio 3.0～15.0, preferred 5.0～10.0 amount adds internal electron donor, and 100～125 ℃ were reacted 1.5～4 hours, and filtered while hot is isolated solid particulate,
(3) pressing the Ti/Mg mol ratio is that 20～50 amount joins solid particulate in the compound titanium solution with a Ti-halogen key at least of preheating, stirs lower 100～125 ℃ of reactions 1～2 hour, and filtered while hot is isolated solid particulate,
(4) wash away chlorion free on particle with the unreactive hydrocarbons solvent of 50～70 ℃, dry in vacuum or 50～80 ℃ of nitrogen gas stream, obtain the spherical solid catalyzer.
In aforesaid method, it is Ti (OR) that described titanium compound of (1) step is selected from general formula
4-nX
nCompound, in formula, R is C
1～C
20Alkyl, X is halogen, n=1～4.The preferred titanium tetrachloride of described titanium compound, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, trichlorine one titanium butoxide, more preferably titanium tetrachloride.
The internal electron donor that described (2) added in the step is selected from the ester of general formula (I) and/or the ether of general formula (II), preferred diisobutyl phthalate.
General formula (I) and (II) in, R
1～R
4Be selected from respectively C
1～C
10Alkyl, aryl or aralkyl.
In above-mentioned method for preparing catalyst, (1) step and (3) step are respectively once carries titanium and secondary carries titanium, carries a titanium and preferably under agitation carries out, preferred 15～60 minutes of churning time.(4) step is C for the unreactive hydrocarbons solvent of washing catalyst
6～C
12Alkane, preferred hexane.
In the solid catalyst of the present invention's preparation, Mg content is 15～25 quality %, and titanium content is 1.0～5.0 quality %, and cl content is 50～70 quality %, preferred 6.0～20 quality % of the content of internal electron donor; The solid catalyst specific surface area is 100～500 meters
2/ gram, pore volume are 0.10～0.50 ml/g.
The catalyzer of the inventive method preparation is applicable to homopolymerization and the copolymerization of alkene, is preferred for homopolymerization and the copolymerization of propylene.
When catalyzer of the present invention is used for propylene polymerization and the promotor of its compatibility be alkylaluminium cpd, preferred triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride, triethyl aluminum most preferably, the promotor consumption is Al/Ti mol ratio 200～1500.
When catalyzer of the present invention is used for propylene polymerization, in order to obtain to have the polypropylene product of high isotactic, also need add external donor compound, external donor compound and internal electron donor compound can be the same or different.It is R that described external donor compound is selected from general formula
1R
2Si (OR)
2Silicon compound, preferred dimethoxydiphenylsilane or Cyclohexyl Methyl Dimethoxysilane, its consumption generally is advisable with Al/Si mol ratio 8～30, is preferably 15～25.
The temperature of reaction of carrying out olefinic polymerization with catalyzer of the present invention is 60～120 ℃, preferred 70～100 ℃, and pressure is 0.1～6.0MPa, preferred 0.4～2.0MPa.
Further illustrate the present invention below by example, but the present invention is not limited to this.
X-ray powder diffraction spectrum: adopt Rigaku DMAX/IIIA x-ray diffractometer to measure, condition determination: CuK α (λ=1.5418), pipe is pressed 35V, pipe stream 25mA, slit 0.3mm, 4 °/minutes of sweep velocitys are 2～70 ° of recording ray diffraction spectra.Analyzed sample grinds under nitrogen protection, compressing tablet, is placed in dry polyester plastics bag, 50 microns of polyester plastics bag thickness.
Water, pure content: adopt U.S. Auto TGA2950 thermal analyzer, carry out 10 ℃/minute of temperature rise rates in nitrogen atmosphere.
Mg content adopts aas determination.With concentrated nitric acid and a small amount of hydrofluoric acid dissolution analyte, heating, cooling after, quantitative with distilled water, use the PE-460 atomic absorption detecting.
Ti content adopts spectrophotometry.With sulfuric acid (volume ratio 1: 17) solution dissolving analyte, heating, cooling after, adding distil water adds the hydrogen peroxide of 1 30% to certain volume.Then use 721 spectrophotometer colorimetrics, measure absorbancy, the contrast standard curve obtains titanium content.
Surface tissue: specific surface area and pore volume adopt static nitrogen loading capacity method to measure.
