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CN1752114A - Catalyst used for ethylene polymerization or copolymerization, its preparation method and application - Google Patents

Catalyst used for ethylene polymerization or copolymerization, its preparation method and application Download PDF

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Publication number
CN1752114A
CN1752114A CN 200410078279 CN200410078279A CN1752114A CN 1752114 A CN1752114 A CN 1752114A CN 200410078279 CN200410078279 CN 200410078279 CN 200410078279 A CN200410078279 A CN 200410078279A CN 1752114 A CN1752114 A CN 1752114A
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copolymerization
catalyst component
compound
vinyl polymerization
magnesium
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CN100389134C (en
Inventor
王志武
谭忠
郭正阳
寇鹏
杨世峰
周俊领
王宇
严立安
徐慧娟
张玲
王迎
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

A catalyst for the polymerizing or copolymerizing of ethene with wide distribution of molecular weights in dual reactors is composed of a solid carrier containining Mg/Ti, at least one Ti compound, at least one proper donor and at least one hydrogenating performance improver. Its advantages are very good hydrogenating sensitivity, high catalyst activity, and good granular form. Its preparing process is also disclosed.

Description

Be used for catalyst component, its preparation method and the application of vinyl polymerization or copolymerization
Technical field
The present invention relates to a kind of catalyst component that is used for vinyl polymerization or copolymerization, its preparation method and the application in vinyl polymerization thereof.
Background technology
The polyreaction of alkene is particularly closed in the reaction at vinyl polymerization or ethene and alpha-olefin copolymer, adopts with magnesium, titanium, halogen and the electron donor basal component as catalyzer mostly.When this class catalyzer when being used for gas-phase fluidized bed polymerization process, be to guarantee the form of granules of catalyst and the operation that size-grade distribution is more suitable for fluidized state, normally above-mentioned catalyst component is carried on the carrier such as silica gel.For example: US4,302,565, US4,379,759 and CN 1064870A in disclosedly be used for gas-phase fluidized-bed catalyst for reaction, be to be immersed in by the precursor components of titanium compound, magnesium compound and electron donor compound on the carrier substance such as silica gel, handle impregnated precursor components with active compound again and prepare.At US4, the median size of employed silica gel is the 50-150 micron in 302,565, US4,379,759, and surface-area is greater than 50 meters 2/ gram, mean pore size is greater than 80 dusts.
In above-mentioned disclosed patent, in order to make catalyzer, all there is strict requirement in employed carrier-silicon-dioxide median size, surface-area, aperture, and the price of this carrier substance is expensive applicable to gas-phase fluidized bed polymerization process; And the catalyst activity component is to be carried on the carrier by the impregnating method, and owing to carrying reason such as titanium quantitative limitation, its catalyst efficiency is also unsatisfactory.In addition, use in the polyethylene powder of this Catalyst Production fine powder amount bigger, common particle below 150 microns accounts for about the 15Wt% of whole powders, and this point is very undesirable in industrial production.This catalyzer is when being applied to ethene gas fluidised bed polymerisation full scale plant simultaneously, and catalyzer with the charging of solid form, advances the charging process poor stability mostly, is prone to plugging, arch formation.
Among the Chinese patent CN85100997, a kind of olefin polymerization catalysis that is used for is disclosed, it is to be dissolved in organic epoxy compounds by magnesium halide, organo phosphorous compounds forms homogeneous solution, again with at least a precipitation additive, the halogenide and the derivative effect thereof of a kind of multi-carboxylate's electron donor and transition metals Ti prepare, when this catalyzer is used for propylene polymerization, high polymerization activity and stereospecificity have preferably been shown, but activity is on the low side when being used for vinyl polymerization, and the broad particle distribution of polymkeric substance, and the hydrogen response of this catalyzer is not ideal enough.
Chinese patent CN1229092A discloses a kind of catalyzer that is used for vinyl polymerization or copolymerization again, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor activator formation homogeneous solution again, halogenide and derivative effect thereof with at least a precipitation additive and transition metals Ti prepares again, this catalyzer has shown very high activity when being used for the slurry polymerization of ethene, the particle form of resulting polymers is better simultaneously, and apparent density is also higher.But the hydrogen regulation performance of this catalyzer is undesirable.
