CN101519463A - Preparation method of catalyst for ethylene polymerization and copolymerization - Google Patents
Preparation method of catalyst for ethylene polymerization and copolymerization Download PDFInfo
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- CN101519463A CN101519463A CNA2008101910649A CN200810191064A CN101519463A CN 101519463 A CN101519463 A CN 101519463A CN A2008101910649 A CNA2008101910649 A CN A2008101910649A CN 200810191064 A CN200810191064 A CN 200810191064A CN 101519463 A CN101519463 A CN 101519463A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Abstract
Provided is a preparation method of a catalyst for ethylene (co)polymerization, comprising the following steps: (1) preparing a magnesium compound solution by contact-reacting a halogenated magnesium compound with a mixed solvent of cyclic ether and at least one alcohol; (2) reacting the resulted magnesium compound solution from the above step (1) with a silicon compound having at least one alkoxy group; (3) preparing a support by adding a titanium compound to the resulted product from the step (2); and (4) reacting thus obtained support with a titanium compound and optionally a monoester compound, resulting in a catalyst. Catalysts prepared according to the present invention have a regulated particle shape, and their particle size can be easily adjusted. Therefore, with such catalyst, it is possible to produce polymers having high bulk density at high production yield.
Description
Technical field
The present invention relates to the preparation method of a kind of ethene (being total to) polymerisation catalysts, the method that particularly may further comprise the steps: (1) prepares magnesium compound solution by the mixed solvent contact reacts with halogenated magnesium compound and cyclic ethers and at least a alcohol; (2) magnesium compound solution that above-mentioned steps (1) is obtained and silicon compound reaction with at least one alkoxy base; (3) by preparing carrier in the product that titanium compound is joined step (2) acquisition; (4) carrier that will obtain like this and titanium compound and optional monoester compound reaction obtain catalyzer.Catalyzer prepared in accordance with the present invention has the particle shape of rule, and their particle diameter is easy to regulate.Therefore, use this catalyzer, can under high productivity, make polymkeric substance with high-bulk-density.
Background technology
Known the polymkeric substance that Mg catalyst provides significant high catalytic activity and has high-bulk-density that contains that is used for ethene (being total to) polyreaction, and applicable to the liquid and gas polyreaction.The liquid-phase polymerization of ethene is meant that polymerization process is at the ethene body or for example carry out in the medium of iso-pentane or hexane.In this liquid-phase polymerization, according to process adaptability, think that the performance of catalyzer is very important, described catalyst performance for example high reactivity, shape, size, distribution of sizes, tap density, may be dissolved in the content of the lower-molecular-weight component in the medium etc.
In the technical field under the present invention, knownly contain magnesium and based on the multiple Catalysts and its preparation method that is used for olefinic polyreaction of titanium.Especially, known a lot of methods use magnesium solution to obtain the catalyzer of olefinic polyreaction, and it has above-mentioned high-bulk-density.There is the method that is used to obtain magnesium compound solution, by the electron donor(ED) of magnesium compound with for example alcohol, amine, cyclic ethers, organic carboxyl acid or the like reacted, for example U.S. Patent No. 3,642 in the presence of hydrocarbon solvent for they, 746,4,336,360,4,330,649 and 5,106,807, the pure method of having used has wherein been described.In addition, many methods known in the art by with this liquid magnesium solution with such as the magnesium-supported catalyzer of halide-containing prepared in reaction of titanium tetrachloride.The catalyzer of planting the art methods acquisition thus can provide high-bulk-density, but they still need to improve with regard to catalytic activity or H-H reaction.About this point, U.S. Patent No. 4,477,639 and 4,518,706 have described that to use tetrahydrofuran (THF) be the invention of cyclic ethers as the solvent of magnesium compound.
U.S. Patent No. 4,847,227,4,816,433,4,829,037,4,970,186 and 5130284 have described the preparation method of olefin polymerization catalyst, it has excellent polymerization activity, and the polymkeric substance with improved tap density can be provided, and this method is with the magnesium alkoxide with such as the electron donor(ED) and the titanium chloride compound reaction of dialkyl group phthalate, phthalyl chloride etc.
U.S. Patent No. 4,347,158,4,422,957,4,425,257,4,618,661 and 4,680,381 have described the Preparation of catalysts method, wherein make catalyzer by adding such as the Lewis acid of aluminum chloride and subsequently resultant being pulverized in magnesium chloride support.Though catalytic activity increases in the patent of enumerating in the above, they still have problems, and this makes the catalyzer form of catalyzer, and for example shape, size, distribution of sizes are irregular, and tacticity needs to improve.
