CN1230551A - Carried double-metal composite catalyst for the polymerization of olefine and its preparation process - Google Patents

Carried double-metal composite catalyst for the polymerization of olefine and its preparation process Download PDF

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CN1230551A
CN1230551A CN 98101239 CN98101239A CN1230551A CN 1230551 A CN1230551 A CN 1230551A CN 98101239 CN98101239 CN 98101239 CN 98101239 A CN98101239 A CN 98101239A CN 1230551 A CN1230551 A CN 1230551A
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composite catalyst
metal composite
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孙爱武
韩世敏
胡友良
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Institute of Chemistry CAS
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Abstract

The catalyst contains metallocene compound of Ti, V, Zr or Hf, non-metallocene compound of Ti or V, electron donor compound and magnesium chloride as carrier. By using the catalyst, polymer with molecular weight distribution as wide as 2-35 and improved machinability may be produced.

Description

For olefines polymerization carried double-metal composite catalyst and preparation method thereof
The present invention relates to a kind of for olefines polymerization carried double-metal composite catalyst, relate to their a kind of preparation method and the application in olefinic polymerization.
USP4,399,054 have provided a kind of MgCl 2The carried catalyst preparation method, though this catalyzer provides high polymerization activity, the corresponding polymer form is good, complicated process of preparation, cost height.
EP-A-447071 has adopted the solution of first preparation metallocene and aikyiaiurnirsoxan beta, adds MgCl successively 2, Nonmetallocene makes bimetallic catalyst.US4,701,432,5,183,867 have also provided preparation metallocene and Nonmetallocene blended bimetallic catalyst.Pass through a kind of MgR among the EP-A-514594 2(R is an alkyl) class magnesium compound impregnation of silica is handled carrier and is made bimetallic catalyst with Ti compound, metallocene compound successively then.But above-mentioned catalyst activity is not too high, complicated process of preparation, and the polymkeric substance that provides is the molecular weight of polyethylene narrowly distributing particularly.
The present invention has overcome the problem that is difficult to process that narrow molecular weight distribution is brought, utilize this catalyst system,, can adjust molecular weight distribution width (2～35) by changing polymerizing condition, overcome the problem that is difficult to process that narrow molecular weight distribution is brought, effectively improved the polymer processing performance.
Catalyst system of the present invention, its ingredient of solid catalyst is by MgCl 2Carrier earlier and the reaction of the Nonmetallocene compound of Ti or V, in the presence of electron donor(ED), pass through the double-metal composite catalyst precursor of gained after the halogen ion-exchange agent treated and the resulting product of metallocene M compound of Ti, V, Zr or Hf.Also can be earlier metallocene compound to be loaded on MgCl 2On the carrier, the Nonmetallocene compound with Ti or V reacts resulting product again.Wherein Nonmetallocene compound and anhydrous MgCl 2Proportioning is 0.12～8, halogen ion-exchange reagent and MgCl 2Molar ratio be 0.08～12, electron donor(ED) and MgCl 2Molar ratio be 0.1～0.16, the mol ratio of metallocene compound and Nonmetallocene compound is 0.1～10.
The Nonmetallocene compound of above-mentioned Ti or V is the halogenide of Ti, halo alkoxide, VCl 3Or VOCl 3, titanium compound is TiCl 4TiCl 3Or general molecular formula is Ti (OR) 4-nCl nThe halo alkoxide, wherein R be have 1～10 carbon atom alkyl or-the COR base, 0≤n≤4, X is a halogen.
Above-mentioned halogen ion-exchange reagent is carboxylic acid halides, organic aluminum halide, halogenated silanes, siloxanes, hydrogen halide or TiCl 4
1, the general molecular formula of carboxylic acid halides is
Figure A9810123900051
, wherein R is the alkyl that 1～10 carbon atom is arranged, X is a halogen
2, the general molecular formula of organic aluminum halide is R 2AlX, RAlX 2, R 3Al 2X 3, wherein R is the alkyl that 1～10 carbon atom is arranged, X is a halogen
3, the general molecular formula of halogenated silanes or siloxanes is SiR 4-nX n, wherein R is the alkyl that 1～10 carbon atom is arranged, X is a halogen, 0≤n≤4
4, the hydrogen halide general molecular formula is HX, and X is a halogen
Wherein the electron donor(ED) that adds in the carried double-metal composite catalyst preparation can be a carboxylicesters, as ethyl benzoate, diisobutyl phthalate, also can be silicoorganic compound, as tetraethoxy, methyltrimethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, Union carbide A-162, phenyl triethoxysilane.
