CN102050897B - Preparation method of catalyst component for polymerization of vinyl and catalyst for polymerization of vinyl - Google Patents
Preparation method of catalyst component for polymerization of vinyl and catalyst for polymerization of vinyl Download PDFInfo
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- CN102050897B CN102050897B CN2009102366581A CN200910236658A CN102050897B CN 102050897 B CN102050897 B CN 102050897B CN 2009102366581 A CN2009102366581 A CN 2009102366581A CN 200910236658 A CN200910236658 A CN 200910236658A CN 102050897 B CN102050897 B CN 102050897B
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Abstract
The invention relates to a preparation method of catalyst components for polymerization of vinyl and a catalyst for the polymerization of vinyl. The method comprises the following steps: carrying out proper physical modification on a magnesium compound at a certain temperature; and then directly loading active components such as titanium tetrachloride and the like on the magnesium compound so as to prepare the catalyst suitable for the slurry polymerization and gas phase polymerization of vinyl. The catalyst prepared by the method has good hydrogen-regulating sensitivity in the process of catalyzing the polymerization of vinyl, the catalyst particle is strong and has small possibility of breaking, a particle form is good and is of a sphere shape, and the prepared catalyst has the characteristic of higher catalysis activity; and the preparation method is simple and easy to operate, and has small possibilities of generating serious corrosion on a device, and causing serious influence on environment; and the prepared polymer particle is of a sphere shape, and the fine powder is less.
Description
Technical field
The present invention relates to a kind of preparation method and catalyzer thereof of ethylene polymerization catalysts component.
Background technology
In the evolution of olefin polymerization catalysis; Ziegler-Natta catalyst with good particle form is one of target of pursuing of people always; Especially in gas-phase polythene technology; This point is particularly important, because the Ziegler-Natta catalyst of good particle kenel can form the polymkeric substance of good particle form, and so just can not occluding device.
U.S. Pat 4293673 discloses a kind of catalyzer that adopts silica gel and the preparation of magnesium chloride complex carrier, and this catalyst applications has greater activity in gas phase polymerization technology, and prepared ethene polymers has good particle form.But most preparation technology is more loaded down with trivial details for this type catalyzer, and the step that generally includes is to react with organo-aluminium compound with through spray-dired catalyst Precursors.
Chinese patent CN1140722 discloses a kind of elder generation magnesium chloride solids has been dissolved, and then goes out the catalyzer that sedimentary method prepares with halogenated titanium reaction eutectoid, and this catalyzer is used for gas phase polymerization technology, the granules of catalyst irregularity, and sphericity is poor.
European patent EP 0601524 discloses the catalyzer that a kind of mode of premolding magnesium chloride load active ingredient prepares; In this Preparation of catalysts process; Need under 120 ℃～140 ℃ hot conditions, handle with a large amount of titanium tetrachlorides; Easily equipment is produced heavy corrosion, production environment is caused have a strong impact on; This catalyzer is used for gas phase polymerization technology, when polymerization activity is higher, is prone to broken and produces a large amount of fine polymer powders, needs to increase prepolymerization technology usually; The hydrogen response of this catalyzer is poor in addition, and promptly under similar polymerizing condition, hydrogen partial pressure is close, but the melting index of resulting polymers is obviously on the low side.
Summary of the invention
The shortcoming of the catalyzer that the objective of the invention is to overcome above-mentioned method for preparing catalyst and obtained provides a kind of preparation method and catalyzer thereof that is used for the ethylene polymerization catalysts component with not enough.Have good hydrogen response during the catalyst vinyl polymerization of this method preparation, the solid difficult fragmentation of granules of catalyst, particle form is well spherical in shape, has advantages of high catalytic activity; The polymer beads form globulate of gained, fine powder is few; The slurry polymerization that both had been applicable to ethene also is applicable to the gas phase polymerization technology of ethene.
The invention provides a kind of preparation method of catalyst component, it comprises (1) under rare gas element, and magnesium halide alcohol adduct was obtained first kind of product in 1～10 hour 60 ℃～300 ℃ heating, and the pure content in this product is 0.5～30wt%; (2) with first kind of product be scattered in the inert solvent form homogeneous slurry after ,-80 ℃～150 ℃ down with the transition metal halide contact reactss, obtain catalyst component after the reactant that obtains filtered, washs; Described magnesium halide alcohol adduct is the product of contact of magnesium halide and low-carbon alcohol, and wherein the mol ratio of low-carbon alcohol and magnesium halide is 2～3; Said inert solvent is selected from alkane, aromatic hydrocarbon, halohydrocarbon or their mixture; Said transition metal is selected from halogenated titanium; The mol ratio of said magnesium halide alcohol adduct and transition metal halide is 0.1～100.
