CN102344508B - Ethylene polymerization catalyst containing ether compound, preparation method thereof, and application thereof - Google Patents
Ethylene polymerization catalyst containing ether compound, preparation method thereof, and application thereof Download PDFInfo
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Abstract
The invention relates to an ethylene polymerization catalyst containing an ether compound, a preparation method thereof, and an application thereof. The method comprises steps that: (1) a magnesium halide compound and a titanic acid ester compound are subject to a reaction, such that a solution is formed, wherein the titanic acid ester compound is controlled at 1.0 to 10mol relative to each mole of magnesium halide, and a reaction temperature is 120 to 200 DEG C; (2) the formed solution is mixed with an ether compound, wherein the ether compound is controlled at 0.01 to 20mol, and a mixing temperature is 0 to 150 DEG C; (3) the mixed solution obtained in the step (3) is subject to a contact reaction with a chlorine-containing compound, such that a precipitate is obtained, and the catalyst is obtained, wherein the chlorine-containing compound is controlled at 0.5 to 50mol, and a temperature is controlled at 0 to 100 DEG C. The prepared catalyst particles are advantaged in good appearances, uniform particle-size distribution, good hydrogen modulation sensibility, and low polymerization product refinement content, such that the catalyst can be used in gas-phase and slurry polymerization process equipments.
Description
Technical field
The present invention relates to a kind of alkene that contains ether compound particularly catalyzer and the preparation and the application of vinyl polymerization or copolymerization.
Background technology
As everyone knows; The catalyst body that contains the Ti/Mg mixture ties up in the poly suitability for industrialized production occupies an leading position, and its research core is nothing more than the hydrogen response of the particle form of the polymerization activity that is catalyzer, catalyzer and size distribution, catalyzer and copolymerization performance or the like.And in slurry polymerization process of ethylene, except that requiring catalyzer should have the advantages of high catalytic activity, polyvinyl size and size distribution that control is produced are crucial.At vinyl polymerization, particularly in the slurry polymerization process of ethene, be easy to produce fine polymer powder, this fine powder is prone to produce static, is prone to caking, causes the obstruction of equipment pipe.And the effective means of the size of controlling polymers and size distribution is the particle diameter and the size distribution of control catalyst.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, two class methods below people adopt usually prepare catalyzer.
First kind is magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent; And then with this solution and titanium compound and randomly electron donor mix; Obtain containing the solids of magnesium, titanium and optional electron donor through sedimentary method, and obtain granules of catalyst after this solids handled with excessive liquid titanium compound.For example disclosed among Chinese patent CN1099041A, the CN1229092 etc.The shortcoming of this traditional method is that the particle diameter and the size distribution of granules of catalyst controlled through precipitation process fully, and this is the recrystallization process of magnesium carrier composition, and its stable ratio is difficulty.
For example, in patent CN1229092, be carrier with the magnesium chloride, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is following: earlier with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then the precipitation additive phthalic anhydride exist and low temperature under and TiCl
4Reaction is separated out solid catalyst through slow intensification.When the catalyst component that makes was used for vinyl polymerization, though the particle form of polymkeric substance is better, the fine polymer powder that catalyzer prepares in industrial production was still more, and the hydrogen response and the catalytic activity of catalyzer are also unsatisfactory simultaneously.Simultaneously, when synthetic this catalyzer, need adopt organism such as phthalic anhydride to promote sedimentary separating out, and need to add a large amount of titanium tetrachlorides as precipitation additive.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides also can cause a large amount of wastes and pollution.
Second kind is the carrier that preparation earlier has good particle form, carries titanium then, and prepared in reaction obtains highly active polyolefin catalyst.Chinese patent CN85105150 for example, patents such as CN101300278.
Chinese patent CN85105150 at first adopts magnesium halide and titan-alkoxide reaction; Generate solid magnesium-containing carrier with the aluminum alkyls reaction then with better particle form; This carrier and titanium tetrachloride reaction obtain solid catalyst at last, and the polyethylene polymer of this Preparation of Catalyst has characteristics such as tap density height, active height.But magnesium halide and titan-alkoxide reaction product fail to form solution in this Preparation of catalysts process when reacting with aluminum alkyls; The magnesium-containing carrier particle form that obtains is not ideal enough; The polymkeric substance segmentation content of preparation is still more, and the hydrogen regulation performance of this catalyzer is slightly poor simultaneously.
