CN1958624A - Combination of catalysts for polymerization of ethylene, preparation method, and application - Google Patents
Combination of catalysts for polymerization of ethylene, preparation method, and application Download PDFInfo
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- CN1958624A CN1958624A CN 200510117437 CN200510117437A CN1958624A CN 1958624 A CN1958624 A CN 1958624A CN 200510117437 CN200510117437 CN 200510117437 CN 200510117437 A CN200510117437 A CN 200510117437A CN 1958624 A CN1958624 A CN 1958624A
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Abstract
This invention provides a method for preparing catalyst for ethylene polymerization. The catalyst comprises at least one alkyl metal compound, at least one Mg compound containing alkyl, at least one bifunctional compound that can react with the mG compound containing alkyl, at least one halide, and at least one Ti compound. The catalyst is loaded onto an inorganic oxide carrier. The catalyst has high hydrogen sensitivity and high activity balance. The electrostatic quantities on the catalyst powder are obviously reduced, which is advantageous for the operation of polymerization process. The Mg compound containing alkyl is obtained from magnesium halide/alcohol mixture and alkyl magnesium, thus can reduce alkyl magnesium amount.
Description
Technical field
The present invention relates to a kind ofly be used for the particularly main catalyst component of ethylene homo or copolymerization of alkene, and the preparation method of this catalyst component and purposes.
Technical background
After the seventies, high-efficiency polyethylene catalyst was succeeded in developing, great change had taken place in world's polyethylene industry.Over nearly more than 20 years, follow the development of ethene polymerization process, the catalyzer that matches with polymerization technique has also been got significant progress, and wherein effective catalyst relies on its good polymerization and sophisticated utilisation technology still to occupy an important position in the polyethylene catalysts field.Through exploratory development for many years, Mg-Ti be the preparation method of effective catalyst also by polishing altogether, the suspension pickling process has developed into chemical reaction method.In chemical reaction method, the reaction product that many patents of invention relate to employing dialkyl magnesium, chlorizating agent and transition metal halide etc. is an active ingredient, the catalyzer that is carried on the inorganic oxide ball type carrier and forms has been prepared the catalyzer of number of different types with this class reactant.At Chinese patent CN1158136; CN1299375 and U.S. Pat 3787384; 4148754; 4173547; 4301029; 4508843; Disclose this type catalyst in 4921920 and 5124296.In such Mg-Ti catalyzer, recent development is to add electron donor compound (as the aliphatic alcohols compound) at the catalyst composition preparatory phase, the introducing that experiment showed, the electron donor compound can improve the polymerization activity of catalyzer and the hydrogen regulation performance of catalyzer.
In Chinese patent CN1158136A, disclose and in the process of catalyst composition preparation, used long carbochain fat alcohol compound with α-side chain, the introducing of this compounds, the polymerization activity and the hydrogen regulation performance of catalyzer have been improved, particularly Tu Chu characteristics are when preparation lower molecular weight and high-molecular weight Alathon and multipolymer, under different hydrogen partial pressure conditions, this catalyzer can both keep high polymerization activity, and active balance is good.But in catalyst preparation process owing to directly introduced the chlorination alkyl metal cpd, make the Primary Catalysts powder of preparation have bigger static content, the static inhibitor of having to add in polymerization technique is made troubles to production operation, has also increased production cost simultaneously.
Disclose the silica gel suspension that in the process of catalyst composition preparation, uses halohydrin and a large amount of excessive alkyl magnesium to handle among the US4954470 and reacted, made catalyst component after carrying the titanium active ingredient again.Though this method institute controlling catalyst has overcome high electrostatic problem, and have good hydrogen accent, copolymerization performance,, silica gel treatment is directly used alkyl magnesium, cause the alkyl magnesium consumption excessive, make the Preparation of Catalyst cost improve greatly, and catalyst activity improves not quite.
