CN102558398A - Method for preparing spherical magnesium chloride carrier - Google Patents
Method for preparing spherical magnesium chloride carrier Download PDFInfo
- Publication number
- CN102558398A CN102558398A CN2010106139804A CN201010613980A CN102558398A CN 102558398 A CN102558398 A CN 102558398A CN 2010106139804 A CN2010106139804 A CN 2010106139804A CN 201010613980 A CN201010613980 A CN 201010613980A CN 102558398 A CN102558398 A CN 102558398A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- carrier
- magnesium chloride
- dealcoholysis
- described method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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 magnesium chloride ball type 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, influence catalyst form, cause in the polymerization process fine polymer powder more, magnesium chloride alcohol adducts solid alcohol/magnesium mol ratio should be controlled to be 1～3.Therefore, before the preparation catalyzer, generally to carry out dealcoholation treatment to magnesium chloride alcohol adducts carrier.Carrier through after the dealcoholation treatment has specific X-diffractogram.
USP4,421,674 disclose a kind of preparation method of olefin polymerization catalysis.This method is dissolved in Magnesium Chloride Anhydrous and forms solution in the alcohol, and spraying drying in flowing nitrogen is sloughed part alcohol then, 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 the adducts/magnesium mol ratio is 0.4～2.8: 1.This patent Fig. 3 shows that the X-diffractogram of adducts locates not have diffraction peak at 7～8 ° after the dealcoholysis, and highest peak is positioned at 8.8 ° to be located, and locates two more weak peaks at 9.5～10 ° and 11～11.5 °.
It is the preparing carriers solid catalyst that CN1089622A adopts the magnesium chloride and the adducts of alcohol.The method for preparing adducts is in the presence of inert solvent, in magnesium chloride, adds alcohol and forms 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 in olefin polymerisation and catalyzer of being used for, and carries out dealcoholysis through 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 behind 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, makes that the mol ratio of 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 cut to prepare adducts up to magnesium chloride and the ethanol synthesis of 5 quality %, prepares the spherical solid catalyst component through dispersion, chilling curing and Separation and Recovery again.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of magnesium chloride ball type carrier, the fine powder content that the method for dealcoholized that this method is used can improve activity of such catalysts and reduce polymkeric substance.
The preparation method of magnesium chloride ball type carrier provided by the invention; Comprise that magnesium chloride and fatty alcohol roh are carried out alcohol closes reaction; Solidify after drying through dispersion, chilling and get precursor carrier; Precursor carrier is carried out one section dealcoholysis at 30～40 ℃ in noble gas stream, be warming up to 41～55 ℃ again 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, the olefin polymerization catalysis by gained preparing carriers after the 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 that does not carry 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, the X-diffraction spectra of gained carrier is to have four diffracted rays between 5～10 ° at 2 θ after the dealcoholysis, lays respectively at 6.1 ± 0.1 °, 7.5 ± 0.1 °, 9.0 ± 0.4 ° and 9.8 ± 0.1 ° and locates; Wherein, 7.5 ± 0.1 ° of diffraction intensities of locating increase along with the increase of dealcoholysis degree.
Fluidisation dealcoholysis of the present invention is meant the magnesium chloride alcohol adducts carrier of treating dealcoholysis; Be that precursor carrier places 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 said carrier is 10～30 meters
2/ gram, pore volume are 0.05～0.5 milliliter/gram, and bulk density is 0.6～0.9 grams per milliliter.
The described one section dealcoholysis of the inventive method is carried out under 30～40 ℃ lesser temps, and preferred 0.5～3.0 hour of time, two sections dealcoholysis are carried out under 41～55 ℃ comparatively high temps, preferred 1～5 hour of time.The rare gas element nitrogen that dealcoholysis is used, nitrogen is 2.5～25 hours through the mass space velocity of precursor carrier during dealcoholysis
-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 the 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 of methyl-silicone oil and whiteruss composition, alcohol closes the magnesium chloride of reaction adding 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.The used magnesium chloride of preparation adducts can be a Magnesium Chloride Anhydrous, also can be the magnesium chloride that water-content is lower than 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 of being made up 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 the adduct solution that disperses the back gained is gone to balling-up in-30～-15 ℃ the unreactive hydrocarbons solvent 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.