Degree of isotacticity adopts the Soxhlet extraction method to measure.In round-bottomed flask, add the 200mL normal heptane, the polymer samples of handling well is put into extractor, be heated to boiling, make per hour extracting 20 ± 5 times of normal heptane, extracting 6h takes out oven dry, weighs, and calculates arithmetical av.
The measuring method of polypropylene apparent bulk density (B.D.) is: funnel is placed on funnel support, 100mL sample holder ware is placed under the funnel support base, adjusting hopper outlet and sample holder ware spacing is 10cm, till sample is poured into funnel to sample holder ware and filled with, claims its quality.Apparent bulk density is calculated as follows:
In formula, m
1Be the quality of sample and sample holder ware, g; m
2Be the quality of sample holder ware, g; 100 is the volume of sample holder ware, mL; B.D. be the apparent bulk density of sample, g/mL.
Example 1
Prepare spherical magnesium chloride carrier with the inventive method
(1) alcohol closes reaction
Magnesium chloride (water-content 2.65 quality %), 39mL (0.67mol) dehydrated alcohol, 110mL methyl-silicone oil, the 110mL whiteruss of 20 grams (0.21mol) are joined under nitrogen protection in the 500mL reaction flask that agitator and prolong are housed, be heated to 120 ℃ and stirred 3 hours.The viscosity that described methyl-silicone oil is 20 ℃ is 250 centipoises, and the viscosity that whiteruss is 20 ℃ is 30 centipoises.
(2) disperse
Alcohol is closed reaction gained solution move in the medium that is preheated to 120 ℃, is comprised of 100mL methyl-silicone oil and 100mL whiteruss, the volume ratio of blending agent and adduct solution was 1.4, with the rotating speeds stirrings of 3000 rev/mins 30 minutes.
(3) chilling solidifies
Above-mentioned emulsion was moved in advance in 5 minutes in the 1.0L anhydrous hexane that is chilled to-30 ℃, stirred 30 minutes with the rotating speeds of 130 rev/mins.Leach solids after system temperature rises to 25 ℃ naturally, use anhydrous hexane 3 times, dry under 80 ℃ of decompressions, get precursor carrier ZT-0, alcohol/magnesium mol ratio 2.92,16 meters of specific surface areas
2/ gram, 0.1 ml/g of pore volume, bulk density 0.65 grams per milliliter, its X-diffractogram is seen Fig. 1.
(4) dealcoholysis
Get 5g precursor carrier ZT-0, be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-1First 40 ℃ of fluidisation dealcoholysis 1 hour, then be warming up to 50 ℃ of fluidisation dealcoholysis 1 hour, obtaining dealcoholysis carrier ZT-1, alcohol/magnesium mol ratio is 2.75,13 meters of specific surface areas
2/ gram, 0.09 ml/g of pore volume, bulk density are 0.65g/mL, the X-diffractogram is seen Fig. 2.Fig. 2 shows, increases than ZT-0 at the peak intensity of the 2 7.42 ° of appearance in θ angle.
Example 2
Get 5g precursor carrier ZT-0 and be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-1First 40 ℃ of fluidisation dealcoholysis 1 hour, then be warming up to 50 ℃ of fluidisation dealcoholysis 2 hours, obtaining dealcoholysis carrier ZT-2, its alcohol/magnesium mol ratio is 2.60,18 meters of specific surface areas
2/ gram, 0.12 ml/g of pore volume, bulk density are 0.68g/mL, the X-diffractogram is seen Fig. 3.
Example 3
Get 5g precursor carrier ZT-0 and be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-1First 40 ℃ of fluidisation dealcoholysis 1 hour, then be warming up to 50 ℃ of fluidisation dealcoholysis 3 hours, obtaining dealcoholysis carrier ZT-3, its alcohol/magnesium mol ratio is 2.52,20 meters of specific surface areas
2/ gram, 0.16 ml/g of pore volume, bulk density are 0.63g/mL, the X-diffractogram is seen Fig. 4.
Example 5
Get 5g precursor carrier ZT-0 and be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-1First 40 ℃ of fluidisation dealcoholysis 1 hour, then be warming up to 50 ℃ of fluidisation dealcoholysis 4 hours, obtain dealcoholysis carrier ZT-4, alcohol/magnesium mol ratio 2.49,17 meters of specific surface areas
2/ gram, 0.13 ml/g of pore volume, bulk density are 0.70g/mL, the X-diffractogram is seen Fig. 5.
