CN103772550A - Catalyst ingredient used for ethylene polymerization, and catalyst thereof - Google Patents
Catalyst ingredient used for ethylene polymerization, and catalyst thereof Download PDFInfo
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- CN103772550A CN103772550A CN201210407844.9A CN201210407844A CN103772550A CN 103772550 A CN103772550 A CN 103772550A CN 201210407844 A CN201210407844 A CN 201210407844A CN 103772550 A CN103772550 A CN 103772550A
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Abstract
The invention relates to a catalyst used for ethylene polymerization. The catalyst comprises following ingredients, A, a titanium-containing solid catalyst ingredient, and B, an organic aluminium compound. The titanium-containing solid catalyst ingredient is prepared by following steps: magnesium halide is dissolved in an organic epoxy compound and an organic phosphorous compound; an electron donor compound is added so as to obtain a uniform solution; a silica compound and a precipitation accessory ingredient are added; and an obtained mixture is mixed with a halide or a derivative of titanium so as to obtain the titanium-containing solid catalyst ingredient; general formula of the organic aluminium compound is AlR<n>X<3-n>, wherein R is used for representing alkyl with 1 to 20 hydrogen or carbon atoms, X is used for representing halogen atom, and n is an integer, 0<n<=3. The catalyst is high in activity, and excellent in hydrogen regulation performance, is suitable for ethylene slurry polymerization or gas phase polymerization, and is especially suitable for ethylene gas phase fluidized bed polymerization technology in which the catalyst is charged in a slurry form.
Description
Technical field
The present invention relates to preparation method and its catalyzer of a kind of catalyst component for vinyl polymerization or copolymerization, this catalyst component.More particularly, relate to a kind of catalyst component of silicon compound, preparation method and its catalyzer of this catalyst component of adding in preparation process.
Background technology
In the polyreaction of alkene, particularly, in the copolymerization of vinyl polymerization or ethene and alpha-olefin, mostly adopt the catalyst component using magnesium, titanium, halogen and electron donor as basal component.When this class catalyzer is when for gas-phase fluidized bed polymerization process, for the form and the size-grade distribution that guarantee granules of catalyst are more suitable for fluidized state operation, normally above-mentioned catalyst component is carried on the carriers such as silica gel.For example US4,302,565, US4,379,759 and CN 1064870A in the disclosed catalyzer for gas-phase fluidized-bed reaction, be that the precursor components of being prepared by titanium compound, magnesium compound and electron donor compound is immersed on the carrier substance such as silica gel, then process prepared by impregnated precursor components with active compound.
In above-mentioned disclosed patent, in order to make catalyzer be applicable to gas-phase fluidized bed polymerization process, all there is stricter requirement in median size to used carrier silicon-dioxide, surface-area, aperture, and the price of this carrier substance is more expensive, need before use silica supports to carry out strict activation, these all cause the increase of the production cost of catalyzer simultaneously; And catalyst activity component is to be carried on carrier by impregnating method, due to the limited reasons such as titanium amount of carrying, its catalyst efficiency is also unsatisfactory.In addition, use in the polyethylene powder of this Catalyst Production fine powder amount larger, common 150 microns of following particles account for the 15Wt% left and right of whole powders, and this point does not wish to see in industrial production very much.
CN 1085915A discloses a kind of production method of catalyzer, although overcome foregoing some shortcomings, but need to use in process of production MAGNESIUM METAL as reductive agent, and still need to use a large amount of silica supports materials, the catalyst particles granule product finally obtaining also needs to adopt spray-dired method, facility investment is large, complicated operation, and overall manufacturing cost is still higher.
CN85100997A discloses a kind of catalyzer for olefinic polymerization, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds formation homogeneous solution by magnesium halide, then prepares with the halogenide or derivatives thereof effect of at least one precipitation additive, a kind of multi-carboxylate's electron donor and transition metals Ti.This catalyzer when the propylene polymerization, has shown higher polymerization activity and stereospecificity preferably, but activity is on the low side during for vinyl polymerization, and the broad particle distribution of polymkeric substance, and the hydrogen response of this catalyzer is bad.
On the basis of above-mentioned CN85100997A, CN1229092A discloses a kind of catalyzer for vinyl polymerization or copolymerization, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor activator to form homogeneous solution again, then prepares with the halogenide or derivatives thereof effect of at least one precipitation additive and transition metals Ti.This catalyzer has shown very high activity during for the slurry polymerization of ethene, and the particle form of resulting polymers is better simultaneously, and apparent density is also higher.But in fact, this catalyst component that has added alcohols activator is for ethene gas-phase polymerization technique, particularly when fluidized bed polymerization process, in the starting stage of polyreaction, polyreaction is very fast, makes the easily fragmentation of polymkeric substance generating, polymer beads is thinner, 70～150 microns of size-grade distribution account for 50Wt%～60Wt%, and the regular shape of polymer beads is also bad, result is unsatisfactory.
On the basis of above-mentioned CN85100997A, CN1463991A discloses a kind of catalyzer for vinyl polymerization or copolymerization, magnesium compound is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, after forming homogeneous solution, mix with titanium compound, under precipitation additive exists, separate out solids; Under the existence of electron donor compound, obtained solids is reacted with titanium compound, then adopt activator to activate reaction product, obtain catalyst component.Catalyzer prepared by this technique during for fluidized bed polymerization process reactive behavior higher, the fine powder content of polymer powders also has substantial degradation, but this catalyst preparation process flow process is longer, complex process.
CN101274967A discloses a kind of catalyst component for vinyl polymerization or copolymerization, and it comprises a kind of magnesium mixture, at least one titanium compound, at least one carbonatoms and is greater than 5 organic alcohol compound and the reaction product of at least one silicoorganic compound.The catalyzer of this invention is easy to separate out granules of catalyst in the preparation, does not need to impel separating out of precipitation with a large amount of titanium tetrachlorides, does not also need repeatedly to process precipitation with titanium tetrachloride, and therefore the add-on of titanium tetrachloride greatly reduces.The catalyzer that simultaneously prepared by this invention has improved the granule regularizing degree of catalyzer and has further improved the particle form of polymkeric substance.The catalyzer of this invention is for ethene slurry polymerization processes, show good over-all properties, it has the advantages such as higher catalytic activity, better hydrogen response and narrower polymkeric substance particle diameter distribution, is highly suitable for the slurry polymerization processes of ethene and needs in the polymerization mix technique of high activated catalyst.But the prepared catalyst grain size of this technique is generally less than normal, use in the polymkeric substance that this catalyzer obtains fine powder content higher, this catalyzer is not suitable for gas-phase fluidized bed polymerization process and uses.
Therefore, be starved of the ingredient of solid catalyst that provides a kind of technique simply and to be efficiently suitable for ethene slurry polymerization or vapour phase polymerization, this ingredient of solid catalyst is particularly useful for the gas-phase fluidized-bed ethene polymerization process with the charging of slurries form.This ingredient of solid catalyst should have relatively narrow particle size dispersion and less median size, has higher catalytic activity and higher hydrogen response simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of ingredient of solid catalyst being applicable to the gas-phase fluidized-bed ethene polymerization process of slurries form charging, this ingredient of solid catalyst should have relatively narrow particle size dispersion and less median size, has higher catalytic activity and higher hydrogen response.
A kind of catalyst for ethylene polymerization, comprises following component:
The ingredient of solid catalyst of A, titaniferous, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor compound formation homogeneous solution again, then with silicon compound and precipitation additive effect, mix with the halogenide or derivatives thereof of titanium again, obtain ingredient of solid catalyst;
B, organo-aluminium compound, its general formula is AlR
nx
3-n, in formula, R is the alkyl that hydrogen or carbonatoms are 1～20, and X is halogen atom, and n is the integer of 0 < n≤3;
Ratio between B component and component A, take the molar ratio computing of magnesium and titanium as 5～1000;
The general formula of wherein said silicon compound is Si R '
cx '
d, R ' is that carbonatoms is 1～14 saturated alkyl or alkoxyl group, and X ' is halogen atom, and c is 0～4 integer, and d is 0～3 integer, c+d=4;
Wherein said electron donor compound is that carbonatoms is 1～20 straight chain alcohol or isomery alcohol;
Wherein said precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone;
The wherein feed molar ratio of halogenide or derivatives thereof, silicon compound and the precipitation additive of magnesium halide, organic epoxy compounds, organo phosphorous compounds, electron donor compound, transition metals Ti, in every mole of magnesium halide, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, 0.1～3 mole of electron donor compound, 0～1 mole of silicon compound, 0.5～120 mole of the halogenide or derivatives thereof of transition metals Ti, 0.03～1.0 mole of precipitation additive compound.
Detailed description of the present invention:
The preparation of magnesium halide solution: magnesium halide solution is that magnesium halide is dissolved in the solvent system of organic epoxy compounds and organo phosphorous compounds composition and electron donor is added to the homogeneous solution obtaining in magnesium halide solution, and the solvent system of indication comprises use or do not use inert diluent here.
The described magnesium halide of catalyst component of the present invention (A) comprises a kind of or its mixture in the derivative that one of them halogen atom in the complex compound such as water or alcohol, magnesium dihalide molecular formula of magnesium dihalide, magnesium dihalide replaced by-oxyl or halogen-oxyl, and above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, two magnesium iodides.Wherein take magnesium dichloride as best.
The magnesium halide granularity using is dissolved as under stirring, and solvent temperature is-10 ℃～150 ℃, with 20 ℃～130 ℃ for well.When dissolving, can add or not with inert diluent as benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.Wherein benzene,toluene,xylene is that toluene, dimethylbenzene are best preferably.
Organic epoxy compounds comprises that carbonatoms is the compounds such as the oxide compound, glycidyl ether, inner ether of 2～8 aliphatics alkene, diolefine, halogenated aliphatic alkene or diolefine.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.Wherein, be preferably oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), take tetrahydrofuran (THF), epoxy chloropropane as best.
Organo phosphorous compounds comprises hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, phosphorous acid benzene methyl etc.Wherein be preferably ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl and ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid tri-n-butyl is best.
The electron donor that catalyst component of the present invention (A) is described, as Organic Alcohol comprises C
1～C
20straight chain alcohol or isomery alcohol, for example: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, glycerol, amylalcohol, decyl alcohol, dodecanol, Stearyl alcohol, Bian alcohol, phenylethyl alcohol, with C
1～C
8straight chain alcohol be best.
The described magnesium halide of catalyst component of the present invention (A) forms in the process of homogeneous solution in dissolving, also can add alkyl metal cpd as zinc alkyl(s) and or aluminum alkyls.
The general formula of silicon compound of the present invention is Si R '
cx '
d, R ' is that carbonatoms is 1～14 saturated alkyl or alkoxyl group, and X ' is halogen atom, and c is 0～4 integer, and d is 0～3 integer, c+d=4; Preferably tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon, silicon tetrachloride and Silicon bromide.
The halogenide or derivatives thereof general formula of transition metals Ti of the present invention is Ti (O R ")
nx
4-n, R in formula " and be C
1～C
14alkyl, X is halogen atom, 0≤n≤4, comprising: TiCl
4, TiBr
4, TiCl
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3, Ti (OC
2h
5) Br
3, Ti (OC
2h
5)
2cl
2, Ti (OCH
3)
2cl
2, Ti (OCH
3)
2l
2, Ti (OC
2h
5)
3cl, Ti (OCH
3)
3cl, Ti (OC
2h
5)
3l, Ti (OC
2h
5)
4, Ti (OC
3h
7)
4, Ti (OC
4h
9)
4deng.Preferably TiCl
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3, Ti (OC
4h
9)
4.With TiCl
4for the best.
Precipitation additive of the present invention is selected from the one in organic acid, organic acid anhydride, organic ether, organic ketone, or their mixture.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether etc.
The feed molar ratio of halogenide or derivatives thereof, silicon compound and the precipitation additive of magnesium halide of the present invention, organic epoxy compounds, organo phosphorous compounds, electron donor compound, transition metals Ti, in every mole of magnesium halide, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, 0.1～3 mole of electron donor compound, 0～1 mole of silicon compound, 0.5～120 mole of the halogenide or derivatives thereof of transition metals Ti, 0.03～1.0 mole of precipitation additive compound.
In the catalyst component obtaining in the present invention, titanium: 1～10%, magnesium: 10～20% (weight contents).
The present invention also provides the preparation method of a kind of component A of catalyst for ethylene polymerization, comprise the steps: under agitation magnesium halide to be dissolved in and in organic epoxy compounds, organo phosphorous compounds, add again electron donor compound, form homogeneous transparent solution, under the condition of then 20 ℃～130 ℃ with silicon compound and precipitation additive effect, being cooled to-35 ℃～-20 ℃ mixes with the halogenide or derivatives thereof of titanium again, filter, remove mother liquor, wash solids with inert solvent, make the ingredient of solid catalyst of titaniferous.
Organo-aluminium compound of the present invention, its general formula is AIR
nx
3-n, in formula, R is the alkyl that hydrogen or carbonatoms are 1～20, and X is halogen atom, and n is the integer of 0 < n≤3; Preferably AlEt
3, Al (iso-Bu)
3, Al (n-C
6h1
3)
3, Al (n-C
8h
17)
3, AlEt
2cl etc.
In catalyst system of the present invention, aluminium is 5～1000 with the mol ratio of the middle titanium of component (A) in component (B), with 20～800 for well.
Catalyzer of the present invention is applicable to the equal polymerization of ethene or the copolymerization of ethene and other alpha-olefin, and wherein alpha-olefin adopts the one in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methylpentene-1.Its polymerization technique can adopt vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation, particularly gas-phase fluidized-bed condensation technology.Meanwhile, because the activity of catalyzer of the present invention is very high, therefore can adopt inert diluent by catalyst dilution, for example mineral wet goods, realizes catalyst slurry charging equably by pumping feeding manner.
The present invention compared with the prior art tool has the following advantages:
The invention provides a kind of ingredient of solid catalyst being applicable to the gas-phase fluidized-bed ethene polymerization process of slurries form charging, this catalyst activity is higher, hydrogen regulation performance excellence, the fine polymer powder content obtaining is few, be suitable for ethene slurry polymerization or vapour phase polymerization, be specially adapted to the gas-phase fluidized bed polymerization process of catalyzer with the ethene of slurries form charging.
Embodiment
With embodiment, the present invention is described below, but and unrestricted invention scope.
Testing method
1, melting index (MI): measure according to ASTM D1238-99;
2, size-grade distribution: according to the method for the optical diffraction principle based on one-wavelength laser, with " MalvernInstr.2600 " tester.
Embodiment 1
1, the preparation of catalyst component
Under nitrogen protection, by 4.8 grams of magnesium chlorides, 90 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliter tributyl phosphate, 0.5ml ethanol joins in reactor, at mixing speed 450rpm, temperature is under the condition of 60 ℃, react two hours, add 3.5ml silicon tetrachloride and 1.4 grams of Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to gradually 85 ℃, constant temperature one hour, elimination mother liquor, it is dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain 6.8 grams of catalyst components, wherein contain Ti 3.5% (weight).
2, polymerization
Volume is the stainless steel cauldron of 2 liters, after hydrogen is fully replaced, be pressed into approximately 0.5 liter of hexane with nitrogen, with syringe implantation concentration be 1mmol/ml triethyl aluminum-hexane solution 2ml, under stirring, add again the above-mentioned catalyst component of 20mg, supplement hexane total amount and be about 1 liter.
After reinforced, heat up and successively pass into hydrogen and ethene, 2.8 × 10
5pa H
2, 7.5 × 10
5pa ethene, polymerization temperature is 85 ℃, reacts two hours, and overbottom pressure in the still of lowering the temperature, drain, emits polymer syrup liquid material, and elimination hexane is dried polymkeric substance, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 2
Method for preparing catalyst is with embodiment 1.
Polymerization appreciation condition: volume is the stainless steel cauldron of 2 liters, after hydrogen is fully replaced, be pressed into approximately 0.5 liter of hexane with nitrogen, with syringe implantation concentration be 1mmol/ml triethyl aluminum-hexane solution 2ml, under stirring, add again the catalyst component of 50mg, supplement hexane total amount and be about 1 liter.
After reinforced, heat up and successively pass into hydrogen and ethene, 6.8 × 10
5pa H
2, 3.5 × 10
5pa ethene, polymerization temperature is 85 ℃, reacts two hours, and overbottom pressure in the still of lowering the temperature, drain, emits polymer syrup liquid material, and elimination hexane is dried polymkeric substance, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 3
Method for preparing catalyst is with embodiment 1, SiCl
4consumption changes 1.5ml into.Obtain 6.5 grams of pellet type catalyst components, wherein contain Ti 3.2% (weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Embodiment 4
Method for preparing catalyst is with embodiment 3.
Polymerization appreciation condition, with embodiment 2, the results are shown in Table 1.
Embodiment 5
Method for preparing catalyst is with embodiment 1, SiCl
4change Si (OEt) into
42.2ml.Obtain 7.2 grams of pellet type catalyst components, wherein contain Ti 3.1% (weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Embodiment 6
Method for preparing catalyst is with embodiment 5.
Polymerization appreciation condition, with embodiment 2, the results are shown in Table 1.
Embodiment 7
Method for preparing catalyst is with embodiment 1, SiCl
4change Si (OEt) into
41.1ml+SiCl
41.5ml.Obtain 7.1 grams of pellet type catalyst components, wherein contain Ti 3.5% (weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Embodiment 8:
Method for preparing catalyst is with embodiment 7.
Polymerization appreciation condition, with embodiment 2, the results are shown in Table 1.
Comparative example 1
Method for preparing catalyst, with embodiment 1, does not use SiCl
4.Obtain 6.1 grams of pellet type catalyst components, wherein contain Ti 3.8% (weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Comparative example 2
According to the disclosed method Kaolinite Preparation of Catalyst of Chinese patent CN1463991A component
4.8 grams of Magnesium Chloride Anhydrouss, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reactor of fully replacing through nitrogen, are, under the condition of 60 ℃, to react two hours in mixing speed 450rpm, temperature.Add 1.4 grams of Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, with within 1 hour, dripping 56 milliliters of titanium tetrachlorides, be warming up to gradually 85 ℃, constant temperature one hour with 2 hours, in temperature-rise period, separate out gradually solids, elimination mother liquor, dry after toluene and twice washing of hexane, obtain the solids H containing magnesium/titanium.
10 grams of solids H are joined in another reactor of fully replacing through nitrogen, add 90ml iso-pentane, 0.3 gram of titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, under normal temperature, react one hour, filter solution, add again 90ml iso-pentane, the aluminium diethyl monochloride hexane solution that 3.5 ml volumes concentration are 26.43% at room temperature reacts one hour, obtains pellet type catalyst component through evaporation drying.
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Comparative example 3
Method for preparing catalyst is with comparative example 1.
Polymerization appreciation condition, with embodiment 2, the results are shown in Table 1.
Comparative example 4
According to US4,302,565, US4,379,759 disclosed composition and content, adopt the method Kaolinite Preparation of Catalyst component of pickling process.
The activation of silica gel: 948# spherical silica gel (Grace company of the U.S.) is activated to 4 hours at 600 ℃.In reactor, add 100mlTHF, titanous chloride 0.74g, magnesium chloride 1.13g, be warming up to 70 ℃ of reactions 1 hour, for subsequent use as masterbatch.Add iso-pentane 60ml to another reactor, add silica gel 10g, triethyl aluminum 4.3ml after above-mentioned activation, normal-temperature reaction 30min, iso-pentane at 55 ℃ in still kettle, make the aluminium content of material in still reach 1.65%, then ready masterbatch is transferred in this reactor, being warming up to refluxes produces, constant temperature 1 hour.THF in distillation reactor, makes the THF content of material in still reach 12.6%, adds under iso-pentane 86ml, aluminium diethyl monochloride 5.3ml normal temperature and reacts 30min, adds under tri-n-hexyl aluminum 3.3ml normal temperature and reacts 30min.Obtain particulate solid catalyzer through vacuum-drying.In final catalyst component, contain Ti 0.78% (weight), Mg 1.58% (weight), tetrahydrofuran (THF) 10.9% (weight).
Polymerization appreciation condition, with embodiment 1, the results are shown in Table 1.
Comparative example 5
According to the disclosed method Kaolinite Preparation of Catalyst of Chinese patent CN101274967A component:
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add successively 4.0g magnesium dichloride, toluene 60ml, epoxy chloropropane 2.0ml, tributyl phosphate 6.0ml, ethanol 3.4ml, under stirring, be warming up to 65 ℃, when solid dissolves after the solution that forms homogeneous completely, drip 2-Ethylhexyl Alcohol 5.5ml (ethanol and 2-Ethyl Hexanol mol ratio are 1.4: 1.0), under 65 ℃ of conditions, react 1 hour.This system is cooled to-5 ℃, slowly drips 60ml titanium tetrachloride, then add 3ml tetraethoxysilane, react 0.5 hour, be slowly warming up to 85 ℃, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, washs solid with hexane, then is dried up with high pure nitrogen, obtains good fluidity, the narrower solid catalyst particle of size distribution.
(2) vinyl polymerization: the stainless steel cauldron that volume is 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, the hexane solution that adds catalyzer (containing the 0.3 milligram of titanium) solid of above-mentioned preparation, is warming up to 70 ℃, passes into hydrogen and makes still internal pressure reach 0.28Mpa, passing into ethene makes stagnation pressure in still reach 0.73Mpa (gauge pressure), polymerization 2 hours under 80 ℃ of conditions again.Polymerization result is in table 1.
Table 1 polymerization result
As can be seen from Table 1, this catalyst activity is higher, hydrogen regulation performance excellence, and the fine polymer powder content obtaining is few, is suitable for ethene slurry polymerization or vapour phase polymerization, is specially adapted to the gas-phase fluidized bed polymerization process of catalyzer with the ethene of slurries form charging.
Claims (11)
1. a catalyst for ethylene polymerization, comprises following component:
The ingredient of solid catalyst of A, titaniferous, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor compound formation homogeneous solution again, then with silicon compound and precipitation additive effect, mix with the halogenide or derivatives thereof of titanium again, obtain ingredient of solid catalyst;
B, organo-aluminium compound, its general formula is AlR
nx
3-n, in formula, R is the alkyl that hydrogen or carbonatoms are 1～20, and X is halogen atom, and n is the integer of 0 < n≤3;
Ratio between B component and component A, take the molar ratio computing of magnesium and titanium as 5～1000;
The general formula of wherein said silicon compound is SiR '
cx '
d, R ' is that carbonatoms is 1～14 saturated alkyl or alkoxyl group, and X ' is halogen atom, and c is 0～4 integer, and d is 0～3 integer, c+d=4;
Wherein said electron donor compound is that carbonatoms is 1～20 straight chain alcohol or isomery alcohol;
Wherein said precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone;
The wherein feed molar ratio of halogenide or derivatives thereof, silicon compound and the precipitation additive of magnesium halide, organic epoxy compounds, organo phosphorous compounds, electron donor compound, transition metals Ti, in every mole of magnesium halide, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, 0.1～3 mole of electron donor compound, 0～1 mole of silicon compound, 0.5～120 mole of the halogenide or derivatives thereof of transition metals Ti, 0.03～1.0 mole of precipitation additive compound.
2. catalyst for ethylene polymerization according to claim 1, is characterized in that described silicon compound is selected from least one in tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon, silicon tetrachloride and Silicon bromide.
3. catalyst for ethylene polymerization according to claim 1, is characterized in that described precipitation additive is selected from least one in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.
4. catalyst for ethylene polymerization according to claim 1, is characterized in that described magnesium compound is selected from least one in the derivative that one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula replaced by-oxyl or halo-oxyl.
5. catalyst for ethylene polymerization according to claim 1, is characterized in that described organic epoxy compounds comprises that carbonatoms is at least one in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine.
6. catalyst for ethylene polymerization according to claim 1, is characterized in that described organo phosphorous compounds is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
7. catalyst for ethylene polymerization according to claim 1, is characterized in that described electron donor compound is the fatty alcohol compounds that contains 1～8 carbon atom.
8. catalyst for ethylene polymerization according to claim 1, the halogenide or derivatives thereof general formula that it is characterized in that described transition metals Ti is Ti (O R ")
nx
4-n, R in formula " and be C
1～C
14alkyl, X is halogen atom, 0≤n≤4.
9. catalyst for ethylene polymerization according to claim 1, is characterized in that the halogenide or derivatives thereof of described transition metals Ti is TiCl
4.
10. the preparation method of the component A of the catalyst for ethylene polymerization described in one of claim 1～9, comprise the steps: under agitation magnesium halide to be dissolved in and in organic epoxy compounds, organo phosphorous compounds, add again electron donor compound, form homogeneous transparent solution, under the condition of then 20 ℃～130 ℃ with silicon compound and precipitation additive effect, being cooled to-35 ℃～-20 ℃ mixes with the halogenide or derivatives thereof of titanium again, filter, remove mother liquor, wash solids with inert solvent, make the ingredient of solid catalyst of titaniferous.
The described catalyzer of one of 11. claims 1～9 closes the application in reaction or copolymerization at ethylene homo.
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| CN109694424A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization |
| CN114426600A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of solid catalyst for olefin polymerization |
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| CN109694424B (en) * | 2017-10-24 | 2021-08-03 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
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| CN114426600B (en) * | 2020-10-15 | 2024-03-26 | 中国石油化工股份有限公司 | Preparation method of solid catalyst for olefin polymerization |
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