CN102766226A - Main catalyst for ethylene polymerization and catalyst containing same - Google Patents
Main catalyst for ethylene polymerization and catalyst containing same Download PDFInfo
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- CN102766226A CN102766226A CN2012102800820A CN201210280082A CN102766226A CN 102766226 A CN102766226 A CN 102766226A CN 2012102800820 A CN2012102800820 A CN 2012102800820A CN 201210280082 A CN201210280082 A CN 201210280082A CN 102766226 A CN102766226 A CN 102766226A
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Abstract
The invention relates to a main catalyst for ethylene polymerization and a catalyst containing the main catalyst. The main catalyst comprises a magnesium compound, an alcohol compound, a titanium compound and a chlorine-containing compound. A preparation method of the main catalyst comprises the following steps of mixing the magnesium compound with the alcohol compound to form transparent solution; mixing the transparent solution with the titanium compound to obtain magnesium titanium complex solution; mixing the magnesium titanium complex solution with the chlorine-containing compound until completely precipitating to obtain main catalyst suspension; conducting aging reaction on the main catalyst suspension; and washing and drying the main catalyst suspension after aging to obtain the main catalyst. The catalyst comprises the main catalyst and an organo-aluminum compound. The main catalyst has good particle shape and narrow size distribution, and is applicable to a slurry polymerization process of ethylene; and when the main catalyst is matched with a promoter for use, the prepared polymers have the advantages of being even in particles, narrow in size distribution, fewer in fine components and the like.
Description
Technical field
The present invention relates to a kind of be used for olefinic polymerization particularly ethylene homo close or the Primary Catalysts of copolymerization and preparation method thereof, and contain catalyzer of this Primary Catalysts and uses thereof, belong to the olefin polymerization catalysis field.
Background technology
After the seventies, high-efficiency polyethylene catalyst was succeeded in developing, great change had taken place in world's Vilaterm industry.Over nearly more than 20 years; Follow the development of ethene polymerization process; Also obtained significant progress with the catalyzer that polymerization technique matches; Wherein effective catalyst relies on its good polymerization and sophisticated utilisation technology in the polyethylene catalysts field, still to occupy an important position, and still has the number of patents application to occur in recent years.In these patented claims, the 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 CN1099041A, the CN1229092A 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 CN1229092A, 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.For example CN85105150A is disclosed among the CN101300278A etc.
CN85105150B 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, and the magnesium-containing carrier particle form that obtains is not ideal enough, and the polymkeric substance segmentation content of preparation is still more.
Therefore, still having needs a kind of catalyzer that is applicable to slurry polymerization process of ethylene of research and development, makes its catalytic activity height, even, the narrow diameter distribution of particle diameter; And the polymkeric substance that makes its preparation has advantages such as uniform particles, narrow diameter distribution, segmentation content are few.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of vinyl polymerization Primary Catalysts, its have catalytic activity height, particle diameter evenly, advantage such as narrow diameter distribution.
The present invention also aims to provide the preparation method of above-mentioned vinyl polymerization Primary Catalysts.
Another purpose of the present invention is to provide a kind of catalyzer and application thereof that contains above-mentioned Primary Catalysts.
For reaching above-mentioned purpose, the present invention provides a kind of vinyl polymerization Primary Catalysts, and its raw material comprises magnesium compound, alcohol compound, titanium compound and chlorine-containing compound;
Wherein, said magnesium compound is like formula M g (OR
1)
nCl
2-nShown in one or more combination in the compound, in the formula, R
1Be C
2-C
20Alkyl, it can be saturated or undersaturated straight-chain alkyl, branched hydrocarbyl or closed chain alkyl, n is integer and 0≤n≤2;
Said alcohol compound is like general formula R
2The combination of one or more shown in the OH in the compound, in the formula, R
2Be C
2-C
20Alkyl, it can be saturated or undersaturated straight-chain alkyl, branched hydrocarbyl or closed chain alkyl;
Said titanium compound is like general formula Ti (OR
3)
mCl
4-mShown in one or more combination in the compound, in the formula, R
3Be C
2-C
20Alkyl, it can be saturated or undersaturated straight-chain alkyl, branched hydrocarbyl or closed chain alkyl, m=1,2,3 or 4;
Said chlorine-containing compound is like formula M (OR
4)
fCl
4-fShown in one or more combination in the compound, in the formula, M is metal or non-metallic element, R
4Be C
2-C
20Alkyl, it can be saturated or undersaturated straight-chain alkyl, branched hydrocarbyl or closed chain alkyl, f is integer and 0≤f≤4;
The mol ratio of said magnesium compound, said alcohol compound, said titanium compound and said chlorine-containing compound is 1: (1-10): (0.01-20): (0.01-20), and respectively in the molar weight of magnesium elements, the molar weight of OH, the molar weight of titanium elements and the molar weight of chlorine element.
