CN1274721C - Catalyst for ethene polymerization or multipolymer, preparing method thereof - Google Patents
Catalyst for ethene polymerization or multipolymer, preparing method thereof Download PDFInfo
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- CN1274721C CN1274721C CN 03123950 CN03123950A CN1274721C CN 1274721 C CN1274721 C CN 1274721C CN 03123950 CN03123950 CN 03123950 CN 03123950 A CN03123950 A CN 03123950A CN 1274721 C CN1274721 C CN 1274721C
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Abstract
The present invention provides a composite supported catalyst for ethene polymerization and copolymerization and a preparation method thereof. The catalyst is prepared by dissolving magnesium halide in an organic epoxide, an organic phosphorus compound and an inert diluent, adding a porous inert carrier with a large specific surface area to the magnesium halide solution in the existence of an alkane separation assisting agent, adding the halide of the transitional metal of titanium for coprecipitation, and adding an alcohol compound according to different activity requirements and density ranges and (or) adding an electron donor compound after adding the halide of the transitional metal of the titanium. When used for catalyzing ethene polymerization or copolymerization, the catalyst shows high activity; simultaneously, the catalyst has goof copolymerization performance and high hydrogen regulation sensitivity; the produced copolymer has a wide density range from 0.900 to 0.950 g/ml; the polymer has the advantages of good particle shape and less fine powder and is capable of being used for slurry polymerization and gas-phase polymerization.
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, and the application in vinyl polymerization or copolymerization.
Background technology
Later 1970s, it is the titanium-magnesium high-effective carrier catalyst of carrier with the magnesium chloride that companies such as Mitsui petroleum chemistry company and U.S. Meng Ai have succeeded in developing, owing to adopted carrier to improve titanium atom active centre utilization ratio, simplified the polymerization technique flow process, therefore made world's polyolefin industry obtain fast development.Mitsui petroleum chemistry company Preparation of catalysts method of disclosed vinyl polymerization and copolymerization in JP49-51378 is: magnesium dichloride through grinding and ethanol synthesis generate MgCl in the mineral oil medium again
26C
2H
5OH alcohol adduct slurries remove most of ethanol with aluminium diethyl monochloride generation esterification again, carry the titanium reaction with titanium tetrachloride at last, obtain Ti/MgCl
2High-effective carrier catalyst.This method for preparing catalyst is simple, the reaction conditions gentleness, and activity is higher during the catalyst vinyl polymerization.But in the Preparation of catalysts process, the irregular platy shaped particle that produces when there be former grinding in the carrier magnesium chloride in the slurry reaction system causes the solid catalyst particle form that obtains relatively poor, and thickness is inhomogeneous, thereby polymer morphology is also bad, and fine powder is more.
This is that the catalyzer of preparing carriers is general mobile relatively poor with single magnesium chloride, has limited the application of catalyzer in industrial production, special application on gas-phase fluidized-bed reactor.Therefore people by introducing a kind of effective carrier or weighting material, promptly adopt complex carrier type catalyzer to improve the particle form of catalyzer again.Common way is that the halogenide with the halogenide of titanium and magnesium is dissolved in the solvent, forms homogeneous solution, adds inert silica gel carrier or alumina load then, steams solvent at last and obtains efficient complex carrier type catalyzer.As US4302565, CN1064870 discloses the halogenide with tetrahydrofuran (THF) dissolving magnesium dichloride and titanium, add silica gel then, more progressively excessive tetrahydrofuran (THF) evaporate to dryness, the halogenide of magnesium dichloride and titanium is separated out and loads on the silica gel last preparation catalyzer gradually.Though it is good that this catalyzer has a particle form, good fluidity, the advantage that the polymer beads form is good, the dissatisfactory shortcoming of activity when all there is the complicated and polymerization of preparation method in the catalyzer of this method preparation.
In order to improve the preparation method who has narrated a kind of Ziegler-Natta catalyst among the activity of such catalysts CN1085915.In tetrahydrofuran (THF), make the tetrahydrofuran solution of titanous chloride with the magnesium metal reduction titanium tetrachloride, magnesium chloride is dissolved in this tetrahydrofuran solution again, filter out unreacted metal magnesium and undissolved magnesium chloride, filtering gained solution and silica gel thorough mixing, carry out the discrete particles that spraying drying obtains catalyzer then.This catalyzer titaniferous amount height, active high, when catalyzed ethylene and a-olefinic polymerization, can reduce hexane extractable content exponentially.But, employed silica gel particle diameter is between 0.1 μ m～1.0 μ m during this Preparation of Catalyst, have only through complicated spraying drying operation, just can obtain comparatively uniform catalyst particle, need during use catalyzer is dispersed in the mineral oil, if convection drying, gained granules of catalyst wider distribution, fine powder is many and mobile poor.