The mixture that chilling obtains after solidifying is warmed up to the room temperature after-filtration naturally, and the solids that leaches is used nitrogen drying with inert solvent washing back down in 50～150 ℃ of normal pressures or decompression, obtains spherical magnesium chloride support precursor.
In aforesaid method, alcohol closes reaction and disperses in the used blending agent 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 back gained promptly gets spheric magnesium chloride alcohol adducts carrier with fluidisation method for dealcoholized of the present invention dealcoholysis.
Method with magnesium chloride alcohol adducts preparing carriers catalyzer 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-s is 30～60 by the Ti/Mg mol ratio; Preferred 35～45 amount joins in precooling to-20～0 ℃ the compound titanium solution that has a Ti-halogen key at least
(2) system slowly is warming up to 40～80 ℃, the amount of pressing Mg/ internal electron donor mol ratio 3.0～15.0, preferred 5.0～10.0 adds internal electron donor, and 100～125 ℃ were reacted 1.5～4 hours, and filtered while hot is isolated solid particulate,
(3) be that 20～50 amount joins solid particulate in the compound titanium solution that has a Ti-halogen key at least of preheating by the Ti/Mg mol ratio, stir down 100～125 ℃ of reactions 1～2 hour, filtered while hot is isolated solid particulate,
(4) with free cl ions on 50～70 ℃ the unreactive hydrocarbons solvent flush away particle, dry in vacuum or 50～80 ℃ of nitrogen gas stream, obtain the spherical solid catalyzer.
In the aforesaid method, it is Ti (OR) that described titanium compound of (1) step is selected from general formula
4-nX
nCompound, R is C in the formula
1～C
20Alkyl, X is a 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 adds in said (2) 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 C respectively
1～C
10Alkyl, aryl or aralkyl.
In the above-mentioned method for preparing catalyst, (1) step is respectively with (3) step and once carries titanium and secondary carries titanium, and a year titanium preferably under agitation carries out preferred 15～60 minutes of churning time.(4) going on foot the unreactive hydrocarbons solvent that is used for washing catalyst is C
6～C
12Alkane, preferred hexane.
Mg content is 15～25 quality % in the solid catalyst of the present invention's preparation, 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 milliliter/gram.
The catalyzer of the inventive method preparation is applicable to the homopolymerization and the copolymerization of alkene, is preferred for the 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 an Al/Ti mol ratio 200～1500.
When catalyzer of the present invention is used for propylene polymerization, in order to obtain to have high normal polypropylene product, also need add the external electron donor compound, external electron donor compound and internal electron donor compound can be the same or different.It is R that described external electron donor compound is selected from general formula
1R
2Si (OR)
2Silicon compound, preferred dimethoxydiphenylsilane or cyclohexyl methyl dimethoxy silane, its consumption generally is advisable with Al/Si mol ratio 8～30, is preferably 15～25.
The temperature of reaction of using catalyzer of the present invention to carry out olefinic polymerization is 60～120 ℃, preferred 70～100 ℃, and pressure is 0.1～6.0MPa, preferred 0.4～2.0MPa.
Further specify the present invention through instance below, but the present invention is not limited to this.
X-ray powder diffraction spectrum: adopt Japanese DMAX/IIIA x-ray diffractometer of science to measure, condition determination: CuK α (λ=1.5418), pipe is pressed 35V, pipe stream 25mA, slit 0.3mm, 4 °/minute of sweep velocitys are 2～70 ° of recording ray diffraction spectra.By analytic sample under nitrogen protection, grind, compressing tablet, place exsiccant 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 the nitrogen atmosphere.
Mg content adopts aas determination.With concentrated nitric acid and a small amount of hydrofluoric acid dissolution analyte, heating, quantitative after the cooling with zero(ppm) water, use the PE-460 atomic absorption detecting.