A kind of catalyzer that is used for vinyl polymerization or copolymerization is disclosed in the Chinese patent 02120861, it is to be dissolved in organic epoxy compounds by magnesium halide, in the homogeneous solution of organo phosphorous compounds and inert solvent, the solids that obtains titaniferous magnesium with the halogenide and the derivative effect thereof of at least a precipitation additive and transition metals Ti again, at least a electron donor of load and at least a activator on the solids of this titaniferous/magnesium again, this catalyzer has shown very high activity when being used for the slurry polymerization of ethene, the particle form of resulting polymers is better simultaneously, and apparent density is also higher.But this catalyzer hydrogen response is undesirable, will be unfavorable for the polymkeric substance with a kind of Catalyst Production wide molecular weight distribution.
Summary of the invention
In order to overcome the defective of prior art, the invention provides a kind of hydrogen response height, efficiently and can obtain the ingredient of solid catalyst that low fine contains weight polymers, this catalyst component has narrow relatively particle size dispersion and less median size, the polymerization catalyst activity is higher, be suitable for the slurry polymerization or the vapour phase polymerization of ethene, be specially adapted to the gas-phase fluidized bed polymerization process of catalyzer, be particularly suitable for producing broad molecular weight distribution polymers with the ethene of slurries form charging.
The present invention is used for the catalyst component of vinyl polymerization or copolymerization, and it is by on a kind of solids of titaniferous/magnesium, the compound of at least a transition metals Ti of load, at least a electron donor and at least a hydrogen regulation performance improving agent and obtain.
The solids of the described titaniferous/magnesium of catalyst component of the present invention can adopt a large amount of solids that contains magnesium/titanium well-known to those skilled in the art, wherein comparatively preferably with the compound dissolution of magnesium, form uniform solution, in the presence of the halogenide of titanium and derivative thereof, separate out the precipitation of solid material that contains magnesium/titanium again then, can add suitable precipitation additive in case of necessity.
Highly preferred scheme is to form homogeneous solution after magnesium compound is dissolved in organic epoxy compounds, organo phosphorous compounds and inert solvent, obtains with the compound effects of transition metals Ti in the presence of analysing helping.
Wherein said magnesium compound 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.
Wherein said organic epoxy compounds is selected from and comprises the compounds such as oxide compound, glycidyl ether and inner ether of carbonatoms at 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether etc.
Wherein said organo phosphorous compounds is selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, for example: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl etc.
Wherein said inert solvent is pentane, hexane, heptane, octane, benzene,toluene,xylene, 1,2 ethylene dichloride and other hydro carbons or halogenated hydrocarbon compound.
Wherein said precipitation additive is selected from a kind of in organic acid, organic acid anhydride, organic ether, the 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.
Described hydrogen regulation performance improving agent described in the catalyst component of the present invention is the silicon compounds, and its general formula is Si (OR) aX b, R is C in the formula 1～C 14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0 to 4 integer, b is 0 to 4 integer, a+b=4.Concrete as trichlorine methoxyl group silicon, three chloroethoxy silicon, trichlorine propoxy-silicon, trichlorine butoxy silicon, dichloro dimethoxy silicon, dichloro diethoxy silicon, dichloro dipropoxy silicon, dichloro dibutoxy silicon, one chlorine trimethoxy silicon, a chlorine triethoxysilicane, a chlorine tripropoxy silicon, one chlorine, three butoxy silicon, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon, silicon tetrachloride etc., preferred silicon tetrachloride, tetraethoxy-silicane.
The general formula of the transition metal titanium compound described in the catalyst component of the present invention is Ti (OR) aX b, R is C in the formula 1～C 14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0 to 2 integer, b is 0 to 4 integer, a+b=3 or 4.Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, the titanous chloride or their mixture for use, preferred titanium tetrachloride, trichlorine one ethanolato-titanium, titanous chloride etc.
Electron donor compound described in the catalyst component of the present invention is selected from aliphatic ether, aromatic oxide, mixed ether, cyclic aliphatic ether and aliphatic ketone; Be preferably C 2～C 6Aliphatic ether, C 3～C 4Cyclic ethers, C 3～C 6Aliphatic ketone.Be specially ether, n-butyl ether, ethyl isobutyl ether, hexyl ether, phenyl ethyl ether, tetrahydrofuran (THF), acetone, methyl iso-butyl ketone (MIBK), butanone, pimelinketone, 2,4 hexanediones, 4-methyl-3 amylene-2 ketone etc.; This class electron donor can use separately or several being used.
Above-mentioned catalyst component of the present invention, preferably adopt the following step to be prepared:
Contain the preparation of the solids of magnesium/titanium: magnesium compound is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, mixes with the joint compound of transition metals Ti behind the formation homogeneous solution, in the presence of precipitation additive, separate out the solids that contains magnesium/titanium.
This preparation method who contains the solids of magnesium/titanium is disclosed among the CN85100997, at this its full content is introduced the present invention as a reference.