Patent CN85100997 discloses a kind of catalyst system that is used for olefinic polymerization and copolymerization, this catalyst system comprises: (first) contains the ingredient of solid catalyst of Ti, (second) alkylaluminium cpd, (the third) organosilicon, wherein (first) component is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous solution by magnesium halide, this solution mixes with the titanium tetrahalide or derivatives thereof, in the presence of compounds such as precipitation additive such as organic acid anhydrides, organic acid, ether, ketone, separates out solids; This solids is handled with the multi-carboxylate, and it is attached on the solids, handles with titanium tetrahalide and inert diluent and obtains.When this catalyst system was used for propylene polymerization, catalyst activity was higher, and the degree of isotacticity of resulting polymers is higher, and apparent density is big.But this catalyzer is when being used for vinyl polymerization, still existing is the granules of catalyst poor morphology, be difficult on gas-phase fluidized-bed, use, and activity is lower, hydrogen is transferred shortcoming such as sensitivity inadequately, particularly this dissolution system need add relatively large titanium tetrachloride in the presence of as precipitation additive at organic acid anhydride and could come out the magnesium dichloride precipitating, not only strengthen the treatment capacity of waste liquid, also easily equipment has been caused corrosion simultaneously, strengthened the cost of catalyzer.For example disclosed under 85 ℃, the condition of hydrogen pressure 0.25Mpa, ethylene pressure 0.75Mpa in embodiment 24, vinyl polymerization 2 hours, polymerization activity are 537Kg polyethylene/gTi (about 7000gPE/gcat).
Patent CN1229092 has improved the method for preparing catalyst among the CN85100997, in the Preparation of catalysts process, add ethanol magnesium halide is carried out modification, activity increases substantially when making the catalyst vinyl polymerization for preparing, but this system has still adopted the magnesium halide dissolution system among the CN85100997, thereby still need relatively large titanium tetrahalide to carry out precipitating, simultaneously this catalyzer still with single magnesium dichloride as carrier, so the particle form of catalyzer is still not very good, the easily broken fine polymer powder that easily produces of granules of catalyst.
Summary of the invention
The shortcoming that the objective of the invention is to overcome above-mentioned catalyst preparation technology provides a kind of new class spherical catalyst component that is used for vinyl polymerization or copolymerization employing complex carrier and preparation method thereof with not enough.Has advantages of high catalytic activity during the catalyst vinyl polymerization of this method preparation, polymkeric substance has the variable density scope 0.900-0.950g/ml of broad, has good hydrogen response, the solid difficult fragmentation of granules of catalyst, particle form well is the class sphere, size distribution is narrow, and median size is 40 μ m～50 μ m.Both be suitable for the ethene slurry polymerization and also be suitable for the vapour phase polymerization mode, and the polymer beads form is good, fine powder is few, and slurry polymerization is less than less than the fine powder of 75 μ m or equals 1.0%, and vapour phase polymerization does not exist less than 75 μ m fine powders.
The present invention is different with CN85100997 and CN1229022, though also adopted organic epoxy compounds, organo phosphorous compounds and inert diluent dissolve magnesium halide, but all need adding organic acid anhydride, organic ether or ketone compounds, above-mentioned patent solids is separated out as precipitation additive and relative a large amount of halogenated titanium, the present invention only need adopt alkane as precipitation additive, and get final product with quite a spot of halogenated titanium, thereby reduced the liquid waste disposal amount, reduced pollution.
The present invention also adopts the large specific surface porous silica gel as complex carrier, but different with US4302565, CN1064870, has adopted and the diverse magnesium halide dissolution system of above-mentioned patent.Above-mentioned patent all adopts tetrahydrofuran (THF) to dissolve magnesium halide and halogenated titanium, and will spend the long time hot nitrogen, and tetrahydrofuran (THF) is dried up, and just can reach magnesium halide, halogenated titanium are deposited in purpose on the silica gel.Generally, all need prepare parent, again with the parent secondary load on silica gel, so preparation method's complexity.
The present invention compares with CN1085915, except that adopting different dissolution system, in active ingredient, a carrier scope and load with drying means on have bigger different.
Another object of the present invention provides a kind of preparation method of composite carried catalyst.Adopt magnesium halide and porous inert carrier as complex carrier, the porous inert carrier shape is spherical in shape, particle size range is at 0.1 μ m～150 μ m, preferable particle size is 5 μ m～50 μ m, select bigger serface porous inert carrier for use, help improving magnesium halide in its surperficial load, help improving the content of magnesium in the catalyzer, the irregular aggregate of magnesium halide occurs in the catalyzer when also helping preventing high Mg content and cause the bad phenomenon of granules of catalyst to occur.