U.S. Patent No. 5,459,116 have described a kind of catalyzer, the polymkeric substance that it can provide high polymerization activity and have high-bulk-density, wherein this catalyzer will be by having the magnesium compound solution of the ester of at least one oh group as containing of electron donor(ED), and the solid titanium catalyst that obtains a kind of load with the titanium compound contact reacts is prepared from.But it still needs to improve with regard to particle form.
Technical problem
As previously mentioned, need a kind of new catalyst that is used for ethene (being total to) polyreaction of exploitation, it can be prepared from by simple method, and, because particle shape and size that it is easy to regulate can provide high polymerization activity and the polymkeric substance with high-bulk-density.
Summary of the invention
The purpose of this invention is to provide the novel preparation method of a kind of ethene (being total to) polymerisation catalysts, it has high catalytic activity, and can provide the polymkeric substance with high-bulk-density by shape, particle size and the distribution of sizes of adjusting catalyzer.Especially, the invention provides the simple and effective preparation method of a kind of ethene (being total to) polyreaction ingredient of solid catalyst, it can be regulated the shape of catalyzer and very high tap density is provided.
The preparation method of ethene of the present invention (being total to) polymerisation catalysts is characterised in that and may further comprise the steps:
(1) by mixed solvent contact reacts with halogenated magnesium compound and cyclic ethers and at least a alcohol, the preparation magnesium compound solution;
(2) magnesium compound solution that above-mentioned steps (1) is obtained and silicon compound reaction with at least one alkoxy base;
(3) by preparing carrier in the product that will join step (2) acquisition by the titanium compound of general formula (I) expression:
Ti(OR)
aX
(4-a)......(I)
[wherein R has C
1-10Alkyl group; X is a halogen atom; And a is the integer of 0-4]; With
(4) with carrier that obtains and titanium compound and optional monoester compound reaction, obtain catalyzer with above-mentioned general formula (I).
In the step that is used for preparing magnesium compound solution (1), for halogenated magnesium compound, can use to be selected from following at least a or two compounds, for example: magnesium dihalide is magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide for example; Alkyl halide magnesium is methylmagnesium-halide, ethyl magnesium halide, propyl group magnesium halide, butyl magnesium halide, isobutyl-magnesium halide, hexyl magnesium halide and amyl group magnesium halide for example; The alkoxyl group magnesium halide is methoxyl group magnesium halide, oxyethyl group magnesium halide, isopropoxy magnesium halide, butoxy magnesium halide and octyloxy magnesium halide for example; And aryloxy magnesium halide for example phenoxy group magnesium halide and tolyloxy magnesium halide, or the coordination compound of magnesium and other metals.
Though above-named compound can be used simple chemical formulation, under some other situations, according to the preparation method of magnesium compound, some compounds can not be used the simple-type subrepresentation.Can think the mixture of the magnesium compound enumerated usually in this case.For example, can also use by magnesium compound and polysiloxane compound among the present invention, contain the compound that reaction such as halo silane compound, ester, alcohol obtains, and in the presence of thionyl chloride by MAGNESIUM METAL and halosilanes or with the compound of alcohol, phenol or ether reaction acquisition.Preferred magnesium halide, particularly magnesium chloride; Alkylmagnesium chloride preferably has C
1-C
10Alkyl group; Alkoxy-magnesium chloride preferably has C
1-C
10Alkoxy base; And aryloxymagnesium chloride, preferably have C
6-C
20Aryloxy group.
In the step that is used for preparing magnesium compound solution (1), when magnesium compound is converted into magnesium compound solution, preferably use the mixed solvent of cyclic ethers and at least a alcohol.The cyclic ethers of Shi Yonging is cyclic ethers and the derivative thereof that has 3-6 carbon atom in the ring herein.Preferred especially tetrahydrofuran (THF) and 2-methyltetrahydrofuran, most preferably tetrahydrofuran (THF).The alcohol of Shi Yonging can be monobasic or the polyvalent alcohol with 1-20 carbon atom herein, preferably mentions the alcohol with 2-12 carbon atom.