Fig. 3～Fig. 5 demonstration, along with the increase of dealcoholysis degree, the peak intensity of the 2 7.42 ° of appearance in θ angle continues to increase.
Comparative Examples 1
Get 5g precursor carrier ZT-0 and be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-140 ℃ of fluidisation dealcoholysis 4 hours, obtain carrier ZT-5, its alcohol/magnesium mol ratio 2.62,18 meters of specific surface areas
2/ gram, 0.12 ml/g of pore volume, bulk density are 0.62g/mL.
Comparative Examples 2
Get 5g precursor carrier ZT-0 and be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-150 ℃ of fluidisation dealcoholysis 4 hours obtain dealcoholysis carrier ZT-6, its alcohol/magnesium mol ratio 2.35,15 meters of specific surface areas
2/ gram, 0.13 ml/g of pore volume, bulk density are 0.65g/mL.
Comparative Examples 3
Get 5g precursor carrier ZT-0 and be placed in fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours by the mass space velocity of precursor carrier
-140 ℃ of fluidisation dealcoholysis 2 hours, obtain carrier ZT-7, its alcohol/magnesium mol ratio 2.82,18 meters of specific surface areas
2/ gram, 0.12 ml/g of pore volume, bulk density are 0.64g/mL.
Example 6
Kaolinite Preparation of Catalyst.
With a four-hole reaction flask N with mechanical stirring device
2Fully displacement, add 36mL (327mmol) TiCl under nitrogen protection
4Be cooled to-20 ℃, the suspension that adds 2.0g ZT-1 carrier and 10mL hexane to form, stop 30min at-20 ℃, naturally be warming up to 40 ℃, when being heated to 80 ℃, add the diisobutyl phthalate of 0.31mL (1.2mmol), 80 ℃ of stirring reaction 30min continue to be warming up to 115 ℃ of reaction 2h.Then sedimentation, suction filtration add 18mL (164mmol) TiCl in the solid that leaches
4, 120 ℃ of stirring reaction 60min, sedimentation, suction filtration, solid washs hexane consumption 30mL with hexane washing 6 times at every turn.After washing, solid in 70 ℃ of dryings, obtains solid catalyst C-1, wherein contains Ti2.94 quality %, Mg17.60 quality %, diisobutyl phthalate 11.20 quality %, chlorine 60.30 quality %, 149 meters of specific surface areas
2/ gram, 0.19 ml/g of pore volume.
Example 7
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-2, contains Ti2.87 quality %, Mg19.2 quality %, diisobutyl phthalate 11.4 quality %, chlorine 66.31 quality % in the catalyzer C-2 that makes, 168 meters of specific surface areas
2/ gram, 0.23 ml/g of pore volume.
Example 8
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-3, contains Ti3.2 quality %, Mg17.8 quality %, diisobutyl phthalate 11.8 quality %, chlorine 62.10 quality % in the catalyzer C-3 that makes, 204 meters of specific surface areas
2/ gram, 0.28 ml/g of pore volume.
Example 9
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-4, contains Ti3.3 quality %, Mg18.5 quality %, diisobutyl phthalate 11.4 quality %, chlorine 65.2 quality % in the catalyzer C-4 that makes, 204 meters of specific surface areas
2/ gram, 0.28 ml/g of pore volume.
Comparative Examples 4
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-0, contains Ti2.98 quality %, Mg17.9 quality %, diisobutyl phthalate 11.5 quality %, chlorine 62.70 quality % in the catalyzer C-4 that makes, 156 meters of specific surface areas
2/ gram, 0.22 ml/g of pore volume.
Comparative Examples 5
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-5, contains Ti3.1 quality %, Mg18.5 quality %, diisobutyl phthalate 11.5 quality %, chlorine 65.0 quality % in the catalyzer C-5 that makes, 160 meters of specific surface areas
2/ gram, 0.20 ml/g of pore volume.
Comparative Examples 6
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-6, contains Ti3.4 quality %, Mg18.6 quality %, diisobutyl phthalate 11.4 quality %, chlorine 66.2 quality % in the catalyzer C-6 that makes, 150 meters of specific surface areas
2/ gram, 0.21 ml/g of pore volume.
Comparative Examples 7
Press the method Kaolinite Preparation of Catalyst of example 6, different is that the carrier that adds is ZT-7, contains Ti3.0 quality %, Mg17.6 quality %, diisobutyl phthalate 11.7 quality %, chlorine 61.8 quality % in the catalyzer C-7 that makes, 159 meters of specific surface areas
2/ gram, 0.21 ml/g of pore volume.