In the presence of the electron donor compound, will contain the solids and the reaction of transition metal titanium compound of magnesium/titanium, the product that obtains is handled with at least a hydrogen regulation performance improving agent and is obtained catalyst component.
The ratio between each component wherein, in every mole of magnesium compound, organic epoxy compounds is 0.2～10 mole, organo phosphorous compounds is 0.1～3 mole, precipitation additive is 0.03～1.0 mole, 0.5～150 mole of titanium compound, 0.1～10 mole of electron donor compound, hydrogen is transferred 0.01～10 mole of properties-correcting agent.
In the resulting catalyst component of the present invention, titanium: 1～10%, silicon: 0.01～10%, electron donor: 1～60%, (weight content).
The invention still further relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, it contains the above-mentioned catalyst component of the present invention and the reaction product of alkylaluminium cpd, the general formula of wherein used alkylaluminium cpd is AlRnX3-n, R can be 1～8 alkyl, particularly alkyl, aralkyl, aryl for carbonatoms in the formula; X is halogen, particularly chlorine and bromine; N is the integer of 0＜n≤3.Particular compound as: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum,, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter aluminium triethyl etc., wherein with triethyl aluminum, triisobutyl aluminium for well.
Ratio between catalyst component and the alkylaluminium cpd, count with every gram catalyst component: 0.1mmol～10mmol is preferably 0.5mmol～3mmol.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts C 3～C 8Alpha-olefin; Concrete as propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation and slurry polymerization particularly gas-phase fluidized-bed condensation technology.Because activity of such catalysts of the present invention is very high, so can adopt inert diluent with catalyst dilution, for example the mineral wet goods is realized catalyst slurry charging equably by the pumping feeding manner, charging is even, stable operation simultaneously.
Compared with the prior art the present invention has following advantage:
The invention provides a kind of ethene slurry polymerization processes that is very suitable for, gas-phase polymerization process is particularly suitable for adopting the vinyl polymerization of double-reactor production wide molecular weight distribution and the catalyzer of copolymerization.This catalyzer is compared its advantage with existing catalyzer be that hydrogen response is better, catalytic activity height, catalyzer and polymer beads form are good, characteristics such as fine powder content is low, be highly suitable for the ethene slurry polymerization processes, be particularly suitable for adopting the polyvinyl production technique of double-reactor production wide molecular weight distribution.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.
Scope of the present invention proposes in claims.
Embodiment 1:
1, the preparation of catalyst component
4.8 gram Magnesium Chloride Anhydrouss, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined through in the abundant metathetical reactor of nitrogen, be under 60 ℃ the condition in mixing speed 450rpm, temperature, reacted two hours, add 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, with 56 milliliters of 1 hour dropping titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature one hour with 2 hours. in temperature-rise period, separate out solids gradually; The elimination mother liquor through toluene and twice washing of hexane after drying, obtains containing the solids A of magnesium/titanium.
10 gram solids A are joined through in another reactor of the abundant metathetical of nitrogen, add 90 milliliters of iso-pentane, 0.3 gram titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, normal temperature reacted one hour down, filter solution, add the 90ml iso-pentane again, 10 milliliters of silicon tetrachlorides at room temperature reacted one hour, obtained particulate solid catalyst component B through evaporation drying.
2, ethene slurry polymerization
Condition 1:
Volume is 2 liters a stainless steel cauldron, after hydrogen gas is fully replaced, be pressed into about 0.5 liter of hexane with nitrogen, with the syringe implantation concentration hexane solution 2ml of 1mol/L triethyl aluminum, stir the above-mentioned ingredient of solid catalyst B that adds 10 milligrams down again, replenish the hexane total amount and be about 1 liter.Heat up and successively feed hydrogen and ethene, 2.8 * 10 in the reinforced back that finishes 5Pa H 2, 7.5 * 10 5Pa ethene, polymerization temperature are 85 ℃, react two hours, and overbottom pressure in the still of lowering the temperature, drain is emitted the polymer slurries material, and the elimination hexane with the polymkeric substance oven for drying, obtains polyethylene powder, the results are shown in Table 1.
Condition 2:
Volume is 2 liters a stainless steel cauldron, after hydrogen gas is fully replaced, be pressed into about 0.5 liter of hexane with nitrogen, with the syringe implantation concentration hexane solution 2ml of 1mol/L triethyl aluminum, stir the above-mentioned solid ingredient B that adds 40 milligrams down again, replenish the hexane total amount and be about 1 liter.