In above-mentioned Primary Catalysts, preferably, said magnesium compound is magnesium chloride (MgCl
2), chlorination magnesium ethylate (Mg (OEt) Cl), diethoxy magnesium (Mg (OEt)
2) and the alkoxyl magnesium compound of long-chain etc. in one or more combination.More preferably, said magnesium compound is one or more the combination in diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, the two octyloxy magnesium.
In above-mentioned Primary Catalysts, preferably, said alcohol compound is for containing C
6-C
20The alcohol compound of straight-chain alkyl or branched hydrocarbyl in one or more combination.More preferably, said alcohol compound is one or more the combination in 2-methyl amyl alcohol, 2-ethylpentanol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, hendecanol, dodecanol, tetradecanol, oleyl alcohol, hexalin and the methyl-cyclohexanol etc.Particularly preferably, said alcohol compound is a 2-Ethylhexyl Alcohol.
In above-mentioned Primary Catalysts, preferably, said titanium compound is TiCl
4, Ti (OCH
3) Cl
3, Ti (OCH
3)
2Cl
2, Ti (OCH
3) Cl
3, Ti (OC
2H
5) Cl
3, Ti (OC
2H
5)
2Cl
2, Ti (OC
2H
5)
3Cl, Ti (OC
4H
9) Cl
3, Ti (OC
4H
9)
2Cl
2And Ti (OC
4H
9)
3The combination of one or more among the Cl etc.More preferably, said titanium compound is TiCl
4
In above-mentioned Primary Catalysts, preferably, said chlorine-containing compound is one or more the combination in silicon tetrachloride, titanium tetrachloride, zirconium tetrachloride, boron trichloride, phosphorus trichloride and the aluminum chloride etc.More preferably, said chlorine-containing compound is a silicon tetrachloride.
In above-mentioned Primary Catalysts, preferably, the mol ratio of said magnesium compound, said alcohol compound, said titanium compound and said chlorine-containing compound is 1: (2-5): (0.2-1): (1-10).
The present invention also provides the preparation method of above-mentioned vinyl polymerization Primary Catalysts, and it comprises the steps:
At 25 ℃-200 ℃, magnesium compound and alcohol compound to be mixed, sustained reaction 10 minutes to 20 hours is so that form clear solution;
At-10 ℃ to 50 ℃, said clear solution to be mixed with titanium compound, sustained reaction 30 minutes to 5 hours obtains magnesium titanium complex solution;
At-20 ℃ to 150 ℃, said magnesium titanium complex solution to be mixed with chlorine-containing compound, sustained reaction obtained Primary Catalysts suspension-s to precipitating fully in 1 minute to 10 hours;
At 25 ℃ to 100 ℃, said Primary Catalysts suspension-s was carried out slaking reaction 0.5 to 15 hour;
With the Primary Catalysts suspension-s after the said slaking wash, drying, obtain Primary Catalysts.
In the preparation method of above-mentioned Primary Catalysts; The temperature of magnesium compound and alcohol compound hybrid reaction depends on the character of reactant; Be typically chosen in and react comparatively favourable under the higher relatively temperature; Preferably below the decomposition temperature of reactant, temperature of reaction is not higher than 200 ℃ usually, generally is not higher than 150 ℃.The time of reaction is depended on the character and the operational condition of reactant, and general selection of time is with till can obtaining transparent fully solution, and the reaction times, preferably, the reaction times was 4 to 10 hours generally at 10 minutes to 20 hours.
In the preparation method of above-mentioned Primary Catalysts, said clear solution is mixed formation magnesium titanium complex with titanium compound, the temperature of reaction during mixing can be controlled at-10 to 50 ℃, and the time of hybrid reaction is more than half a hour.After mixing completion; Can dilute the magnesium titanium complex solution that obtains with inert diluent, inert diluent can be aliphatic hydrocarbon, for example the combination of one or more in Trimethylmethane, pentane, hexane, heptane or the hexanaphthene; Wherein, hexane is proper inert solvent.