As everyone knows; In slurry polymerization process of ethylene; Except that requiring catalyzer should have advantages of high catalytic activity and preferably the size distribution,, also requiring catalyzer should have better hydrogen regulation sensitivity in order to produce Alathon or multipolymer with better performance; The melting index of promptly regulating final polymkeric substance through hydrogen dividing potential drop in the polymerization process at an easy rate is to obtain the polyvinyl resin of the different commercial trades mark.And the hydrogen response of above-mentioned catalyst system is also unsatisfactory.
Therefore; Being starved of provides a kind of catalyzer that is applicable to slurry polymerization process of ethylene; Not only catalytic activity is high for it, particle diameter evenly, narrow diameter distribution, and have good hydrogen response, the polymkeric substance of its preparation has advantages such as uniform particles, narrow diameter distribution, segmentation content are few.
Summary of the invention
The purpose of this invention is to provide a kind of contain ether compound be used for that ethylene homo closes or ethene and other a-alpha-olefinic copolymerization catalyzer and preparation and application.
The preparation method who is used for ethylene rolymerization catalyst who contains ether compound of the present invention comprises:
(1) reaction of halogenated magnesium compound and titanate ester compound forms solution;
(2) solution that forms is mixed with ether compound;
(3) mixed solution and the chlorine-containing compound contact reacts that step (2) are obtained form deposition, obtain catalyzer.
Catalyzer of the present invention has advantages such as advantages of high catalytic activity, better hydrogen regulation sensitivity and narrow grain size distribution of polymers, segmentation content are few, is highly suitable for slurry polymerization process of ethylene and needs in the polymerization mix technology of high activated catalyst.
Halogenated magnesium compound described in the preparation method such as general formula (I) Mg (OR
1)
nCl
2-nShown in, R in the formula
1Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤2, concrete compound such as MgCl
2, Mg (OEt) Cl, Mg (OEt)
2And the alkoxyl magnesium compound of long-chain, the organo-magnesium compound that uses in the reaction is preferably diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, two octyloxy magnesium etc.
Described metatitanic acid lipoid substance such as general formula (II) Ti (OR
2)
nCl
4-nShown in, R in the formula
2Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, tetravalent titanium compound is preferably used in 0≤n≤4, because they are in a liquid state usually at normal temperatures, and also fine with the consistency of some solvents under normal conditions.The compound of n=4 and their mixture in the titanium compound preferred formula of specifically using in the reaction, like purity titanium tetraethoxide, four titanium butoxide; The tetramethoxy titanium; Dimethoxy diethylammonium titanium, four hexyloxy titaniums, four the last of the ten Heavenly stems oxygen base titanium, benzyloxy-4 titanium, four phenoxide titaniums etc.; Wherein preferred four titanium butoxide
Described ether compound is alkyl, the cycloalkyl ethers that contains the 2-20 carbon atom; Object lesson is ether, dipropyl ether, dibutyl ether, diamyl ether, isoamyl ether, THF, dioxy six change rings etc.; Wherein preferred cycloalkyl ethers compounds, most preferably THF, dioxy six are changed ring.
Described chlorine-containing compound such as general formula (III) M (OR
3)
nCl
4-nShown in, M is metal or non-metallic element in the formula, R
3Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤4.The example of chlorine-containing compound comprises: silicon tetrachloride, tetracol phenixin, zirconium tetrachloride, boron trichloride, phosphorus trichloride aluminum chloride etc., wherein preferred silicon tetrachloride.
In Preparation of catalysts process of the present invention, the ratio between the each component is, in every mole of general formula (I) compound; General formula (II) compound is controlled at 1.0～10 moles; Preferred 2.1～3.5 moles, ether compound is controlled at 0.01～20 mole, preferred 0.2～12 mole; General formula (III) chlorine-containing compound consumption is controlled at 0.5～50 mole, preferred 2～20 moles.
In the first step of preparation catalyzer; The temperature that magnesium compound and titanium compound are in contact with one another depends on the character of reactant; Be typically chosen in dissolve under the higher relatively temperature comparatively favourable; Preferably below the decomposition temperature of reactant, temperature is generally 120～200 ℃, is generally 120～150 ℃.The dissolved time is depended on the character and the operational condition of reactant, and general selection of time be with till can obtaining fully transparent solution, and required time is generally at 10 minutes to 20 hours, preferred 4 to 10 hours.After treating the dissolving of magnesium compound and titanium compound; The magnesium titanium complex solution that forms can mix use with inert diluent; Inert diluent is selected from aliphatics or aromatic hydrocarbon based usually; For example benzene,toluene,xylene, Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, general toluene or hexane are proper inert solvents.