Ti content adopts spectrophotometry.After sulfuric acid (volume ratio 1: 17) solution dissolving analyte, heating, cooling, adding distil water adds 1 30% hydrogen peroxide to certain volume.Use 721 spectrophotometer colorimetrics then, 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 cable-styled extraction process 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 Vestolen PP 7052 apparent bulk density (B.D.) is: funnel is placed on the funnel support; 100mL sample holder ware places under the funnel support base; Apart from being 10cm, till sample poured into funnel to sample holder ware and fill with, claim its quality between adjustment hopper outlet and sample holder ware.Apparent bulk density is calculated as follows:
In the 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.
Instance 1
Prepare the magnesium chloride ball type carrier with the inventive method
(1) alcohol closes reaction
Magnesium chloride (water-content 2.65 quality %), 39mL (0.67mol) absolute ethyl alcohol, 110mL methyl-silicone oil, the 110mL whiteruss of 20 grams (0.21mol) are joined under nitrogen protection in the 500mL reaction flask that whisking appliance and prolong are housed, be heated to 120 ℃ and stirred 3 hours.The viscosity that said 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 made up of 100mL methyl-silicone oil and 100mL whiteruss, the volume ratio of blending agent and adduct solution was 1.4, with 3000 rev/mins rotating speeds stirrings 30 minutes.
(3) chilling solidifies
Above-mentioned emulsion was moved in 5 minutes in precooling to-30 ℃ the 1.0L anhydrous hexane, stirred 30 minutes with 130 rev/mins rotating speeds.Treat to leach solids after system temperature rises to 25 ℃ naturally, with anhydrous hexane 3 times, 80 ℃ of decompressions are dry down, precursor carrier ZT-0, alcohol/magnesium mol ratio 2.92,16 meters of specific surface areas
2/ gram, 0.1 milliliter/gram 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, place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through the mass space velocity of precursor carrier
-140 ℃ of fluidisation dealcoholysis 1 hour, be warming up to 50 ℃ of fluidisation dealcoholysis 1 hour more earlier, obtain dealcoholysis carrier ZT-1, alcohol/magnesium mol ratio is 2.75,13 meters of specific surface areas
2/ gram, 0.09 milliliter/gram of pore volume, bulk density is 0.65g/mL, the X-diffractogram is seen Fig. 2.Fig. 2 shows, increases than ZT-0 at the peak intensity of the 7.42 ° of appearance in 2 θ angles.
Instance 2
Get 5g precursor carrier ZT-0 and place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through the mass space velocity of precursor carrier
-140 ℃ of fluidisation dealcoholysis 1 hour, be warming up to 50 ℃ of fluidisation dealcoholysis 2 hours more earlier, obtain dealcoholysis carrier ZT-2, its alcohol/magnesium mol ratio is 2.60,18 meters of specific surface areas
2/ gram, 0.12 milliliter/gram of pore volume, bulk density is 0.68g/mL, the X-diffractogram is seen Fig. 3.
Instance 3
Get 5g precursor carrier ZT-0 and place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through the mass space velocity of precursor carrier
-140 ℃ of fluidisation dealcoholysis 1 hour, be warming up to 50 ℃ of fluidisation dealcoholysis 3 hours more earlier, obtain dealcoholysis carrier ZT-3, its alcohol/magnesium mol ratio is 2.52,20 meters of specific surface areas
2/ gram, 0.16 milliliter/gram of pore volume, bulk density is 0.63g/mL, the X-diffractogram is seen Fig. 4.
Instance 5
Get 5g precursor carrier ZT-0 and place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through the mass space velocity of precursor carrier
-140 ℃ of fluidisation dealcoholysis 1 hour, be warming up to 50 ℃ of fluidisation dealcoholysis 4 hours more earlier, obtain dealcoholysis carrier ZT-4, alcohol/magnesium mol ratio 2.49,17 meters of specific surface areas
2/ gram, 0.13 milliliter/gram of pore volume, bulk density is 0.70g/mL, the X-diffractogram is seen Fig. 5.
Fig. 3～Fig. 5 shows that along with the increase of dealcoholysis degree, the peak intensity of the 7.42 ° of appearance in 2 θ angles continues to increase.
Comparative Examples 1
Get 5g precursor carrier ZT-0 and place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through 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 milliliter/gram of pore volume, bulk density is 0.62g/mL.
Comparative Examples 2
Get 5g precursor carrier ZT-0 and place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through 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 milliliter/gram of pore volume, bulk density is 0.65g/mL.