Wherein metallocene M compound is the compound with following structure:
Cp ⅠMR 1R 2R 3 (Ⅰ)
Cp ⅠCp ⅡMR 1R 2 (Ⅱ)
Cp I-A-Cp IIMR 1R 2(III) wherein M is Ti, V, Zr or Hf; Cp IAnd Cp IIBeing the monocycle of band conjugation ∏ electronics or the ligand of polynuclear plane, can be cyclopentadienyl, the cyclopentadienyl of replacement or indenyl; R 1, R 2, R 3Be hydrogen atom, halogen atom, alkyl or alkoxyl group; A is a chain Ji Qiao, can be alkenyl bridge or group with following structure
Figure A9810123900053
S wherein 1Be Si, Ge or S n, R 1, R 2It is the aryl that the alkyl of 1～5 carbon atom is arranged or 6～10 carbon atoms are arranged.
The solid ingredient of the present invention inert solvent of selecting that contacts is hexane, heptane, benzene or toluene.
Olefin polymerization catalyst system comprises above-mentioned ingredient of solid catalyst and a kind of alkylaluminium cpd, this alkylaluminium cpd can be a trialkyl aluminium compound, wherein alkyl has 1～10 carbon atom, it also can be the alkylaluminoxane that 1～50 repeating unit-RAlO-is arranged, wherein R is the alkyl that 1～5 carbon atom is arranged, or the cycloalkyl or the aryl of 6～10 carbon atoms or the above two mixture arranged.
(1) trialkyl aluminium compound can be a trimethyl aluminium, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, three hexyl aluminium or three isohexyl aluminium.
(2) alkylaluminoxane can be poly-methylaluminoxane.
The mol ratio of alkylaluminium cpd and metallocene compound is 100～5000 in the catalyst system of the present invention.
The present invention has following characteristics:
When 1, alkylaluminium cpd was a kind of trialkyl aluminium compound that does not contain MAO or similarly poly-alkylaluminoxane in the catalyst system of the present invention, component of the present invention still can provide a kind of very highly active catalyzer that has.
2, catalyst system of the present invention is applicable to and produces LLDPE, is characterized in that low density value is arranged with respect to alpha-olefin content.
3, carried double-metal composite catalyst system of the present invention has high activity, and catalyzer is stable.
4, the polymkeric substance of catalyst system preparation of the present invention has
5, wide molecular weight distribution width, and width-adjustable can effectively improve the polymer processing performance, and having enlarged it should
Use scope.
6, catalyst system preparation method of the present invention is simple, and cost is low, and it is good to repeat performance, is easy to industrialization.
In order to further specify characteristics of the present invention, provide some examples below, but scope of the present invention is not limited thereto.Relevant data is listed as follows in the experiment: embodiment catalyzer promotor catalyst activity * 10 -3M w/ M n
(gPE/gCat.h)1 Cat-Ⅰ MAO 8.6 3.12 Cat-Ⅱ Al(iBu) 3 7.5 13.53 Cat-Ⅲ Al(iBu) 3 10.6 15.24 Cat-Ⅳ MAO 12.6 3.35 Cat-Ⅳ AlEt 3 9.4 27.46 Cat-Ⅴ AlEt 3 7.7 18.17 Cat-Ⅴ AlEt 3/MAO 9.4 12.98 Cat-Ⅵ MAO 7.6 3.0
Example 1Ti catalyzer is synthetic:
To the process thorough drying.With adding 2.2g Magnesium Chloride Anhydrous, 100ml hexane and 31mlTi (OBu) in the high pure nitrogen metathetical 300ml sand core reactor 4, maintain the temperature at 60 °, and continue to stir 3 hours, after the question response liquid cooling but, in ice-water bath, 0.9ml diisobutyl phthalate, 60ml AlEt 2Cl (25wt%in n-hexane) successively joins in the product of front, obtains slurries, and slurries continue to be stirred half an hour approximately, take out from ice-water bath then, filter slurries, repeatedly wash with the exsiccant hexane, obtain the Ti series catalysts.The preparation of zirconocene/triethyl aluminium solution:
Pass through thorough drying in advance to one, pump drainage is equipped with in the 50ml two-mouth bottle that stirs magneton with the high pure nitrogen metathetical and adds 6ml (1.8M) AlEt 3Hexane solution and 0.25gC 2H 4(Ind) 2ZrCl 2(EBI), with this system under nitrogen atmosphere in 20 ° of continuously stirring 2 hours, obtain settled solution during EO.