In second step of preparation catalyzer, the mixing temperature of magnesium titanium complex solution and ether compound generally will be lower than the decomposition temperature of material, for simplicity, generally selects between 0～150 ℃, between preferred 15～50 ℃.The mixing time of magnesium titanium complex solution and ether compound is general selects 0.5 minute to 5 hours, preferred 30 minutes to 1 hour.
The 3rd step of Preparation of Catalyst also can be described as settling step, in this step, accomplishes the chlorination reaction of magnesium titanium complex, and just the chlorine element replaces the alkoxyl group in magnesium compound and the titanium compound, separates out thereby liquid title complex is precipitated from solution.The contact method of magnesium titanium complex solution and chlorine-containing compound can adopt any known suitable method to carry out; Can adopt magnesium titanium complex solution progressively is added drop-wise to the mode in the chlorine-containing compound solution, also can adopt chlorine-containing compound solution progressively is added drop-wise to the mode in the magnesium titanium complex solution.Rate of addition is selected to be as the criterion with the local superheating that does not induce reaction usually, in the dropping process, stirs steadily carrying out of being beneficial to react usually.In this precipitin reaction step, temperature can be controlled between 0～100 ℃, preferably between 20～80 ℃.The reaction times of settling step should be long enough to obtain deposition completely, and the reaction times can be lasted 1 minute to 10 hours, preferred 0.5～5 hour.
Experiment is found; After settling step; Reacting for some time at a certain temperature, to carry out maturation process more favourable to the grain type of catalyzer; It can make the size distribution narrow of catalyzer, also can improve the intensity of catalyst particle simultaneously, thereby reduces the particle fragmentation phenomenon of catalyzer in the catalyzed ethylene polymerization process.The temperature of maturation process generally is equal to or higher than the temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5～15 hour, preferred 1～5 hour.
After carrying out maturation process; Generally to wash; So that remove the by product that forms in excessive reactant and the preparation process; Any inert solvent all can be used for this washing step, for example can select Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof etc., selects the inert solvent of hexane for washing in the experiment usually.After washing, catalyst suspension can be through carrying out drying with nitrogen purging, to obtain catalyst fines under heating state.
The invention still further relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, it contains the above-mentioned catalyst component of the present invention and the reaction product of alkylaluminium cpd, and the general formula of wherein used alkylaluminium cpd is AlR " '
3, R " ' be C identical or inequality
1-8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls mix to use, preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other terminal olefins, and wherein terminal olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1.
Embodiment
The median size of catalyzer and the test of size-grade distribution thereof
Catalyst sample is dispersed in the hexane, adopts the size distribution curve of Malversizer laser particle size analyzer specimen, wherein
The median size of catalyzer provides with D (50)
The size-grade distribution Span=of catalyzer (D (90)-D (10))/D (50)
D in the formula (50) is the diameter value that the diameter of whole particulate 50% in the size distribution curve of Malversizer laser particle size analyzer test is lower than this value; D (10) is the diameter value that the diameter of whole particulate 10% is lower than this value; D (90) is the diameter value that the diameter of whole particulate 90% is lower than this value.Polymerization catalyst performance evaluation
1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in the 2L stainless steel stirring tank, then temperature is brought up to 90 ℃, the hydrogen of disposable adding 0.4MPa; With ethene the total pressure of system is maintained 1.0MPa then and carry out polyreaction, react after 2 hours, stop to add ethene; Cooling, pressure release, polyethylene powder is weighed; Calculate activity of such catalysts, and the polyethylene powder that obtains is sieved.
Embodiment 1:
(1) takes by weighing 10.2 gram magnesium chlorides, add 78 milliliters of tetrabutyl titanates, until forming clear solution, solution temperature is reduced to room temperature, add 200 milliliters of dry hexane diluted for use 140 ℃ of stirring and dissolving.
(2) get 20 milliliter of (1) solution that obtains of step, mix with 0.3 milliliter of THF and place and spend the night.Under the normal temperature, this solution slowly is added drop-wise in the mixed solution of 30 milliliters of hexanes and 20 milliliters of silicon tetrachlorides, after being added dropwise to complete, bathed 45 ℃ of stirring reactions of temperature 1 hour, bathed 65 ℃ of stirring reactions of temperature 2 hours, obtain catalyst suspension.
(3) the catalyst suspension temperature is reduced to room temperature, leaves standstill, sedimentation, with hexane wash three times, the consumption of each hexane is 50 milliliters, after washing is accomplished, under the situation of bathing 65 ℃ of temperature, purge with high pure nitrogen dry, the solids flowability powder.