Based on the halogenated magnesium compound of 1mol, the consumption of the mixed solvent of cyclic ethers and at least a alcohol is preferably 1-20mol in the magnesium compound solution preparation process, more preferably 2-10mol.When consumption during less than 1mol, be difficult to reach the dissolving of magnesium compound, and when it during greater than 20mol, for the amount that obtains the titanium compound that granules of catalyst adds can sharply increase, this causes and is difficult to adjust particle size.In addition, in above-mentioned mixed solvent, the mol ratio of cyclic ethers and at least a alcohol (cyclic ethers: alcohol) be preferably 1:0.05-1:0.95.When beyond the above-mentioned scope, owing to be difficult to prepare spherical catalyst, thereby not by preferably.
In the step that is used for preparing magnesium compound solution (1), in order to prepare magnesium compound solution, the contact reacts of the mixed solvent of halogenated magnesium compound and cyclic ethers and at least a alcohol is following the carrying out of situation that has or do not exist hydrocarbon solvent.The hydrocarbon solvent of Shi Yonging can comprise herein: aliphatic hydrocarbon is pentane, hexane, heptane, octane, decane and kerosene for example; Alicyclic hydrocarbon is hexanaphthene and methylcyclohexane for example; Aromatic hydrocarbon is benzene,toluene,xylene, ethylbenzene, isopropyl benzene and cymene for example; Perhaps for example propylene dichloride, Ethylene Dichloride, trieline, tetracol phenixin and chlorobenzene of halon.
In the step that is used for preparing magnesium compound solution (1), though be used to prepare the solvent temperature of magnesium compound solution because the type of cyclic ethers and alcohol with consumption and different, is preferably dissolved more preferably from about 50 ℃-150 ℃ under the temperature in room temperature to 200 ℃ scope.
In the step (2) of magnesium compound solution and silicon compound reaction,, preferably has R for silicon compound with at least one alkoxy base
nSi (OR
1)
4-nThe compound of general formula, wherein R and R
1Be to have C independently
1-12Hydrocarbon; And n is the integer of 0-3.Especially, can use dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, the phenylbenzene diethoxy silane, ethyl trimethoxy silane, vinyltrimethoxy silane, methyltrimethoxy silane, phenyltrimethoxysila,e, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, the butyl triethoxyl silane, phenyl triethoxysilane, ethyl three isopropoxy silane, vinyl three butoxy silanes, tetraethyl silicate, butyl silicate, methyl three aryloxy silanes etc.Based on the halogenated magnesium compound of 1mol, the consumption of the silicon compound with at least one alkoxy base of Shi Yonging is preferably 0.005-3mol herein, more preferably 0.05-2mol.When the consumption of the silicon compound with at least one alkoxy base is beyond above-mentioned scope, owing to can not obtain required support shapes, therefore not by preferably.
In the step (2) that magnesium compound solution and the silicon compound with at least one alkoxy base react, catalytic temperature is preferably 0-100 ℃, more preferably 10-70 ℃ between magnesium compound solution that is obtained by step (1) and the silicon compound with at least one alkoxy base.
In the step that is used for preparing carrier (3), at the titanium compound that in the product of step (2), adds following general formula (I) expression under 20-50 ℃.This mixture of elevated temperature and ageing subsequently obtains the solid particulate as carrier:
Ti(OR)
aX
(4-a)......(I)
Wherein R is the alkyl group with 1-10 carbon atom; X is a halogen atom; And a is the integer of 0-4.
For the titanium compound that satisfies above-mentioned general formula (I), for example can use for example TiCl of titanium tetrahalide
4, TiBr
4And TiI
4Three halogenated alkoxy titaniums are Ti (OCH for example
3) Cl
3, Ti (OC
2H
5) Cl
3, Ti (OC
2H
5) Br
3And Ti (O (i-C
4H
9)) Br
3The dihalide titan-alkoxide is Ti (OCH for example
3)
2Cl
2, Ti (OC
2H
5)
2Cl
2, Ti (O (i-C
4H
9))
2Cl
2And Ti (OC
2H
5)
2Br
2Four titan-alkoxides are Ti (OCH for example
3)
4, Ti (OC
2H
5)
4And Ti (OC
4H
9)
4Or its mixture.Preferred titanium compound is a titanium tetrachloride.