The preparation of bimetal carried catalyst:
Under the protection of 20 ° and nitrogen atmosphere; pass through thorough drying in advance to one; pump drainage is equipped with adding 30ml anhydrous hexane and the above-mentioned Ti catalyzer of 3g in the churned mechanically 100ml sand core reactor with the high pure nitrogen metathetical, the EBI/AlEt that makes above adding when stirring then 3Solution, and with solution 50 ° the heating 3 hours, behind the EO, drain the removal solvent, obtain the catalyzer Cat-I that 3.3g has following characteristic: Cl 45.5% Mg 14.0% Ti 3.3% Zr, 0.55% polyreaction (HDPE)
Purged 3 hours at 90 ° with nitrogen in advance at one, be equipped with in the autoclave of anchor stirrer, 11 hexanes of packing into, successively add 0.55gMAO, 0.05g above-mentioned catalyzer, reactor is warmed up to 70 °, and feeds the ethene of 0.7MPa, keeping under temperature and the ethylene pressure constant condition polyreaction being carried out 1 hour.Obtain white spheroidal particle shaped polyethylene, the 430g that weighs, productive rate are 8600g polyethylene/g catalyzer.Polyethylene melting index (MI) is 2.1; M w/ Mn=3.1.
Embodiment 2 prepares Ti catalyzer methylaluminoxane (MAO)/zirconocene formulations prepared from solutions by the step identical with example 1
Pass through thorough drying in advance to one, pump drainage, the 50ml two-mouth bottle that stirs magneton is equipped with in the high pure nitrogen displacement, adds the 20ml dry toluene, 1.2gMAO and 0.3gEBI, this system continuously stirring 2 hours under nitrogen atmosphere obtains settled solution during EO.
The preparation of Zr catalyst:
At 20 °; the nitrogen atmosphere protection down; pass through thorough drying in advance to one; pump drainage; replace and be equipped with in the churned mechanically 100ml sand core reactor with high pure nitrogen; add 30ml dry toluene and the above-mentioned Ti catalyzer of 4g; the EBI/MAO solution that is worth above then adding; and in 40 ° with solution heating 10 hours; stir when finishing suction filtration, washing; at last solvent is steamed, obtain the catalyzer Cat-II that about 4.4g has following characteristic: Cl=46.0% Mg=13.5% Ti=3.4% Zr=0.35% polyreaction (HDPE)
Use the above-mentioned catalyzer of 0.05g, carry out polyreaction, but use 0.13g Al (iBu) according to example 1 step 3Replace 0.55g MAO, obtain 376g.Spherical polyethylene (productive rate 7520g polyethylene/g catalyzer) with following characteristic, MI=1.4 M w/ Mn=13.5.
Example 3Ti Preparation of catalysts:
To the process thorough drying.With adding 3.81g Magnesium Chloride Anhydrous, 100ml hexane and 27.2gTi (OBu) in the high pure nitrogen metathetical 300ml sand core reactor 4, maintain the temperature at 60 °, and continue to stir 3 hours, after the question response liquid cooling but, in ice-water bath, 5.1g AlEtCl 2Join in the product of front, obtain slurries, slurries continue to be stirred half an hour approximately, take out from ice-water bath then, filter slurries, repeatedly wash with the exsiccant hexane, obtain the Ti series catalysts.The step identical with example 1 prepares Cp 2ZrCl 2/ AlEt 3Solution prepares Zr catalyst by the step identical with example 2, obtains catalyzer Cat-III Cl=46.3% Mg=13.4% Ti=3.5% Zr=1.22% polyreaction (HDPE)
Prepare polyethylene by the step identical with example 2, catalytic activity is 10600 polyethylene/g catalyzer, MI=1.5, M w/ Mn=15.2.