In the preparation method of above-mentioned Primary Catalysts; Magnesium titanium complex solution also can be described as settling step with mixing of chlorine-containing compound; In this step, accomplish the chlorination reaction of magnesium titanium complex; 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 blending means 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 of reaction can be controlled at-20 to 150 ℃, and preferably, temperature of reaction is 0 to 50 ℃.The reaction times of this settling step should be long enough to obtain deposition completely, and the reaction times can be 1 minute to 10 hours, and preferably, the reaction times is 0.5 to 1 hour.
In the preparation method of above-mentioned Primary Catalysts; There is favorable influence in said slaking reaction to the grain type of catalyzer; This slaking reaction can make the size distribution narrow of catalyzer; Also can improve simultaneously the intensity of catalyst particle, thereby reduce the particle fragmentation phenomenon of catalyzer in the catalyzed ethylene polymerization process.The temperature of said slaking reaction generally is equal to or higher than the temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5 to 15 hour, and preferably, the reaction times is 1 to 5 hour.
After carrying out slaking reaction, generally the major catalyst suspension after the said slaking to be washed, so that remove the accessory substance that forms in excessive reactant and the preparation process.Any inert solvent all can be used for this washing step, the for example combination of one or more in Trimethylmethane, pentane, hexane, heptane or the hexanaphthene etc., and selecting hexane usually is the inert solvent of washing.After washing, said Primary Catalysts suspension-s need pass through drying step and obtain solid main catalyst, this drying step can under heating state with the said Primary Catalysts suspension-s of nitrogen purging.
The present invention also provides a kind of ethylene polymerization catalysts, and it comprises following component:
Above-mentioned vinyl polymerization Primary Catalysts;
Organo-aluminium compound (promotor), it is like general formula AlR
5 gX
3-gShown in one or more combination in the compound, in the formula, R
5Be C
1-C
20Alkyl, X is a halogen, g is integer and 1＜g≤3;
The mole of said organo-aluminium compound and said Primary Catalysts is 1: (5-1000), and respectively in the molar weight of Al element and Ti element.
In above-mentioned catalyzer, preferably, said organo-aluminium compound is AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3And AlEt
2The combination of one or more among the Cl etc.
The present invention also provides the application in the copolymerization of equal polymerization or ethene and other terminal olefins of above-mentioned catalyzer at ethene.Said terminal olefin can be propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
Primary Catalysts of the present invention has good particle form and very narrow size-grade distribution, is highly suitable for slurry polymerization process of ethylene, is particularly suitable for the double-reactor slurry polymerization processes.Itself and promotor are used, and make the polymkeric substance for preparing have advantages such as uniform particles, narrow diameter distribution, segmentation content are few.
Embodiment
Below in conjunction with embodiment the present invention is described further, but protection scope of the present invention is not limited only to following 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 the Mastersizer laser particle size analyzer specimen of Britain Malvern Instruments Ltd. company, 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 Mastersizer 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
The Primary Catalysts of 1L hexane, 1mmol triethyl aluminum (promotor) and 50mg is joined in the 2L stainless steel stirring tank, then temperature is risen 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 with the weight of polyethylene powder divided by the consumption of Primary Catalysts, the melting index of polyethylene powder (MI) is according to ASTM D 1,238 2004 standard testings, and testing load is 2.16Kg, and the polyethylene powder that obtains is sieved.
Embodiment 1
Present embodiment provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization, and it prepares according to following method:
(1) take by weighing 10.2 gram magnesium chlorides, add 67 milliliters of 2-Ethylhexyl Alcohols, isothermal reaction is until forming clear solution under 140 ℃ of agitation conditions.
(2) get 12 milliliters of titanium tetrachlorides, slowly be added drop-wise at normal temperatures in the solution of step (1) preparation, stirring reaction adds the magnesium titanium complex solution that 100 milliliters of hexane dilutions obtain after half a hour.
(3) get the solution that 20 milliliter of (2) 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.
(4) the catalyst suspension temperature is reduced to room temperature, leave standstill, sedimentation is 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 drying with high pure nitrogen, obtain Primary Catalysts, it is the solids flowability powder.
Promotor is a triethyl aluminum, and itself and above-mentioned Primary Catalysts are formed the catalyzer of present embodiment, and the two merges in use.
The median size of the Primary Catalysts of present embodiment (D (50)) is 21 microns, and particle diameter distribution width Span is 0.7, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 2
Present embodiment provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization, and the consumption of its preparation method and each reactant is with embodiment 1, and difference is the consumption of 2-Ethylhexyl Alcohol is adjusted into 50 milliliters by 67 milliliters.