Based on the halogenated magnesium compound of 1mol, be preferably 0.1-500mol at the consumption of the step that is used for preparing carrier (3) titanium compound, 0.1-300mol more preferably, and most preferably be 0.2-200mol.When the consumption of titanium compound is beyond above-mentioned scope, owing to can not obtain required support shapes, therefore not by preferably.When magnesium compound solution and titanium compound reaction, the shape and size of recrystallization solid ingredient become according to reaction conditions.Therefore, being reflected under the suitable temperature between magnesium compound solution and the titanium compound carried out, with the preparation solid ingredient.Preferably, contact reacts is carried out in 10-70 ℃ scope, more preferably 20-50 ℃.After contact reacts, temperature of reaction raises gradually, makes reaction further fully to carry out 0.5-5 hour in 50-150 ℃ scope.
In the step (4) of Preparation of Catalyst, make carrier that step (3) obtains and titanium compound or with titanium compound and monoester compound reaction, to prepare catalyzer.Reaction can by once or twice or three times or more times reaction finish, and ideally by considering that catalyst performance, the material of adding and the economic benefit of reaction determine.
For the titanium compound that in step (4), uses, the titanium compound of preferred following general formula (I) expression:
Ti(OR)
aX
(4-a)......(I)
Wherein R is the alkyl group with 1-10 carbon atom; X is a halogen atom; And a is the integer of 0-4.
For the titanium compound that satisfies above-mentioned general formula (I), for example can use for example TiCl of titanium tetrahalide
4, TiBr
4And TiI
4Three halogenated alkoxy titaniums are Ti (OCH for example
3) Cl
3, Ti (OC
2H
5) Cl
3, Ti (OC
2H
5) Br
3And Ti (O (i-C
4H
9)) Br
3The dihalide titan-alkoxide is Ti (OCH for example
3)
2Cl
2, Ti (OC
2H
5)
2Cl
2, Ti (O (i-C
4H
9))
2Cl
2And Ti (OC
2H
5)
2Br
2Four titan-alkoxides are Ti (OCH for example
3)
4, Ti (OC
2H
5)
4And Ti (OC
4H
9)
4Or its mixture.Preferred titanium compound is a titanium tetrachloride.Based on the halogenated magnesium compound of 1mol, the consumption of titanium compound is preferably 0.5-1000mol, and most preferably is 1-500mol.In this scope, can obtain to have the catalyzer of optimum catalytic performance.
The monoester compound of choosing use in above-mentioned steps (4) wantonly refers to have one synoptically and uses general formula R
1COOR
2The organic compound of the ester group of expression, wherein R
1And R
2Be respectively to have C independently
1-25Alkyl or aryl.For example can mention alkyl aromatic ester and derivative thereof, for example ethyl benzoate, bromo-benzoic acid ethyl ester, butyl benzoate, isobutyl benzoate, hexyl-benzoate, phenylformic acid cyclohexyl etc.Based on the halogenated magnesium compound of 1mol, the consumption of the monoester compound of Shi Yonging is preferably 0.01-500mol herein, and 0.1-50mol more preferably.When not in above-mentioned scope, owing to can not obtain to have the catalyzer of optimum catalytic performance, thereby not by preferably.
The catalyzer of step (1)-(4) preparation by the inventive method is advantageously used in ethene (being total to) polyreaction.Especially, catalyzer can be used in ethylene homo reaction or ethene and have in the copolyreaction of alhpa olefin of 3 or more a plurality of carbon atoms, and described alhpa olefin is propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene and 1-hexene for example.Polyreaction is undertaken by using catalyst system, this catalyst system comprises (i) solid composite titanium catalyzer that contains magnesium, titanium, halogen and electron donor(ED) by method for preparing of the present invention, and the (ii) organometallic compound of period of element Table II family or III family.
Before using as a kind of component of polymerization process, solid composite titanium catalyzer of the present invention (i) can use with ethene or alhpa olefin prepolymerization.Prepolymerization reaction makes granules of catalyst be aggregated thing and surrounds, and can keep catalyst shape like this and help the improvement of polyreaction post polymerization thing form.In enough low temperature with under the pressure of ethene or alhpa olefin, in the presence of such as the hydrocarbon solvent of hexane, the prepolymerization reaction can be used aforesaid catalyst component and carry out such as the organo-aluminium compound of triethyl aluminum.After the prepolymerization reaction, polymkeric substance: the weight ratio of catalyzer is about 0.1: 1-60: 1.