Example 4Ti Preparation of catalysts:
In through thorough drying, with high pure nitrogen metathetical 300ml sand core reactor, add 3.81g Magnesium Chloride Anhydrous, 100ml hexane and 27.2gTi (OBu) 4Maintain the temperature at 60 °, and continue to stir 3 hours, after the question response liquid cooling but, in ice-water bath, the 32.2g methyl hydrogen siloxane is joined in the product of front, obtain slurries, slurries continue to be stirred half an hour approximately, from ice-water bath, take out then, filter slurries, repeatedly wash, obtain the Ti series catalysts with the exsiccant hexane.Prepare Zr catalyst by the step identical, just use Cp with example 2 2ZrCl 2Replaced C 2H 4(Ind) 2ZrCl 2, obtain having the catalyzer Cat-IV of following characteristic:
Cl=45.5% Mg=14.1% Ti=3.3% Zr=1.50% polyreaction: (LLDPE)
Purged 3 hours at 90 ° with nitrogen in advance at one, be equipped with in the autoclave of anchor stirrer, the 1L hexane of packing into successively adds 0.9gMAO, 0.05g above-mentioned catalyzer, be warmed up to 70 °, feed 0.7MPa ethene, the 300g butylene, reacted 1 hour, obtain the ethylene-butene copolymer (productive rate is that 12600g multipolymer/g catalysis is neat) that the 630g form of spherical particles has following characteristic: MI=0.8, d=0.917, M w/ Mn=3.3
Embodiment 5 polyreactions: (HDPE)
Purged 3 hours at 90 ° with nitrogen in advance at one, and be equipped with in the autoclave of anchor stirrer, the 1L hexane of packing into successively adds 1.41g AlEt 3, catalyzer in the 0.1g example 4 is warmed up to 70 °, feeds 0.7MP aEthene reacted 1 hour, obtained the polyethylene (productive rate is 9600g polyethylene/g catalyzer) that the 470g form of spherical particles has following characteristic: MI=1.3, M w/ Mn=27.4
Embodiment 6Ti Preparation of Catalyst:
To through thorough drying, pump drainage repeatedly, adding 3.0g Magnesium Chloride Anhydrous and 100ml heptane in the 300ml sand core reactor of replace with high pure nitrogen, 40mlTi (OBu) 4, be warming up to 60 °, and after stirring question response liquid cooling but in 3 hours under this temperature, in ice-water bath, with 43ml SiCl 4Join in the product of front, obtain slurries, remove ice-water bath, suction filtration repeatedly washs with dry hexane, obtains the Ti series catalysts.
The step identical with example 1 prepares EBI/AlEt 3The preparation of solution Zr catalyst:
Under the protection of 20 ° and nitrogen atmosphere, pass through thorough drying in advance to one, pump drainage with the high pure nitrogen displacement and be equipped with and add 20ml anhydrous hexane and the above-mentioned Ti catalyzer of 2.0g in the churned mechanically 100ml sand core reactor, adds EBI/AlEt then 3Solution (0.17g EBI), and with solution 40 ° of heating 3 hours, EO is removed solvent and is obtained the catalyzer Cat-V that 2.2g has following characteristic later on: Cl=45.3% Mg=14.5% Ti=3.8% Zr=0.67% polyreaction: (LLDPE)
Purged 3 hours at 90 ° with nitrogen in advance at one, and be equipped with in the autoclave of anchor stirrer, 11 hexanes of packing into successively add 0.4g AlEt 3, the above-mentioned catalyzer of 0.05g is warmed up to 70 °, feeds 0.7MPa ethene, and the 150g butylene reacted 1 hour, obtained the ethylene-butene copolymer (productive rate is 7720g multipolymer/g catalyzer) that the 386g form of spherical particles has following characteristic: MI=0.35, d=0.916, M w/ Mn=18.1g.
Embodiment 7 uses the above-mentioned catalyzer of 0.05g as example 6 preparation bimetal carried catalyst polyreactions (HDPE), carries out polyreaction under the condition identical with example 1, but uses 0.45g AlEt 3, 0.55g MAO obtains the polyethylene that the 472g spherulitic has following characteristic: MI=2.3, M as promotor w/ Mn=12.9.
The preparation that embodiment 8 prepares Ti series catalysts Zr catalyst by the step identical with example 6:
When stirring under 20 ° and nitrogen atmosphere protection; 50ml dry toluene and the above-mentioned Ti series catalysts of 3.0g are joined 100ml drying in advance; what pump drainage was crossed is equipped with in the churned mechanically sand core reactor; feed 0.3g then and be dissolved in MAO in the 10ml dry toluene; under agitation mixture was heated 3 hours at 40 °; repeatedly wash with toluene; again the catalyzer that obtains is distributed in the 50ml dry toluene again; add 0.15g EBI; and with mixture 40 ° the heating 3 hours; thereafter with dry toluene repeatedly washing under normal temperature; the catalyst slurry that obtains is transferred in the two-mouth bottle; vacuum steams solvent, obtains the catalyzer Cat-VI that 3.3g has following characteristic: Al=1.8% Cl=45.5% Mg=13.3% Ti=3.7% Zr=0.62% polyreaction (HDPE)
Purged 3 hours at 90 ° with nitrogen in advance at one, 11 hexanes of packing in the autoclave of anchor stirrer are housed, successively add the above-mentioned catalyzer of 0.57g MAO, 0.05g, be warmed up to 70 °, feed 7bar ethene, polymerization 1 hour obtains 380g spherulitic polyethylene (7600g polyethylene/g catalyzer): MI=2.1, M w/ Mn=3.0.