Heat up and successively feed hydrogen and ethene, 6.8 * 10 in the reinforced back that finishes 5Pa H 2, 3.5 * 10 5Pa ethene, polymerization temperature are 85 ℃, react two hours, and overbottom pressure in the still of lowering the temperature, drain is emitted the polymer slurries material, and the elimination hexane with the polymkeric substance oven for drying, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 2
In reactor, solids A 10 grams that add preparation among the embodiment 1, add 90 milliliters of iso-pentane, normal temperature drips 5 milliliters of 0.7 milliliter of titanium tetrachloride and tetrahydrofuran (THF)s down, normal-temperature reaction one hour, add 5 milliliters of silicon tetrachlorides again and at room temperature reacted one hour, obtain particulate solid catalyst component B through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 3:
The solid ingredient A10 gram that in reactor, adds preparation among the embodiment 1, add 60 milliliters of toluene, 40 milliliters of titanium tetrachlorides, normal temperature drips 8.3 milliliters of tetrahydrofuran (THF)s down, be warming up to 120 ℃, reacted one hour, filter solution, 100 milliliters of hexane wash three times, add the 90ml iso-pentane again, 10 milliliters of silicon tetrachlorides at room temperature reacted one hour, obtained particulate solid catalyst component B through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 4
4.8 gram Magnesium Chloride Anhydrouss, 92 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition in mixing speed 450rpm, temperature, reacted two hours, and added 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature one hour, solution in the elimination still obtains containing the solids A of magnesium/titanium behind hexane secondary washing and suction filtration.Add 60 milliliters of hexanes in the reactor that fills solid ingredient A, under agitation add 2.4 milliliters of THF, normal-temperature reaction 1 hour adds 10 milliliters of silicon tetrachlorides again and at room temperature reacted one hour, obtains particulate solid catalyst component B through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 5
4.8 gram Magnesium Chloride Anhydrouss, 92 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition in mixing speed 450rpm, temperature, reacted two hours, and added 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature one hour, solution in the elimination still obtains containing the solids A of magnesium/titanium behind hexane secondary washing and suction filtration.In the reactor that fills solid ingredient A, add the 90ml hexane, under agitation add 10 milliliters of TiCl 4, 60 ℃ were reacted 0.5 hour, added 60 milliliters of hexanes behind the suction filtration, under agitation added 1.5 milliliters of THF, and normal-temperature reaction 1 hour adds 10 milliliters of silicon tetrachlorides again and at room temperature reacted one hour, obtains particulate solid catalyst component B through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 6
1, the preparation of catalyst component
6.5 kilograms of Magnesium Chloride Anhydrouss, 124.6 liters of toluene, 5.4 liters of epoxy chloropropane, 16.9 liters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition, to react 3.5 hours in mixing speed 130rpm, temperature, add 1.89 kilograms of Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 80 ℃ gradually, constant temperature one hour, the elimination mother liquor through toluene and 3 washings of hexane after drying, obtains containing the solids A of magnesium/titanium.
2 liter of four titanium butoxide and 6.8 liters of tetrahydrofuran (THF)s are joined in the dissolution kettle, add 680 gram titanous chlorides after stirring again, dissolving forms compound titanium solution under the condition of mixing speed 200rpm.
Solids A is transferred in another reactor, add 100 liters of hexanes, drip 8.26 liters of titanium tetrachlorides under 10 ℃ the condition stirring 130rpm, temperature, normal temperature reacted one hour down, filter solution, and with twice of hexane wash, add 100 liters of hexanes again, 7 liters of silicon tetrachlorides at room temperature reacted one hour, obtained particulate solid catalyst component B through evaporation drying.
2, slurry polymerization
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 7
1, the preparation of catalyst component
4.8 gram Magnesium Chloride Anhydrouss, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition in mixing speed 450rpm, temperature, reacted two hours, add 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 56 milliliters of titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains containing the solids A of magnesium/titanium.Add 100 milliliters of hexanes to the reactor that fills solid ingredient A, under agitation drip 1.5 milliliters of pimelinketone, normal-temperature reaction one hour adds 5 milliliters of silicon tetrachlorides again and at room temperature reacted one hour, obtains particulate solid catalyst component B through evaporation drying.