Comparative Examples 3
Get 5g precursor carrier ZT-0 and place fluidized-bed reactor, fluidisation dealcoholysis under nitrogen, nitrogen is 10 hours through 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 milliliter/gram of pore volume, bulk density is 0.64g/mL.
Instance 6
The preparation catalyzer.
With one have mechanical stirring device the four-hole reaction flask use N
2Fully displacement adds 36mL (327mmol) TiCl under nitrogen protection
4, be cooled to-20 ℃, add the suspension-s that 2.0g ZT-1 carrier and 10mL hexane are formed; Stop 30min at-20 ℃; Naturally be warming up to 40 ℃, during heat temperature raising 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.Sedimentation then, 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 wash 6 times at every turn.To wash the back solid in 70 ℃ of dryings, obtain solid catalyst C-1, wherein contain 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 milliliter/gram of pore volume.
Instance 7
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-2 that makes, 168 meters of specific surface areas
2/ gram, 0.23 milliliter/gram of pore volume.
Instance 8
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-3 that makes, 204 meters of specific surface areas
2/ gram, 0.28 milliliter/gram of pore volume.
Instance 9
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-4 that makes, 204 meters of specific surface areas
2/ gram, 0.28 milliliter/gram of pore volume.
Comparative Examples 4
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-4 that makes, 156 meters of specific surface areas
2/ gram, 0.22 milliliter/gram of pore volume.
Comparative Examples 5
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-5 that makes, 160 meters of specific surface areas
2/ gram, 0.20 milliliter/gram of pore volume.
Comparative Examples 6
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-6 that makes, 150 meters of specific surface areas
2/ gram, 0.21 milliliter/gram of pore volume.
Comparative Examples 7
Method by instance 6 prepares catalyzer, and 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 % among the catalyzer C-7 that makes, 159 meters of specific surface areas
2/ gram, 0.21 milliliter/gram of pore volume.
The polymerization catalyzed performance of following instance evaluate catalysts.
After 1L glass polymermaking autoclave fully replaced with hydrogen, add 5.67mmol triethyl aluminum, 550mL exsiccant hexane, 0.24mmol dicyclohexyl methyl dimethoxysilane and 30mg solid catalyst successively.Be warming up to 70 ℃ of feeding propylene and begin polymerization, controlled 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 PP GRANULES.Each instance catalyst system therefor and Vestolen PP 7052 apparent bulk density and degree of isotacticity active and preparation are seen table 1, and polymer beads distributes and sees table 2.
Table 1
Table 2
Claims (11)
1. the preparation method of a magnesium chloride ball type carrier; Comprise that magnesium chloride and fatty alcohol roh are carried out alcohol closes reaction; Solidify after drying through dispersion, chilling and get precursor carrier; Precursor carrier is carried out one section dealcoholysis at 30～40 ℃ in noble gas stream, be warming up to 41～55 ℃ again and carry out two sections dealcoholysis and obtain spherical magnesium chloride alcohol carrier.
2. according to the described method of claim 1, it is characterized in that the described one dealcoholysis period is 0.5～3.0 hour, two dealcoholysis periods are 1～5 hour.
3. according to the described method of claim 1, it is characterized in that described noble gas is a nitrogen, nitrogen is 2.5～25 hours through the mass space velocity of precursor carrier during dealcoholysis
-1
4. according to the described method of claim 1, alcohol/magnesium mol ratio is 2.0～2.8 in the spherical magnesium chloride alcohol carrier that it is characterized in that making.
5. according to the described method of claim 1, it is characterized in that described ROH preferred alcohol.
6. according to the described method of claim 1, it is characterized in that the temperature of chilling curing after drying is 50～150 ℃.
7. according to the described method of claim 1; It is characterized in that magnesium chloride and fatty alcohol roh are carried out alcohol closes reaction in the blending agent that methyl-silicone oil and whiteruss are formed; Alcohol closes the magnesium chloride of reaction adding 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.
8. according to the described method of claim 1; It is characterized in that described dispersion is alcohol to be closed reaction gained magnesium chloride alcohol adducts solution move in the blending agent of being made up of methyl-silicone oil and whiteruss that is preheated to 110～130 ℃ and disperse, the volume ratio of blending agent and adduct solution is 1.2～2.0.