Example 10～17
The polymerization catalyzed performance of following instance evaluate catalysts.
After 1L high-pressure glass polymeric kettle is fully replaced with hydrogen, add successively hexane, 0.24mmol dicyclohexyl methyl dimethoxysilane and the 30mg solid catalyst of 5.67mmol triethyl aluminum, 550mL drying.Be warming up to 70 ℃ and pass into propylene and begin polymerization, the control polymerization pressure is that 0.9MPa, hydrogen dividing potential drop are 0.2MPa polyreaction 1h.Termination reaction is isolated polymkeric substance and dry from hexane, obtain runny spherical polypropylene GRANULES.Each example used catalyst and polypropylene apparent bulk density and degree of isotacticity active and preparation see Table 1, and polymer beads distributes and sees Table 2.
Table 1
Table 2
Claims (10)
1. the preparation method of a spherical magnesium chloride carrier, comprise with magnesium chloride and fatty alcohol roh being to carry out alcohol in the blending agent that forms of the methyl-silicone oil of 1: 1 and whiteruss to close reaction in volume ratio, the dry precursor carrier that gets after dispersion, chilling solidify, precursor carrier is carried out one section dealcoholysis at 30～40 ℃ in noble gas stream, being warming up to 41～55 ℃ carries out two sections dealcoholysis and obtains spherical magnesium chloride alcohol carrier again, the described one dealcoholysis period is 0.5～3.0 hour, and two dealcoholysis periods are 1～5 hour.
2. in accordance with the method for claim 1, it is characterized in that described noble gas is nitrogen, during dealcoholysis, nitrogen is 2.5～25 hours by the mass space velocity of precursor carrier
-1
3. in the spherical magnesium chloride alcohol carrier that in accordance with the method for claim 1, it is characterized in that making, alcohol/magnesium mol ratio is 2.0～2.8.
4. in accordance with the method for claim 1, it is characterized in that described ROH preferred alcohol.
5. in accordance with the method for claim 1, it is characterized in that it is 50～150 ℃ that chilling solidifies rear dry temperature.
6. in accordance with the method for claim 1, it is characterized in that alcohol closes the magnesium chloride that adds of reaction and the mol ratio of Fatty Alcohol(C12-C14 and C12-C18) is 1～6, temperature of reaction is 110～130 ℃, and the time is 2～4 hours.
7. in accordance with the method for claim 1, it is characterized in that described dispersion be with alcohol close reaction gained magnesium chloride alcohol adducts solution move to be preheated to 110～130 ℃ be to disperse in the blending agent that forms of the methyl-silicone oil of 1: 1 and whiteruss by volume ratio, the volume ratio of blending agent and adduct solution is 1.2～2.0.
8. in accordance with the method for claim 1, it is characterized in that it is that after disperseing, the adduct solution of gained goes in the unreactive hydrocarbons solvent of-30～-15 ℃ that described chilling solidifies, the volume ratio of unreactive hydrocarbons solvent and adduct solution is 2.0～2.5.
9. in accordance with the method for claim 1, it is characterized in that 20 ℃ of viscosity of methyl-silicone oil are 50～600 centipoises, 20 ℃ of viscosity of whiteruss are 30～50 centipoises.
10. in accordance with the method for claim 8, it is characterized in that described unreactive hydrocarbons solvent is C
6～C
12Alkane.
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| CN104177523A (en) * | 2014-09-02 | 2014-12-03 | 淄博新塑化工有限公司 | Polypropylene catalyst spherical carrier and solid catalyst and preparation method thereof |
| CN109096419A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalyst and olefine polymerizing process for olefinic polymerization |
| CN109096421A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalyst and olefine polymerizing process for olefinic polymerization |
| CN109096418A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalyst and olefine polymerizing process for olefinic polymerization |
| CN109096424A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalyst and olefine polymerizing process for olefinic polymerization |
| CN109096420B (en) * | 2017-06-21 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and olefin polymerization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1075485A (en) * | 1992-01-31 | 1993-08-25 | 斯菲里玲有限公司 | Olefin polymerization catalyst components and catalyzer |
| CN1085914A (en) * | 1992-08-18 | 1994-04-27 | 斯菲里玲有限公司 | The polymerization process that is used for the vanadium base component of olefinic polymerization and catalyzer and utilizes them |
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