The median size of the Primary Catalysts of present embodiment (D (50)) is 26 microns, and particle diameter distribution width Span is 0.6, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 3
Present embodiment provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization; The consumption of its preparation method and each reactant is with embodiment 1; Difference is the hexane that uses in the embodiment 1 Primary Catalysts preparation process is adjusted into the toluene with volume, but the hexane with volume the time is still used in the Primary Catalysts washing.
The median size of the Primary Catalysts of present embodiment (D (50)) is 15 microns, and particle diameter distribution width Span is 0.6, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 4
Present embodiment provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization, and the consumption of its preparation method and each reactant is with embodiment 1, and difference is 20 milliliters of silicon tetrachlorides in the Primary Catalysts preparation process (3) are adjusted into 20 milliliters of boron trichlorides.
The median size of the Primary Catalysts of present embodiment (D (50)) is 23 microns, and particle diameter distribution width Span is 1.0, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Embodiment 5
Present embodiment provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization, and the consumption of its preparation method and each reactant is with embodiment 1, and difference is 20 milliliters of silicon tetrachlorides in the Primary Catalysts preparation process (3) are adjusted into 20 milliliters of phosphorus trichlorides.
The median size of the Primary Catalysts of present embodiment (D (50)) is 19 microns, and particle diameter distribution width Span is 0.7, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1
Comparative Examples 1
This Comparative Examples provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization, and it prepares according to following method:
(1) take by weighing 114 gram diethoxy magnesium, add 340 milliliters of tetrabutyl titanates, isothermal reaction is reduced to room temperature until forming clear solution with solution temperature under 140 ℃ of agitation conditions, adds 400 milliliters of dry hexane diluted for use.
(2) get the solution that 9 milliliter of (1) step obtains, with the slow hexane solution (3M) that drips 15 milliliters of ethyl aluminum dichlorides of drop-burette, after being added dropwise to complete, isothermal reaction obtained catalyst suspension in 4 hours under 60 ℃ of agitation conditions.
(3) the catalyst suspension temperature is reduced to room temperature, leave standstill, sedimentation is 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 drying with high pure nitrogen, obtain Primary Catalysts, it is the mobile powder of brown solid.
Promotor is a triethyl aluminum, and itself and above-mentioned Primary Catalysts are formed the catalyzer of present embodiment, and the two merges in use.
The median size of the Primary Catalysts of this Comparative Examples (D (50)) is 30 microns, and particle diameter distribution width Span is 2.0, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1
Comparative Examples 2
This Comparative Examples provides a kind of and has been used for that ethylene homo closes or the catalyzer of copolymerization, and it is to prepare according to CN85105150B embodiment 1 said method, and the full text of CN85105150B is introduced here as a reference.
The median size of the catalyzer of this Comparative Examples (D (50)) is 8.2 microns, and particle diameter distribution width Span is 1.2, and the screening result of activity of such catalysts and polyethylene powder is as shown in table 1.
Table 1
Can know that from the data of table 1 the Primary Catalysts particle shape of embodiment is regular, the particle size homogeneous, macroparticle and small-particle are few.Under same polymerizing condition, the size distribution of the catalyzer resulting polymers of embodiment is narrower, and it is all less to cross thick or meticulous particle in the polymkeric substance.
Claims (10)
1. vinyl polymerization Primary Catalysts, its raw material comprises magnesium compound, alcohol compound, titanium compound and chlorine-containing compound;
Wherein, said magnesium compound is formula M g (OR
1)
nCl
2-nShown in one or more combination in the compound, in the formula, R
1Be C
2-C
20Alkyl, n is integer and 0≤n≤2;
Said alcohol compound is a general formula R
2The combination of one or more shown in the OH in the compound, in the formula, R
2Be C
2-C
20Alkyl;
Said titanium compound is general formula Ti (OR
3)
mCl
4-mShown in one or more combination in the compound, in the formula, R
3Be C
2-C
20Alkyl, m=1,2,3 or 4;
Said chlorine-containing compound is formula M (OR
4)
fCl
4-fShown in one or more combination in the compound, in the formula, M is metal or non-metallic element, R
4Be C
2-C
20Alkyl, f is integer and 0≤f＜4;
The mol ratio of said magnesium compound, said alcohol compound, said titanium compound and said chlorine-containing compound is 1: (1-10): (0.01-20): (0.01-20).