A kind of ethylene polymerization catalysts component, preparation method and catalyzer of being used for is provided among the CN02131464.0, it is an at least a alkyl metal cpd in load on the silicon-dioxide, at least a halogenide, the bifunctional compound of at least a and dialkyl reactive magnesium, at least a alkyl magnesium compound, at least a titanium compound and obtaining.Catalyzer has good activity, and hydrogen regulation performance is good, and the catalyst fines static content descends, and helps production operation, but owing to adopt alkyl magnesium compounds in producing in a large number, makes the catalyzer cost improve greatly.
The inventor is by experiment discovery repeatedly, when the structure that changes the abovementioned alkyl magnesium compound, adopt Magnesium Chloride Anhydrous, alcohol compound reaction, at first form the alcohol adduct solution of magnesium chloride, it is reacted with alkyl magnesium compound again, obtain a kind of magnesium chloride of novelty and the title complex of alkyl magnesium, catalyzer with its preparation, can solve the excessive problem of catalyst fines static content, and catalyzer has good hydrogen mediation copolymerization performance equally, and high polymerization activity, greatly reduce the consumption of alkyl magnesium during the preparation catalyzer, thereby reduced cost.
Summary of the invention
The ethylene polymerization catalysts component that is used for of the present invention, it is to be formed by at least a alkyl metal cpd, at least a magnesium compound that contains alkyl, at least a can loading on a kind of inorganic oxide carrier through reaction with bifunctional compound, at least a halogenide and at least a titanium compound of the magnesium compound reaction that contains alkyl.
Described alkyl metal cpd such as general formula (I) MeR
1R
2R
3Shown in, R in the formula
1, R
2, R
3Be identical or different C
1～C
20Alkyl is with C
1～C
20Straight chain, side chain or cyclic alkyl are good, Me is an IIIA family element in the periodic table of elements, preferred aluminium, relatively exemplary compounds as, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, trioctylaluminum etc. are good with triethyl aluminum, triisobutyl aluminium especially wherein.
Described magnesium compound such as general formula (II) MgX that contains alkyl
2[Mg (OR
4)
mR
5 2-m]
pShown in, Mg represents magnesium atom in the formula, and X represents halogen atom, and O represents Sauerstoffatom, R
4, R
5Represent identical or different C
1～C
20Alkyl, 0＜m＜2; P is 1～20 number, preferred 1～3.The magnesium compound that the present invention contains alkyl is by after magnesium dihalide and the alcohol compound reaction, again the title complex that forms with the dialkyl magnesium compound reaction.Wherein the mol ratio of alcohol compound and magnesium dihalide is represented with q, and q is 1～6 number, the preferred magnesium dichloride of magnesium dihalide; The mol ratio of dialkyl magnesium and alcohol is greater than q/2; Alcohol compound comprises C
1～C
20Straight chain alcohol, cycloalkanol or isomery alcohol, for example: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol etc.; Cycloalkanol, as hexalin, methyl-cyclohexanol; Aromatic alcohol, as Bian alcohol, methyl Bian alcohol, sec.-propyl Bian alcohol etc.Preferred 2-Ethylhexyl Alcohol.Two alkyl in the dialkyl magnesium compound can be identical, also can be inequality, and concrete as dibutylmagnesium, butyl octyl magnesium etc.The preparation method who contains the magnesium compound of alkyl is dispersed in magnesium dihalide in the inert media, under agitation drip alcohol compound, afterwards, keep certain temperature and reaction certain hour to the alcohol adduct that forms magnesium dihalide, at room temperature, the dialkyl magnesium n-heptane solution is added drop-wise in the alcohol adduct of resulting magnesium dihalide, continues reaction for some time, can obtain magnesium compound as general formula (II).Described inert media comprises aromatic hydrocarbons and alkane, and is concrete as toluene, decane etc.The magnesium compound that preferably contains alkyl is the title complex of magnesium dichloride and alkoxyalkyl magnesium, and its general formula is expressed as MgCl
2[Mg (OR
4)
mR
5 2-m]
2, R wherein
4Be preferably C
6～C
16Alkyl, be preferably the 2-ethylhexyl, R
5Be preferably C
2～C
10Identical or different alkyl, 0＜m＜2.Described halogenide such as general formula (III) MX
nShown in, M is three, four, five main group element or transition metal in the formula, and X is a halogen atom, and preferred chlorine, n are the numbers with the M equivalence; Particular compound is as AlCl
3, BCl
3, SiCl
4, TiCl
4, CCl
4, NdCl
2Deng.Sometimes, this halogenide can be replaced by halohydrocarbon.