The median size of magnesium halide alcohol adduct between 5 microns～150 microns, preferred 10 microns～100 microns.
The preparation method of the product of contact of magnesium halide and alcohol is with reference to patent CN1091748A; Step is following: anhydrous magnesium halide such as magnesium dichloride are generated magnesium chloride alcohol adduct melt with alcohol by certain proportioning temperature reaction; After dispersion agent high speed dispersed with stirring; Cool quickly forms the microspheroidal solid particulate of magnesium chloride alcohol adduct again, after washing, drying, promptly obtains the magnesium chloride alcohol adduct.Dispersion agent employing varsol such as kerosene, Yellow Protopet 2A, vash oil, white oil etc. also add some tensio-active agents or silicoorganic compound.Alcohol comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and other high-carbon fatty alcohol compounds, wherein preferred alcohol.Alcohol is 2～3 with the mol ratio of magnesium dichloride, wherein preferred 2～2.8.
Above-mentioned transition metal halide is selected from halogenated titanium, preferred titanium tetrachloride.
The inert solvent that uses is preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, the ethylene dichloride or their mixture, most preferably is a kind of in hexane, toluene, the heptane or their mixture.
Preferred 90 ℃～260 ℃ of the TR that magnesium halide alcohol adduct is heated, preferred 3～5 hours of heat-up time; Through the change of thermal treatment temp, be easy to regulate and control catalyst particulate size.
Preferred-80 ℃～100 ℃ of range of reaction temperature when contacting with transition metal halide.
First kind of product is scattered in and forms homogeneous slurry in the inert solvent, and its concentration in slurries is 2～50wt%, preferred 10～20wt%.
Described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
Adopt the catalyzer of method for preparing, the specific surface area of using the BET method to record is 70～600m
2/ g, porosity is 0.01～4.2ml/g, average pore diameter 3～40nm.
The present invention also provides a kind of catalyzer that is used for olefinic polyreaction, and it comprises the above-mentioned reaction product that contains the catalyst component and the promotor of transition metal.
Above-mentioned promotor is an organo-aluminium compound; Preferred trialkylaluminium, aikyl aluminum halide are like a kind of in trimethylaluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, aluminium diethyl monochloride, dichloro one aluminium triethyl or their mixture.
Preferred 1: 1～100: 1 of the mol ratio of said organo-aluminium compound and the catalyst component that contains transition metal.
The employed solvent of polymerization is selected from alkane or aromatic hydrocarbon; Be preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, trichloromethane, the ethylene dichloride or their mixture, most preferably be a kind of in hexane, toluene, the heptane or their mixture.
Polymerization temperature is-78 ℃～150 ℃, is preferably-50 ℃～90 ℃.
Polymerization pressure is 0.001～10.0MPa, preferred 0.01～2.0MPa.
Catalyst system of the present invention can be used on the various polymerization method, comprises slurry polymerization and vapour phase polymerization.
Catalyst system of the present invention can be used for the polymerization or the copolymerization of alkene; Be specially adapted to that ethylene homo closes or the copolymerization of ethene and other terminal olefin, wherein terminal olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1.
Simple, the easy control of Preparation of catalysts method of the present invention through the change of thermal treatment temp, is easy to regulate and control catalyst particulate size, and the particle form of gained catalyst component is spherical in shape; This catalyzer hydrogen regulation performance is good and have a good vinyl polymerization catalytic activity; Polymkeric substance particle spherical in shape, fine powder is few; This catalyzer is applicable to slurry process and vapor phase process polymerization technique.
Description of drawings
Fig. 1 is the particle form figure of the spherical catalyst of embodiment 2 preparations.
Embodiment
Testing method:
1, the size-grade distribution of carrier and catalyzer: MASTERSIZE particles distribution instrument, normal hexane be as dispersion agent, useful range 0.02～2000 μ m.
2, specific surface area and pore volume:, adopt the specific surface area of BET method working sample, based on N with CE-Instruments Milestone 200 specific surface area analysis appearance
2The capillary condensation method gaging hole of absorption holds and pore distribution.
3, the relative weight per-cent of metal (mainly being titanium, magnesium) in the catalyst system: plasma emission spectrum (ICP).
4, the pattern of carrier, catalyzer and polymkeric substance: ESEM (SEM).