2. Primary Catalysts according to claim 1, wherein, said magnesium compound is one or more the combination in the alkoxyl magnesium compound of magnesium chloride, chlorination magnesium ethylate, diethoxy magnesium and long-chain.
3. Primary Catalysts according to claim 1, wherein, said alcohol compound is for containing C
6-C
20The alcohol compound of straight-chain alkyl or branched hydrocarbyl in one or more combination.
4. according to claim 1 or 3 described Primary Catalystss; Wherein, said alcohol compound is one or more the combination in 2-methyl amyl alcohol, 2-ethylpentanol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, hendecanol, dodecanol, tetradecanol, oleyl alcohol, hexalin, the methyl-cyclohexanol.
5. Primary Catalysts according to claim 1, wherein, said titanium compound is TiCl
4, Ti (OCH
3) Cl
3, Ti (OCH
3)
2Cl
2, Ti (OCH
3) Cl
3, Ti (OC
2H
5) Cl
3, Ti (OC
2H
5)
2Cl
2, Ti (OC
2H
5)
3Cl, Ti (OC
4H
9) Cl
3, Ti (OC
4H
9)
2Cl
2, Ti (OC
4H
9)
3The combination of one or more among the Cl.
6. Primary Catalysts according to claim 1, wherein, said chlorine-containing compound is one or more the combination in silicon tetrachloride, titanium tetrachloride, zirconium tetrachloride, boron trichloride, phosphorus trichloride, the aluminum chloride.
7. Primary Catalysts according to claim 1, wherein, the mol ratio of said magnesium compound, said alcohol compound, said titanium compound and said chlorine-containing compound is 1: (2-5): (0.2-1): (1-10).
8. the preparation method of each described vinyl polymerization Primary Catalysts of claim 1-7, it comprises the steps:
At 25-200 ℃, magnesium compound and alcohol compound to be mixed, sustained reaction 10 minutes to 20 hours is so that form clear solution;
At-10 ℃ to 50 ℃, said clear solution to be mixed with titanium compound, sustained reaction 30 minutes to 5 hours obtains magnesium titanium complex solution;
At-20 ℃ to 150 ℃, said magnesium titanium complex solution to be mixed with chlorine-containing compound, sustained reaction obtained Primary Catalysts suspension-s to precipitating fully in 1 minute to 10 hours;
At 25 ℃ to 100 ℃, said Primary Catalysts suspension-s was carried out slaking reaction 0.5 to 15 hour;
With the Primary Catalysts suspension-s after the said slaking wash, drying, obtain Primary Catalysts.
9. ethylene rolymerization catalyst, it comprises following component:
Each described vinyl polymerization Primary Catalysts of claim 1-7;
Organo-aluminium compound, it is general formula AlR
5 gX
3-gShown in one or more combination in the compound, in the formula, R
5Be C
1-C
20Alkyl, X is a halogen, g is integer and 1＜g≤3.
10. catalyzer according to claim 9, wherein, said organo-aluminium compound is AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3And AlEt
2The combination of one or more among the Cl.
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| CN104130343A (en) * | 2013-05-02 | 2014-11-05 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof |
| CN106243253A (en) * | 2015-06-05 | 2016-12-21 | 中国石油天然气股份有限公司 | For vinyl polymerization or the catalytic component of combined polymerization and preparation method, comprise the catalyst of this catalytic component, preparation method and application |
| CN115246904A (en) * | 2021-04-26 | 2022-10-28 | 中国石油天然气股份有限公司 | Main catalyst component for solution-process ethylene polymerization, preparation method thereof, catalyst system and application thereof |
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| GB2525540A (en) * | 2013-01-30 | 2015-10-28 | Petrochina Co Ltd | Olefin polymerization catalyst and preparation and application thereof |
| US9695257B2 (en) | 2013-01-30 | 2017-07-04 | Petrochina Company Limited | Olefin polymerization catalyst and preparation and application thereof |
| GB2525540B (en) * | 2013-01-30 | 2021-03-03 | Petrochina Co Ltd | Olefin polymerization catalyst and preparation and application thereof |
| CN104130343A (en) * | 2013-05-02 | 2014-11-05 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof |
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| CN115246904A (en) * | 2021-04-26 | 2022-10-28 | 中国石油天然气股份有限公司 | Main catalyst component for solution-process ethylene polymerization, preparation method thereof, catalyst system and application thereof |
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