Described bifunctional compound such as general formula (IV) F-R
6R
7X
4-bShown in, F is a kind of in hydroxyl, acyl group, amido or the ester group in the formula, preferred hydroxyl, R
6, R
7Be C
1～C
20Alkyl or aromatic base, b=1,2 or 3, X is a halogen atom, preferred chlorine, particular compound as:
Cl
3CCH
2OH，Cl
2CHCH
2OH，ClCH
2CH
2OH，Cl
3CC(CH
3)
2OH，ClCH
2CH
2CH
2CH
2OH，
Cl
3COCl, Cl
2CHCOCl, ClCH
2COCl etc. also can be two or more mixtures wherein.Preferred Cl
3CCH
2OH.
Described titanium compound is as logical formula V Ti (OR
8)
4-mX
mShown in, R in the formula
8Be C
1～C
14Aliphatic group, X is a halogen atom, m is 0 to 4 number.Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture for use, preferred titanium tetrachloride.
Inorganic oxide carrier of the present invention is used to support active ingredient, can think, any inorganic oxide carrier of above-mentioned chemical reaction that do not disturb all is suitable for.The example of such inorganic oxide has silicon-dioxide, aluminum oxide, oxidation sial, magnesium oxide, titanium oxide, chromic oxide and zirconium white or the like, preferred silicon-dioxide.In general, inorganic oxide carrier should use with the particle form of exsiccant sphere or elliposoidal.Median size is about 1 micron～250 microns, preferred 10 microns～100 microns; The specific surface area of carrier is 100-800m
2/ g, pore volume are 1-8ml/g.The treatment temp of inorganic carrier is generally at 100 ℃～1000 ℃, and when inorganic carrier was silicon-dioxide, treatment temp was generally more than 200 ℃, and preferred 200 ℃～850 ℃, heat drying was handled 1～16 hour.
Catalyst component of the present invention preferably adopts the following step to be prepared:
(1) inorganic oxide carrier and general formula (I) compound contact reacts obtains first kind of reaction product;
(2) first kinds of reaction product contact with general formula (II) compound and obtain second kind of reaction product;
The bifunctional compound contact reacts of (3) second kinds of reaction product and general formula (III) obtains the third reaction product;
(4) the compound contact reacts of the third reaction product and general formula (IV) obtains the 4th kind of reaction product;
The titanium compound reaction of (5) the 4th kinds of reaction product and logical formula V obtains catalyst component.
In catalyst preparation process, general formula (I) compound add-on is controlled at 0.1～80mmol/g, preferred 0.5～2.5mmol/g in every gram inorganic carrier.The mol ratio of general formula (II) compound and general formula (I) compound is 0.01～100mol/mol, preferred 0.1～10mol/mol.The mol ratio of general formula (III) compound and general formula (II) compound is 0.01～100mol/mol, preferred 0.1～10mol/mol.The mol ratio of general formula (IV) compound and general formula (II) compound is 0.01～100mol/mol, preferred 0.1～5mol/mol.The mol ratio of logical formula V compound and general formula (II) compound is 0.01～100mol/mol, preferred 0.1～5mol/mol.
In the catalyst preparation process, the nonpolar inert media consumption that is used to form slurry can change in relative broad range.Generally according to actual needs, its consumption is between 5ml/g carrier～200ml/g carrier.Preferred nonpolar medium is an alkane, for example pentane, hexane, iso-pentane, normal heptane, octane, nonane and decane etc.It should be purified before use, for example with silica gel or molecular sieve diafiltration, to remove minor amount of water, oxygen, polar compound and other are unfavorable for the material of catalyst activity.After above-mentioned (5) step reaction is finished, can wash with above-mentioned nonpolar inert media, wash generally speaking about 4 times.
Have found that slower reaction process can obtain the catalyst component of better particle form, therefore, preferably lower temperature of reaction.Reaction process among the present invention is generally carried out under about 5 ℃～120 ℃ temperature range, is preferably 20 ℃～110 ℃.Reaction times also can change in relative broad range, is generally 0.5～24 hour, should make the sufficiently long time of reaction between the component under desired reaction temperature.For further improving the particle form of catalyzer and the tap density of polymerisate, can use slight vacuum, means such as elevated temperature or nitrogen purging in intermediate steps.
What need particularly point out is that if use the chlorination alkyl metal cpd in catalyst preparation process, the Primary Catalysts powder of preparation has more static content.And the present invention uses alkyl metal cpd and halogenide to prepare catalyzer, and in conjunction with the use of bifunctional compound, not only can solve the excessive problem of Primary Catalysts powder static electricity amount, the Primary Catalysts of preparation has good hydrogen accent, copolymerization performance equally, the characteristics that high catalytic activity is all arranged under high hydrogen partial pressure or low hydrogen dividing potential drop, the less caking resin that even do not exist in polymerization technique.The catalyzer of preparing is under high polymerization temperature, and activity of such catalysts no longer includes the too fast problem of decay of activity.Be specially adapted to double-reactor and prepare the polyvinyl resin that molecular weight distribution is bimodal pattern.The settling velocity of catalyst solid in slurries accelerated, and helps filtering and washing.The method that the present invention prepares catalyzer is obtaining the active while of same polymeric, and the usage quantity of alkyl magnesium reduces, and greatly reduces cost.
The invention still further relates to a kind of catalyzer that is used for ethylene homo or copolymerization, it contains above-mentioned catalyst component of the present invention and the reaction product that basic aluminum compound is arranged, and the wherein used general formula that basic aluminum compound is arranged is AlR
nX
3-n, R is that hydrogen or carbonatoms are that 1～20 alkyl, X are halogen in the formula, n is the number of 0＜n≤3; Relatively exemplary compounds as, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, trioctylaluminum etc. are good with triethyl aluminum, triisobutyl aluminium especially wherein; Can use separately, also can several mixing use.
The catalyzer that the present invention relates to is applicable to the equal polymerization of ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts at least a in 1-propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, the 4-methylpentene-1.
Embodiment
Embodiment given below is for the present invention is described better, but the present invention is not limited by the following examples.
Testing method:
1, melting index is measured according to ASTM D1238-99
2, catalyst solid powder electrostatic testing method:
As everyone knows, the static content that pressed powder has is big more, and the amount of powder adherence on wall of container will be many more, the static content that can indicate catalyst fines to have basically by the adhesive capacity of test powders.
In the loft drier of nitrogen atmosphere, getting about 80mL glass ampere bottle of a thorough drying weighs, a certain amount of catalyst fines is packed in the ampere bottle, be fixed on the horizontal vibrator and vibrate 5 minutes, afterwards the ampere bottle is inverted, allow catalyst fines flow out naturally, take by weighing adherent amount of powder in the ampere bottle, indicate the static content of Primary Catalysts powder with the adhesive capacity of powder.
Embodiment 1:
(1) preparation of magnesium dichloride and butoxy dibutyl magnesium title complex
4.76 gram (50 mmole) anhydrous magnesium dichlorides, 28.1ml decane and 16.3 gram (125 mmole) 2-Ethylhexyl Alcohols are heated to 128 ℃, make it to react 3 hours, obtain a kind of homogeneous phase solution.After being cooled to room temperature, the dibutylmagnesium n-heptane solution of 100ml, 1M is added drop-wise in this homogeneous phase solution, continues reaction 2 hours, obtain magnesium dichloride and butoxy dibutyl magnesium complex solution.
(2) preparation of catalyst component
In reactor, 10 gram activated silica gel (model 948, U.S. Grace companies.Under nitrogen protection in 600 ℃ of activation 4 hours), the Al (CH of the hexane after 100 milliliters of purification process and 3.5 milliliters, 2.0M
2CH
3)
3Hexane solution reacted 1 hour down at 55 ℃, dripped 19ml (containing the total magnesium amount of 20 mmoles approximately) above-mentioned magnesium dichloride and butoxy dibutyl magnesium complex solution while stirring, continued stirring reaction 0.5 hour.
Cool to 40 ℃, in reactor, slowly drip 1.42 gram (9.5 mmole) Cl
3CCH
2OH, constant temperature stirred after 1 hour, dripped 0.7ml (6.1 mmole) silicon tetrachloride, and stirring reaction is after 2 hours.Drip 0.66ml titanium tetrachloride (with the dilution of 15ml hexane) then, be warming up to 45 ℃ of lasting stirring reactions 3 hours.After reaction is finished, use the nitrogen purging drying, get light brown solids flowability powder.
Adopt the method for describing to measure the size of catalyst solid powder institute static electrification, the results are shown in Table 1.
(3) evaluating catalyst
The slurry polymerization that carries out ethene respectively under different hydrogen contents is to prepare the polyethylene of different melting index; 2L stainless steel stirring tank, the 1L hexane, poly-and stagnation pressure: 1.03MPa, the about 50mg of catalyst levels, the hexane solution of 1ml triethyl aluminum (1M), polymerization temperature: 85 ℃, polymerization time: 1 hour.
During preparation low melt index polyethylene, P
H2/ P
C2H4=0.28/0.75
During preparation high fusion index polyethylene, P
H2/ P
C2H4=0.60/0.43
Polymerization result is shown in table 1.
Embodiment 2
Remove 3.5 milliliters in the catalyst preparation step (2), the Al (CH of 2.0M
2CH
3)
3Hexane solution, be adjusted into 5.0 milliliters of Al (C
2H
5)
3Hexane solution outside, other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Adopt the method for describing to measure the static size of catalyst solid powder, the results are shown in Table 1.
Embodiment 3
Except that the 0.7ml silicon tetrachloride in the catalyst preparation step (2) is adjusted into the 1.0ml, other conditions are with embodiment 2.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Adopt the method for describing to measure the static size of catalyst solid powder, the results are shown in Table 1.
Embodiment 4
0.66ml titanium tetrachloride in the catalyst preparation step (2) is adjusted into 1.0ml, and after reaction was finished, outside hexane 3 * 100ml washing, other conditions were with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Adopt the method for describing to measure the static size of catalyst solid powder, the results are shown in Table 1
Comparative Examples 1
(1) in reaction flask, add the 200ml hexane successively, 2.0ml toluene, the butyl octyl magnesium solution of 20mmol is lower than under 40 ℃ of situations at temperature of reaction system, and slowly 2-ethyl-1-hexanol of Dropwise 5 .6ml obtains pure magnesium complex.
(2) add the 100ml hexanes at 25 ℃ in 5.0g silicon-dioxide (with embodiment 1), the slow hexane solution (2M) of Dropwise 5 .0ml dichloro one aluminium triethyl then 25 ℃ of stirring reactions 0.5 hour, is warming up to 70 ℃, purges drying with high purity nitrogen.
(3) under the normal temperature, in the dried powder in (2) step, add the hexane that the 100ml purifying is crossed, under agitation add the pure magnesium complex of (1) step preparation, be warming up to 50 ℃ of stirring reactions 1.0 hours.
(6) in the reaction system in (3) step, slowly drip the titanium tetrachloride of 0.56ml,, then be warming up to 70 ℃, purge the dry pressed powder that gets with high purity nitrogen 50 ℃ of stirring reactions 1.0 hours.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Adopt the method for describing to measure the static size of catalyst solid powder, the results are shown in Table 1.
Comparative Examples 2
In 8.6g silicon-dioxide (with embodiment 1), add the 100ml hexane at 25 ℃, then slowly drip the dibutylmagnesium n-heptane solution of 17.4ml, 1M, added the back back flow reaction 1 hour, slowly drip 2 of 2.95ml, 2,2-ethapon (with the dilution of 30ml hexane) continued back flow reaction 40 minutes.At last, slowly drip 1ml titanium tetrachloride (with the dilution of 15ml hexane), continued back flow reaction 1 hour.Filter, 3 * 100ml hexane wash is used the nitrogen purging drying, obtains the flow solids powder.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Adopt the method for describing to measure the static size of catalyst solid powder, the results are shown in Table 1.
From the experimental data of table 1 embodiment and Comparative Examples as can be seen, catalyzer of the present invention is except that having high polymerization activity and good hydrogen regulation performance, the static content that catalyst fines has obviously reduces, and can exempt or reduce the add-on of static inhibitor in the vinyl polymerization production operation.Obtaining under the active condition of same polymeric, the usage quantity of alkyl magnesium obtains reducing, and has reduced the cost of preparation catalyzer.
Table 1
| Catalyzer | Low hydrogen dividing potential drop polymerization (H 2/C 2 ＝：0.28/0.75) | High hydrogen partial pressure polymerization (H 2/C 2 ＝：0.60/0.43) | Static content (sticking wall amount g) | ||
| Activity (gPE/gcat) | MI (g/10min) | Activity (gPE/g cat) | MI (g/10min) | ||
| Embodiment 1 | 4142 | 2.11 | 1680 | 42.5 | 0.47 |
| Embodiment 2 | 3979 | 2.32 | 1592 | 41.7 | 0.48 |
| Embodiment 3 | 4346 | 2.28 | 1686 | 43.1 | 0.41 |
| Embodiment 4 | 4560 | 1.86 | 1650 | 38.6 | 0.42 |
| Comparative Examples 1 | 2233 | 0.99 | 1035 | 42.6 | 1.50 |
| Comparative Examples 2 | 2913 | 2.22 | 1312 | 44.6 | 0.43 |
Claims (14)
1, is used for the ethylene polymerization catalysts component, it is formed on a kind of inorganic oxide carrier by at least a alkyl metal cpd, at least a magnesium compound that contains alkyl, at least a can loading to through reaction with bifunctional compound, at least a halogenide and at least a titanium compound of the magnesium compound reaction that contains alkyl, wherein
(1) alkyl metal cpd such as general formula (I) MeR
1R
2R
3Shown in, R in the formula
1, R
2, R
3Be identical or different C
1～C
20Alkyl, Me are IIIA family elements in the periodic table of elements;
(2) contain the magnesium compound such as general formula (II) MgX of alkyl
2[Mg (OR
4)
mR
5 2-m]
pShown in, Mg represents magnesium atom in the formula, and X represents halogen atom, and O represents Sauerstoffatom, R
4, R
5Be identical or different C
1～C
20Alkyl, 0＜m＜2, p is 1～20;
(3) halogenide such as general formula (III) MX
nShown in, M is three, four, five main group element or transition metals in the formula, and X is a halogen atom, and n is the number with the M equivalence;
(4) bifunctional compound such as general formula (IV) F-R
6R
7X
4-bShown in, F is a kind of in hydroxyl, acyl group, amido or the ester group in the formula, R
6, R
7Be C
1～C
20Alkyl or aromatic base, b=1,2 or 3, X is a halogen atom;
(5) titanium compound is as logical formula V Ti (OR
8)
4-mX
mShown in, R in the formula
8Be C
1～C
14Aliphatic group, X is a halogen atom, m is 0 to 4 number.
2, according to the described ethylene polymerization catalysts component that is used for of claim 1, alkyl metal cpd is an alkylaluminium cpd shown in its formula of (I).
3, the ethylene polymerization catalysts component that is used for according to claim 1, the magnesium compound that contains alkyl of its formula of (II) are by after magnesium dihalide and the alcohol compound reaction, again the title complex that forms with the dialkyl magnesium compound reaction.
4, the ethylene polymerization catalysts component that is used for according to claim 3, the magnesium compound that contains alkyl of its formula of (II) is by after magnesium dihalide and the alcohol compound reaction, the title complex that reacts with dialkyl magnesium compound and form, described alcohol is 2-Ethyl Hexanol.
5, the ethylene polymerization catalysts component that is used for according to claim 3, the magnesium compound that contains alkyl of its formula of (II) are that magnesium dichloride and p value are the title complex of 1～3 alkoxyalkyl magnesium.
6, the ethylene polymerization catalysts component that is used for according to claim 1, X is a chlorine in its formula of (III) compound.
7, the ethylene polymerization catalysts component that is used for according to claim 1, its formula of (III) compound is selected from AlCl
3, BCl
3, SiCl
4, TiCl
4, CCl
4, NdCl
2In a kind of.
8, the ethylene polymerization catalysts component that is used for according to claim 1, the F in its formula of (IV) compound is a hydroxyl, X is a chlorine.
9, the ethylene polymerization catalysts component that is used for according to claim 1, the compound in its formula of (V) is a titanium tetrachloride.
10, the ethylene polymerization catalysts component that is used for according to claim 1, wherein said inorganic oxygen compound carrier are at least a in silicon-dioxide, aluminum oxide, oxidation sial, magnesium oxide, titanium oxide, chromic oxide and the zirconium white.
11, any one described preparation method who is used for ethene polymerization catalyst component of one of claim 1-10 comprises the steps:
(1) make inorganic oxide carrier and general formula (I) compound contact reacts obtain first kind of reaction product;
(2) first kinds of reaction product contact with general formula (II) compound and obtain second kind of reaction product;
The bifunctional compound contact reacts of (3) second kinds of reaction product and general formula (III) obtains the third reaction product;
(4) the compound contact reacts of the third reaction product and general formula (IV) obtains the 4th kind of reaction product;
The titanium compound reaction of (5) the 4th kinds of reaction product and logical formula V obtains catalyst component.
12, the preparation method who is used for the ethylene polymerization catalysts component according to claim 11, it is characterized in that in every gram inorganic carrier general formula (I) compound add-on, be controlled at 0.1～80mmol/g, the mol ratio of general formula (II) compound and general formula (I) compound is 0.1～10mol/mol, the mol ratio of general formula (III) compound and general formula (II) compound is 0.1～10mol/mol, the mol ratio of general formula (IV) compound and general formula (II) compound is 0.1～5mol/mol, and the mol ratio of logical formula V compound and general formula (II) compound is 0.1～5mol/mol.
13, a kind of ethylene polymerization catalysts that is used for comprises following component:
(1) any one described ethylene polymerization catalysts component that is used for of claim 1～10;
(2) organo-aluminium compound, its general formula are AlR
nX
3-n, R is that hydrogen or carbonatoms are that 1～20 alkyl, X are halogen in the formula, n is the number of 0＜n≤3.
14, the described application that is used for ethylene polymerization catalysts in vinyl polymerization or copolymerization of claim 13.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565473B (en) * | 2008-04-25 | 2011-06-15 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation and application thereof |
| CN103772540A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Loaded chromium base catalyst, preparation method and application thereof |
| CN112646063A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst and application |
-
2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565473B (en) * | 2008-04-25 | 2011-06-15 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation and application thereof |
| CN103772540A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Loaded chromium base catalyst, preparation method and application thereof |
| CN112646063A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst and application |
| CN112646063B (en) * | 2019-10-11 | 2022-12-30 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst and application |
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