Organometallic compound general formula (ii) is MR
n, wherein M is the metal component of period of element Table II family or III family, for example magnesium, calcium, zinc, boron, aluminium plus gallium; R has C
1-20Alkyl group, for example methyl, ethyl, butyl, hexyl, octyl group and decyl; And n is the atom valency of metal component.For organometallic compound, can advantageously use to have C
1-6The trialkylaluminium of alkyl group, for example triethyl aluminum and triisobutyl aluminium and composition thereof.In some cases, can use organo-aluminium compound, for example ethylaluminium dichloride, diethylaluminum chloride, sesquialter ethylaluminium chloride or diisobutylaluminium hydride with at least one halogen or hydrogenation group.
Polyreaction in the presence of catalyzer of the present invention can be carried out with gas phase or mass polymerization under the situation that does not contain organic solvent, or carries out with the liquid phase slurry polymerization in the presence of organic solvent.Can and may implement polymerisation process under the situation to deleterious other compounds of catalyzer at oxygen-free gas, water.Under the situation of liquid phase slurry polymerization, with respect to the 1L solvent, based on the titanium atom in the catalyzer, the ideal concentration of the solid composite titanium catalyzer of the present invention (i) that exists in polymerization reaction system is about 0.001-5mmol, preferably about 0.001-0.5mmol.Preferred solvent comprises: alkane is pentane, hexane, heptane, n-octane and octane-iso for example; Naphthenic hydrocarbon is hexanaphthene and methylcyclohexane for example; Alkylaromatics is toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, ethyltoluene, n-propylbenzene and diethylbenzene for example; Halogenated aromatic substance is chlorobenzene, chloronaphthalene and orthodichlorobenzene for example; And composition thereof.Under the situation of gas phase polymerization, with respect to 1L polyreaction volume, based on the titanium atom in the catalyzer, the desirable consumption of solid composite titanium catalyzer of the present invention (i) is 0.001-5mmol, preferably about 0.001-1.0mmol, most preferably from about 0.01-0.5mmol.Based on the titanium atom in the 1mol catalyzer of the present invention (i), be benchmark with the aluminium atom, organometallic compound ideal concentration (ii) is about 1-2000mol, more preferably from about 5-500mol in described polyreaction.
When polyreaction is at high temperature carried out, no matter use any polymerization process, all can obtain high speed of polymerization.Usually, preferably about 20-200 ℃ of polymeric reaction temperature, and more preferably 20-95 ℃.In polyreaction, monomer pressure preferably at normal atmosphere to the scope of 100atm, more preferably 2-50atm.
Beneficial effect
By method of the present invention, can under high yield, obtain to have high catalytic activity catalyst, and by in polyreaction, using this catalyzer, the ethylene homo compound or the multipolymer that can obtain to have high-bulk-density and single-size distribution of sizes.
Embodiment
Hereinafter, further specify the present invention by the following example and Comparative Examples.But these embodiment only for illustrative purposes and and do not mean that restriction the present invention.
Embodiment and Comparative Examples
Embodiment 1
In the present embodiment, the productive rate of Catalyst Production accounts for the MgCl of initial adding with the catalyst weight that makes
2The per-cent of weight (%) is represented.
Size of catalyst distributes, and (Mastersizer X MalvernInstruments) measures with the laser particle analyser.In the result, mean sizes is represented with D (v, 0.5), and distribution of sizes (D (v, 0.9)-D (v, 0.1))/D (v, 0.5) represents, D (v wherein, 0.5) be meant the particle size of 50% sample performance, D (v, 0.9) and D (v, 0.1) are meant the size of the sample performance of 90% sample and 10% respectively.The observed value that distributes is more little, and it is narrow more to distribute.The composition of catalyzer is analyzed with ICP.
(i) step of preparation magnesium compound solution
To atmosphere wherein being replaced and is equipped with in the churned mechanically 10L reactor, add 230gMgCl with nitrogen
2, 2800mL toluene, 240mL tetrahydrofuran (THF) and 710mL butanols.Subsequently, stirring the mixture under the speed of 550rpm rises to temperature 110 ℃ simultaneously, and keeps 3 hours to obtain homogeneous solution.
(ii) catalytic step between magnesium compound solution and the alkoxysilane compound containing trialkylsilyl group in molecular structure
Above-mentioned steps (i) is obtained magnesium compound solution be cooled to 70 ℃, and subsequently with tetraethoxy-silicane/MgCl
2Mol ratio is 0.15 to wherein adding tetraethoxy-silicane, and reacts 1 hour.