5, the mensuration of melting index: ASTM-D 1238
6, the mensuration of tap density: DIN-53194
The compound method of the magnesium chloride alcohol adduct that the present invention adopts is following:
Reflux exchanger, mechanical stirrer and TM are being housed; In 250 milliliters of glass reactors after nitrogen is fully replaced; Add 37.8 milliliters of absolute ethyl alcohols, Magnesium Chloride Anhydrous 21.3 grams stir down and heat up; Treat that magnesium chloride all dissolves the back and adds 75 milliliters of white oils, 75 milliliters of silicone oil, keep 120 ℃ of certain hours.In another volume is 500 milliliters the reaction flask that has high speed agitator, add the silicone oil of 112.5 milliliters of white oils and equal volume in advance, be preheating to 120 ℃; The mixture of aforementioned preparation is pressed into rapidly in second reactor drum, keeps under 120 ℃ of temperature, with 3500 rev/mins of high-speed stirring of rotating speed three minutes; Stir down material is transferred to and add 1600 milliliters of hexanes in advance and be cooled in-25 ℃ the 3rd reactor drum; Shift until material and to finish, outlet temperature is no more than 0 ℃, suction filtration, uses hexane wash; Flush away silicone oil and white oil obtain spherical particle magnesium chloride alcohol adduct 43.5 grams through vacuum-drying.Analytical test magnesium chloride alcohol adduct consist of MgCl
22.56C
2H
5OH, median size is 52.1 microns, pure content 55.0% (weight).
Embodiment 1
The preparation method of spherical catalyst component
(1) the modification pre-treatment of magnesium chloride alcohol adduct
Under nitrogen protection, the spherical magnesium chloride alcohol adduct of 40.15 grams is joined in 250 milliliters of glass reactors, be heated to 110 ℃, keep reaction 4 hours, obtain white spheroidal particle 23.54 grams, median size is 52.6 microns, pure content 25.3% (weight).
(2) active ingredient loads with
Under nitrogen protection; Spheroidal particle 5.80 grams that step (1) is obtained join in 250 milliliters of glass reactors, add 40 ml n-hexanes, stir and process slurries; Be cooled to-30 ℃ with the low temperature bath; Slowly drip the hexane solution (containing titanium tetrachloride 0.5ml) of 20.0 milliliters of titanium tetrachlorides, stirring reaction 1 hour slowly is warming up to 50 ℃ then and kept stirring reaction 2 hours.Reaction is left standstill after finishing, and leaches liquid, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtains having magnesium chloride supported catalyst 3.85 grams of good flowability, and its median size is 52.1 microns.
Ultimate analysis (ICP): Ti:1.25% (weight), Mg:6.87% (weight), pure content 18.4% (weight).
BET analyzes: specific surface area is 89.3m
2/ g, porosity is 0.2ml/g, average pore diameter 3.6nm.
Embodiment 2
The preparation method of spherical catalyst component
(1) the modification pre-treatment of magnesium chloride alcohol adduct
Under nitrogen protection, the spherical magnesium chloride alcohol adduct of 40.15 grams is joined in 250 milliliters of glass reactors, be heated to 150 ℃, keep reaction 4 hours, obtain white spheroidal particle 19.69 grams, median size is 56.3 microns, pure content 18.1% (weight).
(2) active ingredient loads with
Under nitrogen protection; Spheroidal particle 4.24 grams that step (1) is obtained join in 250 milliliters of glass reactors, add 40 ml n-hexanes, stir and process slurries; Be cooled to-30 ℃ with the low temperature bath; Slowly drip the hexane solution (containing titanium tetrachloride 0.5ml) of 20.0 milliliters of titanium tetrachlorides, stirring reaction 1 hour slowly is warming up to 50 ℃ then and kept stirring reaction 2 hours.Reaction is left standstill after finishing, and leaches liquid, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtains having magnesium chloride supported catalyst 3.73 grams of good flowability, and its median size is 46.9 microns.
Ultimate analysis (ICP): Ti:0.92% (weight), Mg:7.02% (weight), pure content 9.8% (weight).
BET analyzes: specific surface area is 93.4m
2/ g, porosity is 0.56ml/g, average pore diameter 5.4nm.
Embodiment 3
The preparation method of spherical catalyst component
(1) the modification pre-treatment of magnesium chloride alcohol adduct
Under nitrogen protection, the spherical magnesium chloride alcohol adduct of 37.75 grams is joined in 250 milliliters of glass reactors, be heated to 170 ℃, keep reaction 4 hours, obtain white spheroidal particle 18.90 grams, median size is 65.6 microns, pure content 3.4% (weight).