The median size of catalyzer (D (50)): 21 microns, particle diameter distribution width Span:0.6, the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 2
0.3 milliliter of THF in the catalyst preparation step (2) is adjusted into 0.6 milliliter, and other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 19 microns, particle diameter distribution width Span:0.6, the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 3
0.3 milliliter of THF in the catalyst preparation step (2) is adjusted into 1.2 milliliters, and other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 19 microns, particle diameter distribution width Span:0.6, the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 4
0.3 milliliter of THF in the catalyst preparation step (2) is adjusted into 1.8 milliliters, and other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 17 microns, particle diameter distribution width Span:0.8, the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 5
The hexane that uses in the catalyst preparation step (2) is replaced with the toluene with volume, but still use the hexane with volume during catalyst detergent, other conditions are with embodiment 1.
The median size of catalyzer (D (50)): 8.2 microns, particle diameter distribution width Span:0.6, the screening result of activity of such catalysts and polyethylene powder is as shown in table 1
Comparative Examples 1
(1) takes by weighing 10.2 gram magnesium chlorides, add 78 milliliters of tetrabutyl titanates, until forming clear solution, solution temperature is reduced to room temperature, add 200 milliliters of dry hexane diluted for use 140 ℃ of stirring and dissolving.
(2) get the solution that 20 milliliter of (1) step obtains; This solution slowly is added drop-wise at normal temperatures in the mixed solution of 30 milliliters of hexanes and 20 milliliters of silicon tetrachlorides, after being added dropwise to complete, bathed 45 ℃ of stirring reactions of temperature 1 hour; Bathe 65 ℃ of stirring reactions of temperature 2 hours, and obtained catalyst suspension.
(3) the catalyst suspension temperature is reduced to room temperature, leaves standstill, sedimentation, with hexane wash three times, the consumption of each hexane is 50 milliliters, after washing is accomplished, under the situation of bathing 65 ℃ of temperature, purge with high pure nitrogen dry, the solids flowability powder.
The median size of catalyzer (D (50)): 22 microns, particle diameter distribution width Span:0.6, the quiet photo of scanning electricity of catalyzer is as shown in Figure 1, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Comparative Examples 2
The synthetic CN85105150 embodiment 1 said method of pressing of catalyst component prepares.
The median size of catalyzer (D (50)): 8.2 microns, particle diameter distribution width Span:1.2, the screening result of activity of such catalysts and polyethylene powder is as shown in table 1
Can find out that from the aggregated data of table 1 under same polymerizing condition, catalyst activity of the present invention is higher, hydrogen regulation performance is very good, and the size distribution of resulting polymers is narrower, and it is all less to cross thick or meticulous particle in the polymkeric substance.
Table 1
Claims (3)
1. preparation method who contains the ethylene rolymerization catalyst of ether compound is characterized in that:
(1) reaction of magnesium chloride and tetrabutyl titanate forms solution, and every mole of magnesium chloride meter, tetrabutyl titanate are controlled at 1.0～10 moles, and temperature of reaction is 120-200 ℃;
(2) solution that forms is mixed with THF, THF is controlled at 0.01～20 mole, 0～150 ℃ of mixing temperature;
(3) mixed solution and the silicon tetrachloride contact reacts that step (2) are obtained form deposition, obtain catalyzer, and silicon tetrachloride is controlled at 0.5～50 mole, and temperature is controlled at 0～100 ℃.
2. an ethylene rolymerization catalyst that contains ether compound is characterized in that: preparing method's preparation according to claim 1.
3. the described application that contains the ethylene rolymerization catalyst of ether compound of claim 2 is characterized in that: be used for the slurry polymerization process of ethylene catalyzer.
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| CN105085735B (en) * | 2014-04-29 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN105085742B (en) * | 2014-04-29 | 2018-06-12 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN105085734B (en) * | 2014-04-29 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN105085737B (en) * | 2014-04-29 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN105085741B (en) * | 2014-04-29 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN105085743B (en) * | 2014-04-29 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
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| JP3280477B2 (en) * | 1992-08-31 | 2002-05-13 | 三井化学株式会社 | Method for preparing solid titanium catalyst component for olefin polymerization |
| EP0622379B1 (en) * | 1993-04-29 | 1998-07-08 | Ticona GmbH | Process for the production of a catalyst system for the (co)polymerisation of ethylene into ultra-high molecular weight ethylene (co)polymers |
| BE1007653A3 (en) * | 1993-10-26 | 1995-09-05 | Fina Research | Polyethylene production process with broad molecular weight distribution. |
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