The step that (iii) prepares solid carrier
The magnesium compound solution that above-mentioned steps is (ii) obtained is cooled to 35 ℃, and in 80 minutes to the TiCl that wherein adds 415mL
4In 1 hour, the temperature of reactor is risen to 60 ℃ subsequently, and ageing mixture 1 hour.After reaction, mixture was left standstill 30 minutes, make carrier to precipitate, and remove the top of solution subsequently.Remaining slurry the following step repeated washing 3 times in the reactor: add the 3000mL hexane; Stir the mixture and it is left standstill; And remove its supernatant liquid.
The step that (iv) prepares catalyzer
The carrier that under 5 ℃ step is (iii) obtained adds in the reactor with the toluene of 1600mL.Under the stirring velocity of 250rpm, in mixture, add the TiCl of 1400mL
4, and in 1 hour, the temperature of reactor risen to 70 ℃ and ageing subsequently 2 hours.Subsequently, it is left standstill precipitated in 30 minutes, and remove supernatant liquid.Use the purifying hexane of 1600mL to clean 7 times the catalyst slurry that obtains like this.Ti content is 3.2 weight % (wt%) in the catalyzer that obtains.
[polyreaction]
Autoclave dry and assembling when it is also hot in baking oven with the 2L volume.Replace 3 times with inside reactor atmosphere nitrogen replacement by using nitrogen and vacuum subsequently.In reactor, inject the n-hexane of 1000mL and inject the triethyl aluminum of 2mmol then and the hydrogen of 1000mL.Temperature with reactor under the stirring of 700rpm rises to 80 ℃, and ethylene pressure is adjusted to 120psig.Subsequently, inject above-mentioned catalyzer with consumption based on titanium atom 0.03mmol.Polyreaction was carried out 1 hour.After polyreaction is finished, the temperature of reactor is reduced to room temperature, and in polymerisate, add excess ethanol.Collect the polymkeric substance make like this and in vacuum drying oven drying at least 6 hours, obtain the white powder shaped polyethylene.
Weight (Kg) with the polymkeric substance that obtains is calculated polymerization activity (kg polyethylene/g catalyzer) than the amount (g) of using catalyzer.The tap density of polymerization results and polymkeric substance (g/mL) is represented in table 1.
Embodiment 2
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except step (ii) in, with tetraethoxy-silicane/MgCl
2Mol ratio is 0.10 adding tetraethoxy-silicane, and reacts 1 hour.The result of embodiment 2 represents in table 1.
Embodiment 3
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except step (ii) in, with tetraethoxy-silicane/MgCl
2Mol ratio is 0.05 adding tetraethoxy-silicane, and reacts 1 hour.The result of embodiment 3 represents in table 1.
Embodiment 4
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except step (ii) in, with tetramethoxy-silicane/MgCl
2Mol ratio is that 0.10 adding tetramethoxy-silicane replaces tetraethoxy-silicane, and reacts 1 hour.The result of embodiment 4 represents in table 1.
Embodiment 5
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except step (ii) in, with four butoxy silicon/MgCl
2Mol ratio is that 0.10 adding, four butoxy silicon replace tetraethoxy-silicane, and reacts 1 hour.The result of embodiment 5 represents in table 1.
Embodiment 6
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except step (iv) in: the TiCl that adds 1400mL
4Temperature with reactor in 1 hour rises to 25 ℃; At 25 ℃ of ethyl benzoates that slowly add 55mL down; Temperature with reactor in 1 hour rises to 70 ℃; Ageing 2 hours; It is left standstill precipitated in 30 minutes; Separate supernatant liquid; And use the purifying hexane of 1600mL to clean 7 times the catalyst slurry that obtains.The result of embodiment 6 represents in table 1.
Embodiment 7
With with embodiment 6 in identical method carry out Preparation of Catalyst and polyreaction, except step (iv) in, add the ethyl benzoate of 37mL.The result of embodiment 7 represents in table 1.
Embodiment 8
With with embodiment 6 in identical method carry out Preparation of Catalyst and polyreaction, except step (iv) in, add the ethyl benzoate of 18mL.The result of embodiment 8 represents in table 1.
Embodiment 9
With with embodiment 6 in identical method carry out Preparation of Catalyst and polyreaction, except step (iv) in, the butyl benzoate that adds 42mL replaces ethyl benzoate.The result of embodiment 9 represents in table 1.
Embodiment 10
With with embodiment 6 in identical method carry out Preparation of Catalyst and polyreaction, except step (iv) in, the butyl benzoate that adds 21mL replaces ethyl benzoate.The result of embodiment 10 represents in table 1.
Comparative Examples 1
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except step (ii) in, under the situation of not using tetraethoxy-silicane, react.The result of Comparative Examples 1 represents in table 1.
Comparative Examples 2
With with embodiment 1 in identical method carry out Preparation of Catalyst and polyreaction, except in step (i), used the 960mL tetrahydrofuran (THF) and do not used butanols.The result of Comparative Examples 2 represents in table 1.
Comparative Examples 3
With with embodiment 6 in identical method carry out Preparation of Catalyst and polyreaction, except step (ii) in, under the situation of not using tetraethoxy-silicane, react.The result of Comparative Examples 3 represents in table 1.
Comparative Examples 4
(i) step of preparation magnesium compound solution
To atmosphere wherein being replaced and is equipped with in the churned mechanically 1.0L reactor, add 95gMgCl with nitrogen
2, 4000mL toluene, and under the speed of 300rpm, stir.Rise to 120 ℃ subsequently to the 2-Ethylhexyl Alcohol that wherein adds 620mL, and with temperature.Make it react 3 hours, be cooled to 70 ℃ to obtain homogeneous solution.
(ii) catalytic step between magnesium compound solution and the alkoxysilane compound containing trialkylsilyl group in molecular structure
Above-mentioned steps (i) is obtained magnesium compound solution be cooled to 70 ℃, and subsequently to the tetraethoxy-silicane that wherein adds 100.0mL.Made mixture reaction 1 hour.
The step that (iii) prepares catalyzer
The magnesium compound solution that step is (ii) obtained transfers to room temperature (25 ℃), and in 1 hour to the TiCl that wherein dropwise adds 600mL
4Add fashionablely when finishing, the temperature with reactor in 1 hour rises to 70 ℃, and keeps this high temperature 1 hour.After stopping stirring, remove supernatant liquid and in remaining solid phase, add the toluene of 3000mL and the TiCl of 1000mL continuously
4Temperature is risen to 100 ℃ and kept 2 hours.After reaction, with reactor cooling to room temperature, and with the 4000mL hexane wash until removing unreacted free TiCl
4Ti content in the solid catalyst that obtains is 3.7wt%.Carry out polyreaction with the catalyzer that obtains, and the result represents at table 1.
Comparative Examples 5
With with Comparative Examples 4 in identical method carry out Preparation of Catalyst and polyreaction, except the step of Comparative Examples 4 (ii) in, under the situation of not using tetraethoxy-silicane, reacted 1 hour.The result of this Comparative Examples 5 represents in table 1.
Comparative Examples 6
With with Comparative Examples 4 in identical method carry out Preparation of Catalyst and polyreaction, except the step of Comparative Examples 4 (iii) in, adding TiCl
4The back further adds the ethyl benzoate of 30mL.The result of Comparative Examples 6 represents in table 1.
Comparative Examples 7
With with Comparative Examples 6 in identical method carry out Preparation of Catalyst and polyreaction, except the step of Comparative Examples 6 (ii) in, under the situation of not using tetraethoxy-silicane, reacted 1 hour.The result of Comparative Examples 7 represents in table 1.
Table 1
| Productive rate (%) | The mean sizes of catalyzer (μ m) | Size of catalyst distributes | Polymerization activity (kgPE/g catalyzer) | Tap density (g/mL) | |
| Embodiment 1 | 124 | 6.4 | 0.82 | 17.2 | 0.33 |
| Embodiment 2 | 122 | 5.7 | 0.79 | 17.9 | 0.32 |
| Embodiment 3 | 126 | 5.5 | 0.80 | 16.9 | 0.32 |
| Embodiment 4 | 125 | 6.5 | 0.72 | 18.2 | 0.34 |
| Embodiment 5 | 123 | 5.8 | 0.77 | 16.6 | 0.34 |
| Embodiment 6 | 132 | 6.4 | 0.82 | 14.2 | 0.39 |
| Embodiment 7 | 131 | 5.7 | 0.79 | 17.9 | 0.38 |
| Embodiment 8 | 130 | 5.5 | 0.80 | 22.9 | 0.37 |
| Embodiment 9 | 133 | 6.5 | 0.72 | 19.2 | 0.38 |
| Embodiment 10 | 129 | 5.8 | 0.77 | 21.6 | 0.36 |
| Comparative Examples 1 | 120 | 6.8 | 1.2 | 15.4 | 0.28 |
| Comparative Examples 2 | 120 | 7.7 | 3.5 | 12.7 | 0.25 |
| Comparative Examples 3 | 109 | 6.6 | 1.2 | 13.4 | 0.29 |
| Comparative Examples 4 | 115 | 8.9 | 1.5 | 14.8 | 0.29 |
| Comparative Examples 5 | 110 | 6.5 | 3.9 | 16.2 | 0.23 |
| Comparative Examples 6 | 112 | 8.8 | 1.7 | 11.8 | 0.31 |
| Comparative Examples 7 | 113 | 6.4 | 3.5 | 13.2 | 0.25 |
*) size of catalyst distribution=(D (v, 0.9)-D (v, 0.1))/D (v, 0.5)
By above-mentioned table 1 as seen,, can under high yield, obtain to have high catalytic activity catalyst by in polyreaction, using the catalyzer of the inventive method preparation, and Alathon or multipolymer with high-bulk-density and single-size distribution of sizes.
Claims (7)
1. vinyl polymerization or copolyreaction Preparation of catalysts method is characterized in that may further comprise the steps:
(1) by mixed solvent contact reacts with halogenated magnesium compound and cyclic ethers and at least a alcohol, the preparation magnesium compound solution;
(2) magnesium compound solution that above-mentioned steps (1) is obtained and silicon compound reaction with at least one alkoxy base;
(3) by preparing carrier in the product that will join step (2) acquisition by the titanium compound of general formula (I) expression:
Ti(OR)
aX
(4-a)......(I)
Wherein R has C
1-10Alkyl group; X is a halogen atom; And a is the integer of 0-4; With
(4) with the carrier and the titanium compound reaction that obtain, obtain catalyzer.
2. in step (4), further add monoester compound according to the process of claim 1 wherein.
3. according to the method for claim 1 or 2, wherein cyclic ethers is tetrahydrofuran (THF) or 2-methyltetrahydrofuran in step (1), and alcohol is monobasic or the polyvalent alcohol with 1-20 carbon atom.
4. according to the method for claim 1 or 2, wherein based on the halogenated magnesium compound of 1mol, the consumption of mixed solvent is 1-20mol in step (1).
5. according to the method for claim 1 or 2, the silicon compound that wherein has at least one alkoxyl group in the step (2) has R
nSi (OR
1)
4-nGeneral formula, wherein R and R
1Be to have C independently
1-12Hydrocarbon; And n is the integer of 0-3.
6. according to the method for claim 2, wherein monoester compound has R
1COOR
2General formula, R wherein
1And R
2Be to have C independently
1-25Alkyl or aryl.
7. according to the method for claim 2, wherein based on the halogenated magnesium compound of 1mol, the consumption of monoester compound is 0.01-500mol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080017292A KR20090092023A (en) | 2008-02-26 | 2008-02-26 | A preparation method of catalyst for ethylene (co)polymerization |
| KR1020080017293 | 2008-02-26 | ||
| KR1020080017292 | 2008-02-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686614A (en) * | 2009-12-22 | 2012-09-19 | 巴塞尔聚烯烃股份有限公司 | Catalyst components for the polymerization of olefins and catalysts therefrom obtained |
| CN105622802A (en) * | 2014-11-06 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction, catalyst, and preparation method of catalyst component |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140136239A (en) * | 2013-05-20 | 2014-11-28 | 삼성토탈 주식회사 | A preparation method of the size-controllable catalyst for ethylene (co)polymerization |
-
2008
- 2008-02-26 KR KR1020080017292A patent/KR20090092023A/en not_active Application Discontinuation
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686614A (en) * | 2009-12-22 | 2012-09-19 | 巴塞尔聚烯烃股份有限公司 | Catalyst components for the polymerization of olefins and catalysts therefrom obtained |
| US9051400B2 (en) | 2009-12-22 | 2015-06-09 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins and catalysts therefrom obtained |
| CN105622802A (en) * | 2014-11-06 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction, catalyst, and preparation method of catalyst component |
| CN105622802B (en) * | 2014-11-06 | 2017-12-19 | 中国石油化工股份有限公司 | Catalytic component, catalyst for ethylene polymerization and preparation method thereof |
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