9. according to the described method of claim 1, it is characterized in that it is that the adduct solution that disperses the back gained is gone in-30～-15 ℃ the unreactive hydrocarbons solvent that described chilling solidifies, the volume ratio of unreactive hydrocarbons solvent and adduct solution is 2.0～2.5.
10. according to claim 7 or 8 described methods, the volume ratio that it is characterized in that methyl-silicone oil and whiteruss is 1: 1, and 20 ℃ of viscosity of methyl-silicone oil are 50～600 centipoises, and 20 ℃ of viscosity of whiteruss are 30～50 centipoises.
11., it is characterized in that described unreactive hydrocarbons solvent is C according to the described method of claim 9
6～C
12Alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010613980 CN102558398B (en) | 2010-12-30 | 2010-12-30 | Method for preparing spherical magnesium chloride carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010613980 CN102558398B (en) | 2010-12-30 | 2010-12-30 | Method for preparing spherical magnesium chloride carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102558398A true CN102558398A (en) | 2012-07-11 |
| CN102558398B CN102558398B (en) | 2013-11-06 |
Family
ID=46405123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010613980 Active CN102558398B (en) | 2010-12-30 | 2010-12-30 | Method for preparing spherical magnesium chloride carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102558398B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN109096420A (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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2010
- 2010-12-30 CN CN 201010613980 patent/CN102558398B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN109096420A (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102558398B (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102558398B (en) | Method for preparing spherical magnesium chloride carrier | |
| CN103788259B (en) | A kind of molecular weight narrow ditribution polypropylene | |
| WO2004055068A1 (en) | Method for the preparation of olefin polymerisation catalyst support and an olefin polymerisation catalyst | |
| Kissin et al. | Ziegler-Natta catalysts for propylene polymerization: Chemistry of reactions leading to the formation of active centers | |
| CN101215344B (en) | Olefin polymerization catalyst composition and preparing method thereof | |
| CN104592427A (en) | Olefin polymerization catalyst carrier as well as preparation method and application thereof | |
| CN101190953B (en) | Process for preparing catalyst solid component of olefin polymerization | |
| CN105111336A (en) | Electron donor of ethylene polymerization catalyst, ball-like catalyst and preparation method | |
| CN102898551B (en) | Catalyst component for olefin polymerization, and preparation method and catalyst thereof | |
| CN102746425B (en) | Alkene polymerization catalyst with thienyl substituting silane | |
| CN101880339A (en) | Ziegler-Natta polyethylene catalyst with wide molecular weight distribution, and preparation method thereof | |
| CN103788247A (en) | Catalyst component used for olefin polymerization, applications thereof, catalyst used for olefin polymerization, applications of the catalyst and olefin polymerization method | |
| CN101775086B (en) | Preparation method for ethylene homopolymer and copolymer | |
| CN1039234C (en) | Preparation of spheric polypropylene catalyst and its supporter | |
| CN100549036C (en) | A kind of magnesium-containing carrier reaches and prepares the method for catalyst solid component of olefin polymerization by it | |
| CN1268652C (en) | Spherical carrier catalyst for alpha olefinic polymerization | |
| CN109678995A (en) | A kind of alkene batch polymerization processes | |
| CN101472681B (en) | Catalyst component for the polymerization of olefins | |
| CN100523011C (en) | Process for the preparation of a catalyst component and components therefrom obtained | |
| CN102040682B (en) | Carrier for preparing olefinic polymerization catalyst and preparation method thereof | |
| CN108440692B (en) | Catalyzed ethylene polymerization Ziegler-Natta catalyst internal electron donor, catalytic component and preparation method | |
| CN108084305A (en) | Solid titanium catalyst component for vinyl polymerization and preparation method thereof and ethane polymerization solid titanium catalyst | |
| US4874737A (en) | Silicate-modified magnesium alkoxide polymerization catalysts | |
| CN105622644B (en) | A kind of adduct of magnesium halides and its application | |
| CN105622793B (en) | For the catalytic component and catalyst system of olefinic polymerization and its application and olefine polymerizing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |