CN1229401C - Gas phase ethene polymerization catalyst component and catalyst thereof - Google Patents
Gas phase ethene polymerization catalyst component and catalyst thereof Download PDFInfo
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- CN1229401C CN1229401C CN 02131459 CN02131459A CN1229401C CN 1229401 C CN1229401 C CN 1229401C CN 02131459 CN02131459 CN 02131459 CN 02131459 A CN02131459 A CN 02131459A CN 1229401 C CN1229401 C CN 1229401C
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- catalyst component
- electron donor
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Abstract
The present invention provides a catalyst component and a catalyst for ethylene homopolymerization or the copolymerization of ethylene and other a-alkenes. The catalyst component comprises titanium trichloride, at least one electron donor, at least one shape regulation agent and carrier filler. The shape of an ethylene polymer obtained by the catalyst is in a similar ball shape and has high bulk density and uniform and regular granule diameter. Superfine powder is decreased in large amplitude; the electrostatic phenomenon and the pipe clogging phenomenon are obviously decreased.
Description
Technical field
The present invention relates to a kind ofly be used for that ethylene homo closes or the catalyst component of ethene and other a-alpha-olefinic copolymerizations and preparation method thereof, contain the catalyzer of this catalyst component and this catalyzer in the technologic application of ethene gas-phase polymerization, the particularly application on the ethene gas-phase fluidized bed polymerization process.
Background technology
Ethene gas-phase polymerization technology is a kind of high-efficiency polymerization technology, this technology have the production efficiency height, need not solvent, need not the solvent removal operation, low cost and other advantages, the ratio of the polyethylene of this explained hereafter in the polyethylene ultimate production increases day by day, and particularly the fluidized-bed process of ethene gas-phase polymerization has caused people's extensive concern especially.Therefore developing the ethene gas-phase polymerization catalyzer seems very important.
The Ziegler-Natta catalyst that is used for ethene gas-phase polymerization technology at present mainly is the catalyst system based on titanous chloride or titanium tetrachloride.It is different that titanous chloride or titanium tetrachloride load on the different carriers formed catalyst performance.The adding of carrier may influence bulk density, flowability, granules of catalyst form, the distribution in active centre, the activity of such catalysts of catalyzer, even the molecular weight of impact polymer and distribution and polymer properties.For example, be that the catalyzer of preparing carriers is general mobile relatively poor with the magnesium chloride, limited the application of catalyzer on gas-phase fluidized-bed reactor.Therefore, according to the characteristics of polymerization technique, select a kind of effective carrier or weighting material, the Ziegler-Natta catalyst system of involutory one-tenth excellent property seems extremely important.
A lot of now inventions adopt silica gel for filling carrier, with transition metal-magnesium compound load on silica gel, so both kept the promoter action of magnesium compound to catalytic activity, can improve the flowability and the particle form of catalyzer again, catalyzer is used on gas-phase fluidized-bed reactor well.The common practice is with transition metal and magnesium compound, for example the complex compound of titanium/magnesium is carried on the silica-gel carrier, for example U.S. Pat 4302565 is that the mother liquor component be impregnated on the carrier, but the stability of the composition of the active ingredient of control load on carrier is the comparison difficulty, therefore U.S. Pat 4293673 discloses a kind of catalyzer that adopts spray drying method for preparation again, it is that mother liquor is mixed with silica gel filler (average particulate diameter is less than 50 microns), be prepared by spray-dired method then, the size distribution of gained catalyzer and particle form are easy to control, thereby after making this catalyzer be used for the gas fluidised bed polymerisation reaction of ethene, polyvinyl size distribution of gained and particle form also are easy to control.But also the people is dissatisfied in addition for this activity of such catalysts.
In order to improve the charge capacity of titanous chloride on silica gel, thereby improve the polymerization activity of catalyzer, people adopt particle diameter less, and the silica gel that specific surface area is bigger is carrier, as Chinese patent CNl223267, English Patent GB2112004 etc.
Chinese patent CN1085915A discloses a kind of polyvinyl production method, and the catalyzer that uses in this production method has adopted the silica gel that particle diameter is littler, specific surface area is bigger to be carrier, and the particle diameter of silica gel is between 0.1～1.0 μ m usually.The active ingredient titanous chloride makes by the magnesium metal reduction titanium tetrachloride simultaneously, therefore obtained the catalyzer of greater activity, and hexane extractable content significantly reduces in the ethylene copolymer of gained.But because carrier particle is too little, be easy to assemble, cause the heterogeneity of granules of catalyst easily, therefore can only adopt a kind of method that the silica gel particle after the load is become greatly again, increase flowability.Above-mentioned for this reason patent has adopted spray-dired method in Preparation of Catalyst, make that the average particle size distribution of solid catalyst is about～30 μ m.But this method for preparing catalyst apparatus expensive, complex process, production efficiency is lower, makes the Catalyst Production cost significantly increase, and is unfavorable for the suitability for industrialized production of catalyzer.
Summary of the invention
For this reason, the inventor finds by repetition test, do not adopt above-mentioned spray drying process, but select a kind of so-called " form conditioning agent " for use, as low molecular weight polyethylene wax, the stearic acid binding agent, petroleum cracking byproduct Microcrystalline Wax, silane coupling agent or titante coupling agent etc., join in the catalyst system of ultra-fine silica gel load, carry out drying behind the homodisperse, the solid catalyst of gained, the situation when all more not adding " form conditioning agent " aspect form and particle diameter is greatly improved, and this preparation method have simple, characteristics such as production cost is lower.
The invention provides and a kind ofly be used for that ethylene homo closes or the catalyst component of ethene and other a-alpha-olefinic copolymerizations, this catalyst component contains titanous chloride, at least a electron donor, at least a " form conditioning agent " and carrier weighting material, wherein said " form conditioning agent " is low molecular weight polyethylene wax, stearic acid binding agent, petroleum cracking byproduct Microcrystalline Wax, silane coupling agent or titante coupling agent.Wherein low molecular weight polyethylene wax and Microcrystalline Wax preferred molecular weight are 500～10000, and most preferably molecular weight is 1000～5000; Should be selected from stearic acid binding agent and the silane coupling agent and not contain active hydrogen group, for example: vinyltriethoxysilane, vinyl silanes, methacrylate silanes, polychlorostyrene methylsiloxane etc.
Titanous chloride in the described catalyst component can make the titanium tetrachloride reduction by handle titanium tetrachloride with required stoichiometric MAGNESIUM METAL in described electron donor solvent.
Described electron donor must not contain active hydrogen group, and suitable electron donor compound comprises alkyl ester, aliphatic ether, cyclic aliphatic ether and the aliphatic ketone of aliphatic series or aromatic carboxylic acid.In these electron donors, C preferably
1～C
4The alkyl ester of saturated aliphatic carboxylic acid; C
7～C
8Aromatic carboxylic acid's alkyl ester; C
2～C
8Aliphatic ether, C
4～C
5Cyclic ethers; C
3～C
6Saturated fatty ketone.These electron donors are methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF) (THF), acetone and methyl iso-butyl ketone (MIBK) most preferably.Electron donor can use separately or several being used.If desired, available one or more substituting groups replace these electron donor compounds, and these substituting groups are carrying out being inertia under the residing reaction conditions between polymerization period with this reduzate between the titanium tetrachloride reduction period and subsequently.
According to the present invention, adopting required stoichiometric MAGNESIUM METAL to handle titanium tetrachloride carries out its reaction that is reduced to titanous chloride in the electron donor solvent, products therefrom magnesium dichloride and titanous chloride and this electron donor solvent form the solubility title complex, for example in tetrahydrofuran solvent, form " the MgCl of solubility
2-TiCl
3-THF " title complex.But magnesium/titanium of this moment is lower, forms in order to form the ideal catalyzer, must add the additional magnesium component that contains in this title complex, with magnesium/titanium than being increased to required numerical range.Usually this magnesium component that contains can directly adopt magnesium dichloride, also can adopt magnesium/titanium adducts, for example, adopts magnesium dichloride is dissolved in the adducts that obtains in the mixture of tetrabutyl titanate and electron donor.Control contains the add-on of magnesium component, and making magnesium in the final catalyst component/titanium ratio is 1: 1-60: 1, be preferably 1.5～10: 1.
According to the present invention, the suitable carriers weighting material is the oxide compound of silicon, for example ultra-fine silica gel.Usually its median size is preferably 0.1 μ～1.0 μ less than 1.0 μ.The carrier weighting material be exsiccant when using, and do not contain planar water.Can make the carrier filler drying by heating, generally be heated to 200 ℃ at least and carry out drying.
Should make the carrier filler of sufficient amount, mix with the solution that contains titanous chloride in the presence of the present invention's " form conditioning agent ", the content of carrier filler is about 3% (weight) to 50% (weight) in the slurries, preferred 10% to 30% (weight).The add-on of form conditioning agent is about 0.1% (weight) of carrier filler to 10% (weight), preferred 0.5% to 5% (weight).
In order to make the above-mentioned catalyst component of the present invention be applicable to the production ethene polymers, must activate above-mentioned catalyst component, the activator that is adopted can adopt the alkylaluminium cpd of following general formula:
AlR
mX
3-m, wherein R is C identical or inequality
1-8Alkyl, X is a halogen, m is 1～3 integer.This class activator can use separately, perhaps combines use, comprises as AlEt
3, Al (n-C
6H
13)
3, Al (i-C
4H
7)
3, Al (C
8H
17)
3, AlEt
2Cl etc.
The preparation method of catalyst component of the present invention can may further comprise the steps:
(1) silica gel that median size is less than or equal to 1.0 μ activates,
(2) in electron donor with MAGNESIUM METAL and TiCl
4Reaction generates " TiCl
3-MgCl
2-electron donor " adducts,
(3) with anhydrous MgCl
2Be dissolved in the electron donor, add tetrabutyl titanate, get " MgCl
2-Ti (OBu)
4-electron donor " adducts,
(4) two kinds of adductss that step (2) and step (3) are obtained mix with certain proportion, add by " form conditioning agent ", add the silica gel after the activated processing in the above-mentioned steps 1, and the uniform mixing after drying gets ingredient of solid catalyst,
(5) randomly, in the gained solid catalyst, add aluminium diethyl monochloride successively and/or tri-n-hexyl aluminum fully reduces.
Catalyst system after reduction can be directly used in the slurry or the vapour phase polymerization of ethene.Add in the vinyl polymerization system but more preferably be suspended in the exsiccant mineral oil, all need add an amount of triethyl aluminum during polymerization.
The invention still further relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, it is the reaction product of above-mentioned catalyst component and organo-aluminium compound, and its general formula of wherein used alkylaluminium cpd is AlR ' 3, and R ' is 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.Ratio between catalyst component and the alkylaluminium cpd.Molar ratio computing with titanium and aluminium is: 1: 5～100, be preferably 1: 8～and 30.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation particularly gas-phase fluidized-bed condensation technology.Simultaneously, because catalyzer of the present invention preferably adopts inert diluent with catalyst dilution, for example the mineral wet goods is realized catalyst slurry charging equably by the pumping feeding manner, and charging is even, stable operation.
It is worthy of note and compare, do not use the catalyzer of " form conditioning agent " to be used for the polyethylene that the ethene gas fluidised bed polymerisation obtains and be aggregate than fine particle with catalyzer of the present invention, and loose, bulk density is not high, and this is unfavorable for packing and transportation.Simultaneously ultrafine powder is more, easily produces static, and easily again pipeline connection and the part of expanding produce gathering, cause the generation of phenomenon such as line clogging.And adopt catalyzer of the present invention, and when promptly having used " form conditioning agent ", the polyvinyl form of gained is the class ball-type, and bulk density is higher, and particle diameter is regular than homogeneous, and ultrafine powder reduces by a relatively large margin, and electrostatic phenomenon, line clogging phenomenon obviously reduce.Wherein＜180 the polyethylene particles of μ m can drop to 7.4～9.5wt% from 14.1wt%.Both size distribution can see Table 1.Polyvinyl form is changed into class sphere (particle diameter～30 μ) particle from irregular particle (particle diameter～10 μ).
With specific embodiment catalyst component of the present invention and catalyzer are described below, but are not limited to these embodiment.
Embodiment 1
(a) MgCl
2With TiCL
3The preparation of tetrahydrofuran (THF) adducts
Add the commercially available magnesium powder of 0.15g in the 500ml there-necked flask, the particle diameter of MAGNESIUM METAL is 0.1～5mm, vacuumizes, with nitrogen replacement three times and make total system all the time by nitrogen protection.Add the tetrahydrofuran (THF) of 100ml through processed then, start stirring, normal temperature slowly drips 1.6ml TiCl down
4Be warming up to 67～72 ℃ after dropwising, constant temperature stirred 2～5 hours under reflux state, obtained brown MgCl
2With TiCL
3The tetrahydrofuran (THF) adducts.
(b) MgCl
2Preparation with tetrabutyl titanate and tetrahydrofuran (THF) adducts
In the 250ml there-necked flask, add the anhydrous MgCl of 2.5g
2Vacuumize, with nitrogen replacement three times and make total system all the time by nitrogen protection.Add the tetrahydrofuran (THF) of 150ml then, stir and drip the 0.7ml tetrabutyl titanate after 10～30 minutes, stirred at normal temperatures 10～180 minutes, get MgCl through processed
2Adducts with tetrabutyl titanate and tetrahydrofuran (THF).
(c) supported solid Preparation of catalysts
Under nitrogen protection, above-mentioned gained MgCl
2Under nitrogen protection, add gained MgCl with the adducts of tetrabutyl titanate and tetrahydrofuran (THF)
2With TiCL
3The tetrahydrofuran (THF) adducts in, stirred 2～8 hours at 70 ℃ of constant temperature, purplish red solution.Add 1g low molecular polyethylene (molecular weight is Mw=1500～3000) then and stir dissolving down, the dissolving back added 15g activated silica gel (Cab-O-Sil TS-610), 70 ℃ of following stirring reactions 4～8 hours.Distill excessive tetrahydrofuran (THF), after steaming about 85%～95% tetrahydrofuran (THF), add 300ml hexane (through processed), abundant dispersed with stirring, and with hexane wash three times.Filter, drying obtains solid catalyst.
Embodiment 2
Except " form conditioning agent " changes into " vinyltriethoxysilane ", all the other are with embodiment 1.
Embodiment 3
The ethene slurry polymerization
To the 1 liter of stainless steel still that has stirring wash, drying, vacuumize, with three ethene of nitrogen replacement displacement twice, and carry out purifying treatment with the 1ml triethyl aluminum.Getting 0.1g embodiment 1 prepared solid catalyst is dissolved under nitrogen atmosphere in the 200ml hexane (carrying out processed with sodium Metal 99.5); the back adds the 0.165ml triethyl aluminum; 0.35ml the aluminium diethyl monochloride of concentration 1.903mol/l, ageing is 1 hour under the nitrogen protection.After ageing finishes, catalyst solution is added the stainless steel still, improve ethylene pressure to 0.8Mpa, polymerization is 2 hours under 70 ℃ of conditions, gets 85g white particle shaped polyethylene.Catalyst activity is 850gPE/gcat.
Embodiment 4
Gas-phase fluidized-bed Φ 100 vinyl polymerizations
In the gas-phase fluidized-bed reactor of Φ 100, add 100g through exsiccant polyethylene base-material.Add the 2ml triethyl aluminum, gas circulation 1 hour adds 0.1g embodiment 1 gained loaded catalyst, and adds the 2ml triethyl aluminum and the 1ml aluminium diethyl monochloride activates catalyzer, ageing is warming up to 88 ℃ after 1 hour, carry out ethylene polymerization under the pressure of 1.0Mpa.The consisting of of polymerizable gas (percent by volume): ethene: 44.1%; Hydrogen: 43.6%; Butylene: stopped reaction gets 466g white polyethylene powder after 12.3%, 3 hour.The MI of product
2.16Be 1.91g/10min, density is 0.924g/cm
3, molecular weight distribution is 4.71, activity of such catalysts is 4150gPE/gcat.Product cut size is analyzed as table 1.
Embodiment 5
Gas-phase fluidized-bed Φ 100 vinyl polymerizations
In the gas-phase fluidized-bed reactor of Φ 100, add 100g through exsiccant polyethylene base-material.Add the 2ml triethyl aluminum, gas circulation 1 hour adds 0.055g embodiment 1 gained loaded catalyst, and adds the 2ml triethyl aluminum and the 1ml aluminium diethyl monochloride activates catalyzer, ageing is warming up to 88 ℃ after 1 hour, carry out ethylene polymerization under the pressure of 1.0Mpa.The consisting of of polymerizable gas (percent by volume): ethene: 58.9%; Hydrogen: 22.7%; Butylene: stopped reaction gets 260g white polyethylene powder after 18.4%, 3 hour.The MI of product
2.16Be 0.608g/10min, density is 0.912g/cm
3, molecular weight distribution is 5.98, activity of such catalysts is 4740gPE/gcat.Product cut size is analyzed as table 1.
Embodiment 6
Gas-phase fluidized-bed Φ 100 vinyl polymerizations
In the gas-phase fluidized-bed reactor of Φ 100, add 100g through exsiccant polyethylene base-material.Add the 2ml triethyl aluminum, gas circulation 1 hour adds 0.055g embodiment 2 gained loaded catalysts, and adds the 2ml triethyl aluminum and the 1ml aluminium diethyl monochloride activates catalyzer, ageing is warming up to 88 ℃ after 1 hour, carry out ethylene polymerization under the pressure of 1.0Mpa.The consisting of of polymerizable gas (percent by volume): ethene: 53.0%; Hydrogen: 30.7%; Butylene: stopped reaction gets 245g white polyethylene powder after 16.3%, 3 hour.The MI of product
2.16Be 1.08g/10min, density is 0.918g/cm
3, molecular weight distribution is 3.93, activity of such catalysts is 4460gPE/gcat.Product cut size is analyzed as table 1.
Comparative Examples 1
Do not have " form conditioning agent " Preparation of catalysts: only will not add the form conditioning agent in the step among the embodiment 1 (c), all the other are identical with embodiment 1.
Comparative Examples 2
There is not the olefinic polymerization of " form conditioning agent " catalyzer on gas-phase fluidized-bed:
In the gas-phase fluidized-bed reactor of Φ 100, add 100g through exsiccant polyethylene base-material.Add 2ml three hexyl aluminium purification systems, gas circulation 1 hour adds 0.1g contrast experiment 1 gained catalyzer, carries out polymerization under the condition identical with embodiment 3.Stopped reaction gets 500g white polyethylene powder after 3 hours.The MI of product
2.16Be 1.0g/10min, density is 0.922g/cm
3, molecular weight distribution is 4.28, activity of such catalysts is 5160gPE/gcat.Product cut size is analyzed as table 1.
Table 1: polyvinyl size distribution
Claims (11)
1, a kind ofly be used for that ethylene homo closes or the catalyst component of copolymerization, this catalyst component contains titanous chloride, at least a electron donor, at least a " form conditioning agent " and carrier weighting material,
Wherein said " form conditioning agent " is low molecular weight polyethylene wax, stearic acid binding agent, petroleum cracking byproduct Microcrystalline Wax, in silane coupling agent and the titante coupling agent one or more, wherein the molecular weight of low molecular weight polyethylene wax and Microcrystalline Wax is 500～10000, stearic acid binding agent and silane coupling agent do not contain active hydrogen group, and the add-on of form conditioning agent is 0.1 weight % to 10 weight % of carrier weighting material;
Wherein said electron donor comprises alkyl ester, aliphatic ether, cyclic aliphatic ether and the aliphatic ketone of aliphatic series or aromatic carboxylic acid.
2, catalyst component according to claim 1, wherein electron donor is selected from C
1～C
4The alkyl ester of saturated aliphatic carboxylic acid, C
7～C
8Aromatic carboxylic acid's alkyl ester, C
2～C
8Aliphatic ether, C
4～C
5Cyclic ethers or C
3～C
6Saturated fatty ketone.
3, catalyst component according to claim 2, wherein electron donor is selected from one or more of methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran THF, acetone and methyl iso-butyl ketone (MIBK).
4, catalyst component according to claim 1, wherein titanous chloride makes the titanium tetrachloride reduction by handle titanium tetrachloride with required stoichiometric MAGNESIUM METAL in described electron donor solvent.
5, catalyst component according to claim 4 adds magnesium dichloride again and is dissolved in the adducts that obtains in tetrabutyl titanate and the electron donor mixture, and making magnesium in the final catalyst component/titanium ratio is 1: 1～60: 1.
6, catalyst component according to claim 5 adopts general formula AlR
mX
3-mAlkylaluminium cpd catalyst component is activated, wherein R is C identical or inequality
1-8Alkyl, X is a halogen, m is 1～3 integer.
7, catalyst component according to claim 1, wherein the carrier weighting material is the silica gel that median size is less than or equal to 1.0 μ.
8, the preparation method of the described catalyst component of a kind of claim 1 may further comprise the steps:
(1) silica gel that median size is less than or equal to 1.0 μ activates,
(2) in electron donor with MAGNESIUM METAL and TiCl
4Reaction generates " TiCl
3-MgCl
2-electron donor " adducts,
(3) with anhydrous MgCl
2Be dissolved in the electron donor, add tetrabutyl titanate, get " MgCl
2-Ti (OBu)
4-electron donor " adducts,
(4) two kinds of adductss that step (2) and step (3) are obtained mix with certain proportion, add by " form conditioning agent ", add the silica gel after the activated processing of above-mentioned steps (1), and the uniform mixing after drying gets ingredient of solid catalyst,
(5) randomly, in the gained solid catalyst, add aluminium diethyl monochloride successively and/or tri-n-hexyl aluminum fully reduces.
9, a kind of catalyzer that is applicable to vinyl polymerization or copolymerization comprises the reaction product of following two components:
(1) the described catalyst component of one of claim 1-7;
(2) organoaluminum component.
10, the catalyzer of claim 9 is at vinyl polymerization or ethene and at least a C
3-C
8The application of alpha-olefin copolymer in closing.
11, the application of the catalyzer of claim 9 in ethene gas phase or slurry polymerization or copolymerization.
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| CN 02131459 CN1229401C (en) | 2002-10-16 | 2002-10-16 | Gas phase ethene polymerization catalyst component and catalyst thereof |
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|---|---|---|---|
| CN 02131459 CN1229401C (en) | 2002-10-16 | 2002-10-16 | Gas phase ethene polymerization catalyst component and catalyst thereof |
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| CN104761665B (en) * | 2014-04-18 | 2018-03-02 | 陈伟 | A kind of ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
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