The present invention is in catalyst preparation process, having added electronic donor compound capable makes catalyzer have good copolymerization performance more, the ethylene copolymer of being produced has the variable density scope of broad, the polymkeric substance that not only is suitable for production middle and higher density in slurry process is applicable to the product of producing LLDPE in the vapor phase process simultaneously.
The present invention is used for vinyl polymerization or copolymerization catalyst, comprises following component:
A, titaniferous ingredient of solid catalyst, it is by being dissolved in magnesium halide in organic epoxy compounds, organo phosphorous compounds and the inert diluent, form homogeneous solution, add the porous inert carrier through dehydration in the presence of the alkane precipitation additive, the halogenide or derivatives thereof eutectoid that adds transition metals Ti again goes out to be prepared from;
B, organo-aluminium compound;
Ratio between B component and the component A is 5～1000 with aluminium titanium molar ratio computing.
Magnesium halide described in the catalyst component A of the present invention is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, two magnesium iodides, preferred magnesium dichloride.
The halogenide or derivatives thereof of the transition metals Ti described in the catalyst component A of the present invention is a titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, a kind of in trichlorine one ethanolato-titanium, or their mixture.
Organic epoxy compounds is an oxyethane in the catalyst A component of the present invention, propylene oxide, butylene oxide ring, epoxy chloropropane, a kind of in the methyl glycidyl ether, or their mixture.
Organo phosphorous compounds is the ortho-phosphoric acid trimethyl in the catalyst A component of the present invention, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, a kind of in the phosphorous acid benzene methyl or their mixture.
Inert diluent is benzene, toluene and derivative thereof in the catalyst A component of the present invention.
Used alkane precipitation additive is a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture in the catalyst A component of the present invention, preferred butane, pentane, hexane, hexanaphthene, heptane.
The volume ratio of inert diluent and alkane precipitation additive is in the catalyst A component of the present invention: 1: 0.1～5, be preferably: 1: 0.5～1.5.
The described magnesium halide dissolving of catalyst component A of the present invention forms after the homogeneous solution, can also add alcohol compound as active regulator, alcohol compound wherein is a kind of in the straight chain alcohol of C1～C10 or the isomery alcohol or their mixture, for example, a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, hexanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, hexalin, methyl-cyclohexanol, Bian alcohol, the methyl Bian alcohol etc. or their mixture, preferred fat alcohol is the best with ethanol, butanols, 2-Ethylhexyl Alcohol.
Porous inert carrier is a silicon-dioxide among the catalyst component A of the present invention, wherein a kind of or its mixture of aluminium sesquioxide, and the shape of porous inert carrier is spherical in shape, particle diameter is 0.1 μ m～150 μ m, preferable particle size is 5 μ m～50 μ m, and pore volume is at 1.2～1.8ml/g, and specific surface is at 250-350m
2/ g handles through dehydration and aluminum alkyls before using, and the employed aluminum alkyls of processing porous inert carrier is a kind of in trimethyl aluminium, triethyl aluminum, the triisobutyl aluminium or their mixture, with triethyl aluminum for well.
Magnesium halide and inert support mol ratio among the catalyst component A of the present invention are: 1: 0.5～15.
Titaniferous ingredient of solid catalyst described in the catalyst component A of the present invention, can also add electronic donor compound capable after adding the halogenide or derivatives thereof of transition metals Ti, wherein electronic donor compound capable is a kind of in alkyl ester, fatty ether, alicyclic ethers and the alicyclic ketone of aliphatics and aromatic carboxylic acid or their mixture.Particularly suitable be the alkyl ester that contains the representative examples of saturated aliphatic carboxylic of 1～4 carbon atom; The alkyl ester that contains the aromatic carboxylic acid of 7～8 carbon atoms; Contain 2～8 carbon atoms, preferably the fatty ether of 4～5 carbon atoms; The alicyclic ethers that contains 4～5 carbon atoms preferably contains the monoether or the diether of 4 carbon atoms; With contain 3～6 carbon atoms, preferably contain the aliphatic ketone of 3～4 carbon atoms, most preferred electronic donor compound capable is a tetrahydrofuran (THF).
The mol ratio that adds between described each component of catalyst component A of the present invention is in every mole of magnesium halide, 0.01～10 mole of organic epoxy compounds, with 0.02～4 mole for well; 0.01～10 mole of organo phosphorous compounds, with 0.02～4 mole for well; 0～10 mole of alcohol compound; 3～30 moles of inert diluents, with 5～20 moles for well; 0.5～15 mole of inert support; 0.04～1 mole in the halogenide of transition metals Ti, preferred 0.06～0.5 mole; 0～10 mole of electronic donor compound capable; The volume ratio of inert diluent and alkane precipitation additive is 1: 0.1～5, be preferably 1: 0.5～and 1.5.