(2) active ingredient loads with
Under nitrogen protection; Spheroidal particle 4.20 grams that step (1) is obtained join in 250 milliliters of glass reactors, add 40 ml n-hexanes, stir and process slurries; Be cooled to 30 ℃ with the low temperature bath; Slowly drip the hexane solution (containing titanium tetrachloride 0.5ml) of 20.0 milliliters of titanium tetrachlorides, stirring reaction 1 hour slowly is warming up to 50 ℃ then and kept stirring reaction 2 hours.Reaction is left standstill after finishing, and leaches liquid, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtains having magnesium chloride supported catalyst 3.89 grams of good flowability, and its median size is 32.3 microns.
Ultimate analysis (ICP): Ti:1.14% (weight), Mg:7.38% (weight), pure content 2.3% (weight).
BET analyzes: specific surface area is 120.6m
2/ g, porosity is 0.89ml/g, average pore diameter 20.7nm.
Embodiment 4
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then; Along with the adding of hexane, the triethyl aluminum hexane solution of 1.0 milliliter of 2 mol is added, then add 28.6 milligrams of the spherical magnesium chloride catalyzer that make among the embodiment 1; The hydrogen that adds the 0.28MPa dividing potential drop; Be warming up to 70 ℃ and begin to add ethene, dividing potential drop is 0.75MPa, keeps total pressure 1.03MPa, 85 ℃ of reactions of temperature 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 242 grams, activity of such catalysts is 4230gPE/gcat.h, bulk density (BD) is 0.32g/ml, and is spherical in shape through the electron microscopic observation resin particle, poly MI
2.16=0.27g/10min.
Embodiment 5
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then; Along with the adding of hexane, the triethyl aluminum hexane solution of 1.0 milliliter of 2 mol is added, then add 63.4 milligrams of the spherical magnesium chloride catalyzer that make among the embodiment 1; The hydrogen that adds the 0.60MPa dividing potential drop; Be warming up to 70 ℃ and begin to add ethene, dividing potential drop is 0.43MPa, keeps total pressure 1.03MPa, 85 ℃ of reactions of temperature 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 135 grams, activity of such catalysts is 1060gPE/gcat.h, bulk density (BD) is 0.29g/ml, and is spherical in shape through the electron microscopic observation resin particle, poly MI
2.16=13.61g/10min.
Embodiment 6
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then; Along with the adding of hexane, the triethyl aluminum hexane solution of 1.0 milliliter of 2 mol is added, then add 21.6 milligrams of the spherical magnesium chloride catalyzer that make among the embodiment 2; The hydrogen that adds the 0.28MPa dividing potential drop; Be warming up to 70 ℃ and begin to add ethene, dividing potential drop is 0.75MPa, keeps total pressure 1.03MPa, 85 ℃ of reactions of temperature 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 287 grams, activity of such catalysts is 6644gPE/gcat.h, bulk density (BD) is 0.34g/ml, and is spherical in shape through the electron microscopic observation resin particle, poly M worker
2.16=0.64g/10min.
The poly size-grade distribution of table 1 (weight percent)
| ＞850 μm | 425～850 μm | 250～425 μm | 180～250 μm | 150～180 μm | 106～150 μm | 75～106 μm | ＜75 μm |
| 21.80 | 56.90 | 16.20 | 3.45 | 1.21 | 0.44 | 0 | 0 |
Embodiment 7
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then; Along with the adding of hexane, the triethyl aluminum hexane solution of 1.0 milliliter of 2 mol is added, then add 51.6 milligrams of the spherical magnesium chloride catalyzer that make among the embodiment 2; The hydrogen that adds the 0.60MPa dividing potential drop; Be warming up to 70 ℃ and begin to add ethene, dividing potential drop is 0.43MPa, keeps total pressure 1.03MPa, 85 ℃ of reactions of temperature 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 228 grams, activity of such catalysts is 2209gPE/gcat.h, bulk density (BD) is 0.33g/ml, and is spherical in shape through the electron microscopic observation resin particle, poly MI
2.16=30.96g/10min.
Embodiment 8
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then; Along with the adding of hexane, the triethyl aluminum hexane solution of 1.0 milliliter of 2 mol is added, then add 19.9 milligrams of the spherical magnesium chloride catalyzer that make among the embodiment 3; The hydrogen that adds the 0.28MPa dividing potential drop; Be warming up to 70 ℃ and begin to add ethene, dividing potential drop is 0.75MPa, keeps total pressure 1.03
MPa, 85 ℃ of reactions of temperature 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 204 grams, activity of such catalysts is 5130gPE/gcat.h, bulk density (BD) is 0.28g/ml, and is spherical in shape through the electron microscopic observation resin particle, poly MI
2.16=0.20g/10min.