Claims (8)

1, a kind of carried double-metal composite catalyst of for olefines polymerization is characterized in that described carried double-metal composite catalyst comprises metallocene compound and is stated from MgCl 2On Ti or the composite catalyst precursor that obtains of the Nonmetallocene compound of V and halogen ion-exchange reagent, electron donor(ED) reaction, described metallocene compound has following array structure:
Cp ⅠMR 1R 2R 3 (Ⅰ)
Cp ⅠCp ⅡMR 1R 2 (Ⅱ)
Cp I-A-Cp IIMR 1R 2M is Ti in (III) formula, V, Zr or Hf; Cp IAnd Cp IIBe the monocycle of band conjugation ∏ electronics or the ligand of polynuclear plane; R 1, R 2, R 3Be hydrogen atom, halogen atom, alkyl or alkoxyl group; A is a chain Ji Qiao.
2, a kind of carried double-metal composite catalyst according to claim 1 is characterized in that described monocycle ligand is the cyclopentadienyl of cyclopentadienyl or replacement.
3, a kind of carried double-metal composite catalyst according to claim 1 is characterized in that described many ring ligands are indenyl.
4, a kind of carried double-metal composite catalyst according to claim 1 is characterized in that described chain Ji Qiao is alkenyl bridge or group with following structure: S wherein 1Be Si, Ge or S nR 1, R 2It is the aryl that the alkyl of 1～5 carbon atom is arranged or 6～10 carbon atoms are arranged.
5, a kind of carried double-metal composite catalyst according to claim 1, the Nonmetallocene compound that it is characterized in that described Ti or V are that halogenide, the general molecular formula of Ti is Ti (OR) 4-nX nHalo alkoxide or VCl 3, VOCl 3Wherein R be have 1～10 carbon atom alkyl or-the COR base, 0≤n≤4, X is a halogen.
6, a kind of carried double-metal composite catalyst according to claim 1 is characterized in that described halogen ion-exchange reagent is carboxylic acid halides, organic aluminum halide, halogenated silanes, halo siloxanes, hydrogen halide, or TiCl 4, the general molecular formula of described carboxylic acid halides is
Figure A9810123900031
, the general molecular formula of organic aluminum halide is R 2AlX, RAlX 2, R 3Al 2X 3, the general molecular formula of halogenated silanes or siloxanes is SiR 4-nX n, the hydrogen halide general molecular formula is HX, and wherein R is the alkyl that 1～10 carbon atom is arranged, and X is a halogen, 0≤n≤4.
7, the preparation method of a kind of carried double-metal composite catalyst according to claim 1 is characterized in that step is carried out in the following order:
(1) is stated from MgCl 2On the composite catalyst precursor preparation: MgCl 2Carrier earlier and the Nonmetallocene compound of Ti or V reacts, in the presence of electron donor(ED), through obtaining the double-metal composite catalyst precursor after the halogen ion-exchange agent treated, wherein the proportioning of main raw material (mol ratio) is the Nonmetallocene compound of Ti or V: halogen ion-exchange reagent: electron donor(ED): magnesium dichloride is (0.12～8): (0.08～12): (0.1～0.16): 1
(2) metallocene compound of Ti, V, Zr or Hf and above-mentioned precursor in toluene solution with (0.1～10): 1 mole proportioning is mixed.
8, a kind of carried double-metal composite catalyst according to claim 7 is characterized in that described electron donor(ED) is ethyl benzoate, diisobutyl phthalate, tetraethoxy, methyltrimethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, Union carbide A-162, phenyl triethoxysilane.
CN 98101239 1998-04-01 1998-04-01 Carried double-metal composite catalyst for the polymerization of olefine and its preparation process Pending CN1230551A (en)

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