The described alkylaluminium cpd of catalyst component B of the present invention, its general formula is AlR
nX
3-n, R can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for hydrogen, carbonatoms in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichlorides, wherein with triethyl aluminum, triisobutyl aluminium for well.
In the catalyst system of the present invention, in the B component among aluminium and the component A mol ratio of titanium be 5～1000, be preferably 50～500.
The preparation method of catalyst component A of the present invention is as follows: under agitation magnesium halide is dissolved in organic epoxy compounds, organo phosphorous compounds and the inert diluent, temperature remains on 30 ℃～80 ℃, after forming homogeneous solution, also can add alcohol compound reaction 0.5～2 hour, in the presence of the alkane precipitation additive, add porous inert carrier, then system is cooled in-30～60 ℃ of scopes, temperature is preferably-20～10 ℃; Titanium compound is splashed in the above-mentioned magnesium halide homogeneous solution with inert support, reaction mixture is warming up to 60～100 ℃ again, with suspension after stirring 0.5～8 hour under this temperature, also can add electronic donor compound capable and continue reaction 0.1～2 hour, stopping to stir the back solids separates out from mix slurry, decant or remove by filter mother liquor is used the hexane wash solids, makes titaniferous solid catalytic ingredient.
Catalyst A of the present invention, B component can directly apply to polymerization system, also can be used for polymerization system after the pre-earlier complex reaction.
The catalyzer that is used for vinyl polymerization or copolymerization of the present invention is applicable to slurry polymerization and vapour phase polymerization mode.
Catalyzer of the present invention can be used for the equal polymerization of ethene, also can be used for the copolymerization of ethene and other alpha-olefin, and comonomer can be propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene etc.
Polymerization or copolymerization that catalyzer of the present invention is used for ethene compared with prior art have following tangible advantage:
1, has advantages of high catalytic activity during the catalyst vinyl polymerization, this catalyzer has good copolymerization performance simultaneously, the ethylene copolymer of being produced has the variable density scope 0.900～0.950g/ml of broad, and good hydrogen response, the solid difficult fragmentation of granules of catalyst, particle form well becomes the class sphere, size distribution is narrow, promptly can be used for slurry polymerization and also be suitable for carrying out polymerization on gas phase process, and the polymer beads form is good, fine powder seldom.The slurry polymerization polymkeric substance is less than less than 75 μ m fine powders or equals 1.0%, and there is not the polymkeric substance less than 75 μ m in vapour phase polymerization.
2, magnesium compound of the present invention adopts organic epoxy compounds, organo phosphorous compounds, inert diluent dissolves and forms homogeneous solution, adopts alkane precipitation additive and porous large specific surface inert support, only needs the halogenide of more a spot of titanium that magnesium dichloride is separated out.
3, the add-on of titanium tetrachloride significantly reduces in the catalyst preparation process, and the synthesis technique of catalyzer is simplified greatly, has reduced the cost of catalyzer, has also reduced pollution.And the add-on that can utilize inert support is regulated the titanium content of catalyzer, thereby makes catalyzer adapt to different polymerization techniques.
4, the present invention adopts magnesium halide and porous inert carrier as complex carrier, the porous inert carrier shape is spherical in shape, particle size range is at 0.1 μ m～150 μ m, preferable particle size is 5 μ m～50 μ m, select bigger serface porous inert carrier for use, help improving magnesium halide in its surperficial load, help improving the content of magnesium in the catalyzer, the irregular aggregate of magnesium halide occurs in the catalyzer when also helping preventing high Mg content and cause the bad phenomenon of granules of catalyst to occur.
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively,, be warming up to 80 ℃ under stirring through toluene 40ml, epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that molecular sieve was handled, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.The hexane 30ml that adding is crossed through processed, silica gel 2.3g is (through 600 ℃ of processing in 4 hours, 0.7mmol the triethyl aluminum activation treatment), this system is cooled to-25 ℃, slowly drip the 8ml titanium tetrachloride, slowly be warming up to 80 ℃ then, reacted 2 hours, add the 5ml tetrahydrofuran (THF), 80 ℃ are continued reaction 1 hour down.Stop to stir, leave standstill, the very fast layering of suspension extracts supernatant liquid, hexane wash four times, and high pure nitrogen dries up, and obtains the solid catalyst of good fluidity, narrow diameter distribution.Titanium content is 8.1% (weight) in the catalyzer, and Mg content is 4.9% (weight), and tetrahydrofuran (THF) is 12.7% (weight).
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.
(2) ethene slurry polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.48Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 1.
(2) gas-phase fluidized-bed vinyl polymerization
In the gas-phase fluidized-bed reactor of Φ 150, add 350g and make base-material and 10 gram triethyl aluminums (87mmol) through exsiccant full scale plant base resin DGM-1820 polyethylene powder.According to condition adding proportioning is
Hydrogen 10.93% (volume ratio), 1-butylene 20.43% (volume ratio), ethene 58.32% (volume ratio), the mixed gas of nitrogen 7.02% (volume ratio) makes the gas stagnation pressure to 1.7MPa, simultaneously with the systemic circulation fluidisation and be warming up to 75～80 ℃.Adding catalyzer, be warming up to 85 ℃ and pick up counting, polymerization temperature is controlled at～and 90 ℃, after 4 hours, stopped reaction, emptying, discharging.Weigh and carry out performance test, poly-
Close and the results are shown in Table 2.
Embodiment 4
(1) catalyzer is synthetic with embodiment 1.
(2) gas-phase fluidized-bed vinyl polymerization
In the gas-phase fluidized-bed reactor of Φ 150, add 350g and make base-material and 10 gram triethyl aluminums (87mmol) through exsiccant full scale plant base resin DGM-1820 polyethylene powder.According to condition adding proportioning is hydrogen 8.42% (volume ratio), 1-butylene 28.95% (volume ratio), ethene 52.63% (volume ratio), the mixed gas of nitrogen 10.0% (volume ratio) makes the gas stagnation pressure to 1.7MPa, simultaneously with the systemic circulation fluidisation and be warming up to 75～80 ℃.Adding catalyzer, be warming up to 85 ℃ and pick up counting, polymerization temperature is controlled at～and 90 ℃, after 4 hours, stopped reaction, emptying, discharging.Weigh and carry out performance test, polymerization result sees Table 2.
Embodiment 5
(1) catalyzer is synthetic with embodiment 1.Just the tetrahydrofuran (THF) add-on is 8ml.
(2) the ethene slurry polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 6
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively, under giving toluene 40ml, epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that the son sieve was handled, stirring, be warming up to 80 ℃, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.Add 0.56ml ethanol, reaction is 1 hour under 80 ℃ of conditions.The hexane 30ml that adding is crossed through processed, silica gel 2.3g is (through 600 ℃ of processing in 4 hours, through 0.7mmol triethyl aluminum activation treatment), this system is cooled to 0 ℃, slowly drip the 8ml titanium tetrachloride, slowly be warming up to 80 ℃ then, reacted 2 hours, add the 5ml tetrahydrofuran (THF), continue reaction 1 hour under 80 ℃ of conditions.Stop to stir, leave standstill, the very fast layering of suspension extracts supernatant liquid, hexane wash four times, and high pure nitrogen dries up, and obtains the solid catalyst of good fluidity, narrow diameter distribution.
(2) the ethene slurry polymerization is with embodiment 1, and polymerization result sees Table 1.
Embodiment 7
(1) catalyzer is synthetic with embodiment 6.
(2) the ethene slurry polymerization is with embodiment 2, and polymerization result sees Table 1.
Embodiment 8
(1) catalyzer is synthetic with embodiment 6.
(2) ethene slurry copolymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, the catalyzer that adds the quantitative above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, add 1-hexene 20ml, feed hydrogen and make the still internal pressure reach 0.28Mpa, feeding ethene again makes the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization under 85 ℃ of conditions when the ethene absorption reaches 160g, stops polymerization.Polymerization result sees Table 2.
Embodiment 9
(1) catalyzer is synthetic with embodiment 6, and just amount of alcohol added is 0.3ml.
(2) the ethene slurry polymerization is with embodiment 1, and polymerization result sees Table 1.
Embodiment 10
(1) catalyzer is synthetic with embodiment 9.
(2) copolymerization of ethene slurry is with embodiment 8.
Embodiment 11
(1) catalyzer is synthetic with embodiment 6, and just ethanol changes isooctyl alcohol into, and the isooctyl alcohol add-on is 1.56ml.
(2) the ethene slurry polymerization is with embodiment 1, and polymerization result sees Table 1.
Embodiment 12
(1) catalyzer is synthetic with embodiment 11.
(2) copolymerization of ethene slurry is with embodiment 8, and polymerization result sees Table 2.
Embodiment 13
(1) catalyzer is synthetic with embodiment 6, does not just add tetrahydrofuran (THF).
(2) the ethene slurry polymerization is with embodiment 1, and polymerization result sees Table 1.
Embodiment 14
(1) catalyzer is synthetic with embodiment 13.
(2) the ethene slurry polymerization is with embodiment 2, and polymerization result sees Table 1.
Embodiment 15
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively,, be warming up to 80 ℃ under stirring through toluene 40ml, epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that molecular sieve was handled, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.Add 0.3ml ethanol, 0.8ml isooctyl alcohol, reaction is 1 hour under 80 ℃ of conditions.The hexane 30ml that adding is crossed through processed, silica gel 2.3g is (through 600 ℃ of processing in 4 hours, through 0.7mmol triethyl aluminum activation treatment) this system is cooled to 0 ℃, slowly drip the 8ml titanium tetrachloride, slowly be warming up to 80 ℃ then, reacted 2 hours, and added the 5ml tetrahydrofuran (THF), continue reaction 1 hour under 80 ℃ of conditions.Stop to stir, leave standstill, the very fast layering of suspension, extract supernatant liquid, hexane wash four times, the aluminium diethyl monochloride 1.8ml of adding 2.2mol/l reacts 30min under 50 ℃ of conditions, add 1.5mol/l1.2ml tri-n-hexyl aluminum high pure nitrogen and dry up, obtain the solid catalyst of good fluidity, narrow diameter distribution.
(2) the ethene slurry polymerization is with embodiment 2, and polymerization result sees Table 1.
Embodiment 16
(1) catalyzer is synthetic with embodiment 15.
(2) slurry polymerization is with embodiment 8 altogether for ethene, and just hexene-1 add-on is 30ml.Polymerization result sees Table 2.
Embodiment 17
(1) catalyzer is synthetic with embodiment 6.
(3) slurry polymerization is with embodiment 16 altogether for ethene, and polymerization result sees Table 2.
Embodiment 18
(1) catalyzer is synthetic with embodiment 1, and just tetrahydrofuran (THF) changes n-butyl phthalate into, and add-on is 4ml.
(2) the ethene slurry polymerization is with embodiment 2, and polymerization result sees Table 1.
Embodiment 19
(1) catalyzer is synthetic with embodiment 1, and just tetrahydrofuran (THF) changes the 2-sec.-propyl into, 2-isopentyl 1,3 two mystery, and add-on is 5ml.
(2) the ethene slurry polymerization is with embodiment 2, and polymerization result sees Table 1.
Comparative Examples 1
(1) the synthetic CN85100997 embodiment 1 described method of pressing of catalyzer prepares.
In through the abundant metathetical reactor of high pure nitrogen, add 0.05 mole of Magnesium Chloride Anhydrous successively, 75 milliliters of toluene, be warming up to 50 ℃ under 0.1 mole of epoxy chloropropane and 0.03 mole of stirring of tributyl phosphate, and kept 2 hours, solid dissolves fully, adds 0.008 mole of Tetra hydro Phthalic anhydride then, keeps 1 hour again.Solution is cooled to-25 ℃, in 1 hour, drips 55 milliliters of titanium tetrachlorides, slowly be warming up to 80 ℃, in temperature-rise period, progressively separate out solids.Add 0.0125 mole of diisobutyl phthalate, under 80 ℃, kept 1 hour, filter the back, obtain pale brown look solid sediment with 100 milliliters of washed twice of toluene.Add 60 milliliters of toluene then, 40 milliliters of titanium tetrachlorides were handled 2 hours down at 90 ℃, and after the venting filtrate, re-treatment once again.Add 100 milliliters of washings of ethylene dichloride once, after 100 milliliters of washings of hexane four times, obtain solid catalyst, titanium content (weight) 1.92%, Mg content 17.5%.
(4) the vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 2
(1) the synthetic CN1229092 embodiment 1 described method of pressing of catalyzer prepares.
In the abundant metathetical reactor of high pure nitrogen, add the anhydrous MgCl of 0.042mol successively
2(about 4g), 60ml toluene, 0.032mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.017mol ethanol, be warming up to 80 ℃ under stirring, and keep 15 minutes solids and dissolve fully, form homogeneous solution, add Tetra hydro Phthalic anhydride 0.0074mol then, kept again 1 hour, this solution is cooled to-25 ℃, again 0.5mol titanium tetrachloride (about 55ml) is splashed in it, slowly be warming up to 80 ℃ then, reacted 3 hours, use toluene and hexane wash 6 times after the filtration respectively, vacuum-drying obtains solid catalyst.
(2) the vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 3
(1) catalyzer is synthetic with Comparative Examples 2.
(2) copolymerization of ethene slurry is with embodiment 14, and polymerization result sees Table 2
Table 1
| Numbering | Hydrogen (MPa) | Ethene (MPa) | Active (gPE/gcat) | PE apparent density (g/ml) | MI 2.16 (g/10min ) | Polymkeric substance particle diameter distribution (%) | |||
| ＞850μ m | ～150μ m | ～75μm | ＜75μm | ||||||
| Embodiment 1 | 0.28 | 0.75 | 8900 | 0.29 | 0.36 | 28.0 | 66.0 | 5.6 | 0.4 |
| Embodiment 2 | 0.50 | 0.53 | 4140 | 0.28 | 3.16 | 21.6 | 70.2 | 7.6 | 0.6 |
| Embodiment 4 | 0.28 | 0.75 | 8100 | 0.26 | 0.40 | 32.0 | 61.3 | 6.2 | 0.5 |
| Embodiment 6 | 0.28 | 0.75 | 12500 | 0.28 | 0.50 | 30.1 | 64.0 | 5.4 | 0.5 |
| Embodiment 7 | 0.48 | 0.55 | 7630 | 0.26 | 4.38 | 28.7 | 65.3 | 5.0 | 1.0 |
| Embodiment 9 | 0.28 | 0.75 | 9420 | 0.28 | 0.54 | 31.0 | 62.3 | 5.9 | 0.8 |
| Embodiment 11 | 0.28 | 0.75 | 8510 | 0.34 | 0.73 | 24.7 | 68.4 | 5.9 | 1.0 |
| Embodiment 13 | 0.28 | 0.75 | 28000 | 0.34 | 0.48 | 28.5 | 64.2 | 7.1 | 0.2 |
| Embodiment 14 | 0.48 | 0.55 | 11400 | 0.33 | 4.67 | 26.8 | 69.3 | 3.7 | 0.2 |
| Embodiment 15 | 0.28 | 0.75 | 30750 | 0.31 | 0.56 | 13.5 | 74.8 | 10.7 | 1.0 |
| Embodiment 18 | 0.28 | 0.75 | 9500 | 0.30 | 0.49 | 31.0 | 58.0 | 10.2 | 0.8 |
| Embodiment 19 | 0.28 | 0.75 | 12200 | 0.29 | 0.54 | 29.0 | 65.3 | 5.5 | 0.2 |
| Comparative Examples 1 | 0.28 | 0.75 | 8100 | 0.35 | 25.5 | 27.1 | 40.2 | 7.2 | |
| Comparative Examples 2 | 0.28 | 0.75 | 28000 | 0.36 | 0.50 | 18.0 | 32.4 | 39.6 | 10.0 |
Table 2
| Numbering | Hydrogen (MPa) | Ethene (MPa) | Hexene-1 (ml) | Density (g/cm 3) |
| Embodiment 1 | 0.28 | 0.75 | 0 | 0.9512 |
| Embodiment 3 | 0.9179 | |||
| Embodiment 4 | 0.9069 | |||
| Embodiment 6 | 0.28 | 0.75 | 0 | 0.9469 |
| Embodiment 8 | 0.28 | 0.75 | 20 | 0.9399 |
| Embodiment 9 | 0.28 | 0.75 | 0 | 0.9486 |
| Embodiment 10 | 0.28 | 0.75 | 20 | 0.9409 |
| Embodiment 11 | 0.28 | 0.75 | 0 | 0.9477 |
| Embodiment 12 | 0.28 | 0.75 | 20 | 0.9398 |
| Embodiment 13 | 0.28 | 0.75 | 0 | 0.9469 |
| Embodiment 16 | 0.28 | 0.75 | 20 | 0.9387 |
| Embodiment 17 | 0.28 | 0.75 | 30 | 0.9352 |
| Comparative Examples 3 | 0.28 | 0.75 | 30 | 0.9406 |
Claims (21)
1, a kind of vinyl polymerization or copolymerization catalyst of being used for is characterized in that, comprises following component:
A, titaniferous ingredient of solid catalyst, it is by being dissolved in magnesium halide in organic epoxy compounds, organo phosphorous compounds and the inert diluent, form homogeneous solution, add the porous inert carrier through dehydration in the presence of the alkane precipitation additive, the halogenide or derivatives thereof eutectoid that adds transition metals Ti again goes out to be prepared from;
B, organo-aluminium compound;
Ratio between B component and the component A is 5～1000 with aluminium titanium molar ratio computing.
2, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that, titaniferous ingredient of solid catalyst described in the component A, can also add electronic donor compound capable after adding the halogenide or derivatives thereof of transition metals Ti, wherein electronic donor compound capable is a kind of in alkyl ester, fatty ether, alicyclic ethers and the alicyclic ketone of aliphatics and aromatic carboxylic acid or their mixture.
3, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that, titaniferous ingredient of solid catalyst described in the component A, can also add electronic donor compound capable after the halogenide or derivatives thereof that adds transition metals Ti, wherein electronic donor compound capable is a tetrahydrofuran (THF).
4, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that, titaniferous ingredient of solid catalyst described in the component A, can also add electronic donor compound capable after the halogenide or derivatives thereof that adds transition metals Ti, the consumption mol ratio of wherein said magnesium halide and electronic donor compound capable is: 1: 0～10.
5, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that the magnesium halide described in the component A is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.
6, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, the halogenide or derivatives thereof that it is characterized in that the transition metals Ti described in the component A is a titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, one chlorine triethoxy titanium, dichloro diethoxy titanium, a kind of in trichlorine one ethanolato-titanium, or their mixture.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 7, organic epoxy compounds is an oxyethane in the described A component, propylene oxide, butylene oxide ring, epoxy chloropropane, a kind of in the methyl glycidyl ether, or their mixture.
8, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that organo phosphorous compounds is the ortho-phosphoric acid trimethyl in the described A component, the ortho-phosphoric acid triethyl, the ortho-phosphoric acid tri-n-butyl, a kind of in the phosphorous acid benzene methyl or their mixture.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 9, inert diluent is benzene, toluene and derivative thereof in the described A component.
10, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that used alkane precipitation additive is a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon atoms or their mixture in the described A component.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 10, it is characterized in that 11, used alkane precipitation additive is butane, pentane, hexane, hexanaphthene, heptane in the described A component.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 12, the volume ratio of inert diluent and alkane precipitation additive is in the described A component: 1: 0.1～5.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 13, the volume ratio of inert diluent and alkane precipitation additive is in the described A component: 1: 0.5～1.5
14,, it is characterized in that porous inert carrier is a silicon-dioxide among the component A, wherein a kind of or its mixture of aluminium sesquioxide according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
15, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 14, it is characterized in that the shape of the porous inert carrier among the component A is spherical in shape, particle diameter is 0.1 μ m～150 μ m.
16, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 14, it is characterized in that the shape of the porous inert carrier among the component A is spherical in shape, particle diameter is 5 μ m～50 μ m.
17,, it is characterized in that the porous inert carrier among the component A uses preceding the need handle through aluminum alkyls according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
18,, it is characterized in that magnesium halide and the inert support mol ratio among the component A is: 1: 0.5～15 according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
19,, it is characterized in that being applicable to slurry polymerization and vapour phase polymerization mode according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
20, the preparation method of any one described catalyzer component A that is used for vinyl polymerization or copolymerization is as follows in the claim 1～19: under agitation magnesium halide is dissolved in organic epoxy compounds, organo phosphorous compounds and the inert diluent, temperature remains on 30 ℃～80 ℃, after forming homogeneous solution, also can add alcohol compound reaction 0.5～2 hour, in the presence of the alkane precipitation additive, add porous inert carrier, then system is cooled in-30～60 ℃ of scopes; Titanium compound is splashed in the above-mentioned magnesium halide homogeneous solution with inert support, reaction mixture is warming up to 60～100 ℃ again, with suspension after stirring 0.5～8 hour under this temperature, also can add electron donor(ED) and continue reaction 0.1～2 hour, stopping to stir the back solids separates out from mixture solution, decant or remove by filter mother liquor is used the hexane wash solids, makes titaniferous solid catalytic ingredient.
21, the preparation method according to the catalyzer component A that is used for vinyl polymerization or copolymerization described in the claim 20 is characterized in that after adding porous inert carrier in the presence of the described alkane precipitation additive system cooling scope being-20～10 ℃.
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| CN 03123950 CN1274721C (en) | 2003-05-29 | 2003-05-29 | Catalyst for ethene polymerization or multipolymer, preparing method thereof |
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| CN100417671C (en) * | 2005-03-16 | 2008-09-10 | 中国石油化工股份有限公司 | Catalyst compsns. for olefin polymerization and catalyst thereof |
| EP1970388A4 (en) * | 2006-01-04 | 2010-11-10 | China Petroleum & Chemical | Catalyst component for olefin polymerization or copolymerization,preparation method thereof, catalyst containing said catalyst component and use thereof |
| US7388060B2 (en) | 2006-01-04 | 2008-06-17 | China Petroleum & Chemical Corporation | Catalyst component for olefin (co)polymerization, preparation thereof, a catalyst comprising the same and use thereof |
| CN101173014B (en) * | 2006-10-31 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same |
| CN101519464B (en) * | 2009-03-27 | 2011-05-11 | 迈瑞尔实验设备（上海）有限公司 | Catalyst for vinyl polymerization or copolymerization as well as preparation and application thereof |
| CN102050896B (en) * | 2009-10-27 | 2013-05-01 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and preparation method thereof |
| CN103788249B (en) * | 2012-10-29 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and application thereof |
| CN103788244B (en) * | 2012-10-29 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and application thereof |
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