Embodiment 9
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then; Along with the adding of hexane, the triethyl aluminum hexane solution of 1.0 milliliter of 2 mol is added, then add 61.3 milligrams of the spherical magnesium chloride catalyzer that make among the embodiment 3; The hydrogen that adds the 0.60MPa dividing potential drop; Be warming up to 70 ℃ and begin to add ethene, dividing potential drop is 0.43MPa, keeps total pressure 1.03MPa, 85 ℃ of reactions of temperature 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 150 grams, activity of such catalysts is 1220gPE/gcat.h, bulk density (BD) is 0.28g/ml, and is spherical in shape through the electron microscopic observation resin particle, poly MI
2.16=11.47g/10min.
With the data list of embodiment 4～9, see table 2.
Table 2
| Numbering | The pressure ratio of hydrogen and ethene | Catalyst efficiency gPE/gcat.h | Polymer B D g/ml | Polymkeric substance MI 2.16 g/10min |
| Embodiment 4 | 0.28/0.75 | 4230 | 0.32 | 0.27 |
| Embodiment 5 | 0.60/0.43 | 1060 | 0.29 | 13.61 |
| Embodiment 6 | 0.28/0.75 | 6644 | 0.34 | 0.64 |
| Embodiment 7 | 0.60/0.43 | 2209 | 0.33 | 30.96 |
| Embodiment 8 | 0.28/0.75 | 5130 | 0.28 | 0.20 |
| Embodiment 9 | 0.60/0.43 | 1220 | 0.28 | 11.47 |
Can find out to have good hydrogen response during the catalyst vinyl polymerization of the present invention preparation, and have advantages of high catalytic activity, as can beappreciated from fig. 1 the granules of catalyst form globulate of the present invention's preparation from the data of embodiment 4-9; The fine polymer powder that when table 1 can be found out the catalyst vinyl polymerization that the present invention prepares, obtains seldom.
Claims (8)
1. a preparation method who is used for the ethylene polymerization catalysts component comprises the steps:
(1) under rare gas element, the magnesium chloride alcohol adduct was obtained first kind of product in 1～10 hour 60 ℃～300 ℃ heating, the pure content in this product is 0.5～30wt%;
(2) with first kind of product be scattered in the inert solvent form homogeneous slurry after, 80 ℃～150 ℃ of ﹣ down with the transition metal halide contact reactss, obtain catalyst component after the reactant that obtains filtered, washs;
Described magnesium chloride alcohol adduct is the product of contact of magnesium chloride and low-carbon alcohol; It prepares through following method: Magnesium Chloride Anhydrous generates magnesium chloride alcohol adduct melt with alcohol by certain proportioning temperature reaction; After dispersion agent high speed dispersed with stirring; Cool quickly forms the microspheroidal solid particulate of magnesium chloride alcohol adduct again, after washing, drying, promptly obtains the magnesium chloride alcohol adduct;
Wherein the mol ratio of low-carbon alcohol and magnesium chloride is 2～3; Described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol;
Said inert solvent is selected from alkane, aromatic hydrocarbon, halohydrocarbon or their mixture;
Said transition metal is selected from halogenated titanium;
The mol ratio of said magnesium chloride alcohol adduct and transition metal halide is 0.1～100.
2. the preparation method who is used for the ethylene polymerization catalysts component according to claim 1 is characterized in that first kind of product and the catalytic temperature of reaction of transition metal halide are 80 ℃～100 ℃ of ﹣.
3. the preparation method who is used for the ethylene polymerization catalysts component according to claim 1 is characterized in that the concentration of first kind of product in slurries is 2～50wt%.
4. the preparation method who is used for the ethylene polymerization catalysts component according to claim 1 is characterized in that the concentration of first kind of product in slurries is 10～20wt%.
5. the preparation method who is used for the ethylene polymerization catalysts component according to claim 1 is characterized in that the temperature that the magnesium chloride alcohol adduct is heated is 90 ℃～260 ℃.
6. the preparation method who is used for the ethylene polymerization catalysts component according to claim 1 is characterized in that be 3～5 hours heat-up time.
7. the preparation method who is used for the ethylene polymerization catalysts component according to claim 1 is characterized in that described inert solvent is a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, trichloromethane or the ethylene dichloride or their mixture.
8. be used for ethylene polymerization catalysts, it is characterized in that comprising the reaction product of following component:
One of A, employing claim 1 to 7 catalyst component that described preparation method obtained;
B, organo-aluminium compound;
Mol ratio between B component and the component A is 1～100.
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