2, polymerization
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 8
Other condition of Preparation of Catalyst is with embodiment 8, and pimelinketone changes 4-methyl-3-amylene-2-ketone 1.7ml into for 1.5 milliliters, obtains particulate solid thing B component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 9
Other condition of Preparation of Catalyst only changes pimelinketone into phenyl ethyl ether 1.5ml for 1.5 milliliters with embodiment 8, obtains particulate solid thing B component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 10:
Other condition of Preparation of Catalyst only changes pimelinketone into n-butyl ether 1.5ml for 1.5 milliliters with embodiment 8, obtains particulate solid thing B component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 11
Other condition of Preparation of Catalyst only changes 1.5 milliliters of pimelinketone into butanone 1.5 milliliters with embodiment 8, obtains particulate solid thing B component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 12
Other condition of Preparation of Catalyst only changes pimelinketone into 2 for 1.5 milliliters with embodiment 8, and 4-hexanedione 1.5ml obtains particulate solid thing B component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 13
Other condition of Preparation of Catalyst only changes 1.5 milliliters of pimelinketone into tetrahydrofuran (THF) 1.5 milliliters with embodiment 8, obtains particulate solid thing B component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 14
1, Preparation of catalysts
9.6 gram Magnesium Chloride Anhydrouss, 50 milliliters of toluene, 46.8 milliliters of 2-Ethyl Hexanols are joined in the reactor, are under 110 ℃ the condition, to react about 120 minutes in mixing speed 450rpm, temperature, add 2.22 gram Tetra hydro Phthalic anhydrides, continue about 60 minutes of reaction.Get above-mentioned homogeneous solution 50ml and fill in the reactor of 200ml titanium tetrachloride slow the adding, it is-20 ℃ of stirrings that do not stop that this process keeps still temperature, add the back and be warming up to 110 ℃ gradually with about 180 minutes, and constant temperature 2 hours, the elimination mother liquor obtains solid ingredient A.
In the reactor of solid ingredient A, add the 200ml titanium tetrachloride, be warming up to 110 ℃, constant temperature 2 hours.Remove mother liquor, solid residue adds 100 milliliters of hexanes again with 60 ℃ of hexane wash 3 times, slow adding 3.0ml tetrahydrofuran (THF) also reacted 1 hour, add 5 milliliters of silicon tetrachlorides again and at room temperature reacted one hour, after washing through twice hexane, evaporation drying obtains particulate solid composition B.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 15
Replace toluene to make solvent with decane and obtain particulate solid composition B by the method for embodiment 15.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 16
Get solid ingredient A 8 grams of preparation among the embodiment 15,, add 60 milliliters of toluene, 40 milliliters of titanium tetrachlorides, normal temperature drips 5.0 milliliters of tetrahydrofuran (THF)s down, adds 5 milliliters of silicon tetrachlorides again, is warming up to 110 ℃, reacted 1 hour, after washing through twice hexane, evaporation drying obtains solid ingredient B.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Comparative example 1
1, the preparation of catalyst component
With 4.8 gram Magnesium Chloride Anhydrouss, 93 milliliters of toluene, 4.0 milliliter epoxy chloropropane, 12.5 the milliliter tributyl phosphate joins through in the abundant metathetical reactor of nitrogen, at mixing speed 450rpm, temperature is under 60 ℃ the condition, reacted two hours, add 1.4 gram Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, with dripping 56 milliliters of titanium tetrachlorides in 1 hour, be warming up to 85 ℃ gradually with 2 hours, constant temperature one hour. in temperature-rise period, separate out solids gradually. the elimination mother liquor, through toluene and twice washing of hexane after drying, obtain containing the solids A of magnesium/titanium.
10 gram solids A are joined through in another reactor of the abundant metathetical of nitrogen, add 90ml iso-pentane, 0.3 gram titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, normal temperature reacted one hour down, filter solution, add the 90ml iso-pentane again, 3.5 the aluminium diethyl monochloride hexane solution of ml volumes concentration 26.43% at room temperature reacted one hour, obtained particulate solid thing B component through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Comparative example 2
1, the preparation of catalyst component
6.5 kilograms of Magnesium Chloride Anhydrouss, 124.6 liters of toluene, 5.4 liters of epoxy chloropropane, 16.9 liters of tributyl phosphates are joined in the reactor, be under 60 ℃ the condition, to react 3.5 hours in mixing speed 130rpm, temperature, add 1.89 kilograms of Tetra hydro Phthalic anhydrides, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 80 ℃ gradually, constant temperature one hour, the elimination mother liquor through toluene and 3 washings of hexane after drying, obtains containing the solids A of magnesium/titanium.
2 liter of four titanium butoxide and 6.8 liters of tetrahydrofuran (THF)s are joined in the dissolution kettle, add 680 gram titanous chlorides after stirring again, dissolving forms compound titanium solution under the condition of mixing speed 200rpm.
Solids A is transferred in another reactor, adds 100 liters of hexanes, drip 8.26 liters of titanium tetrachlorides under 10 ℃ the condition stirring 130rpm, temperature.Normal temperature reacted one hour down, filtered solution, and with hexane wash twice, added 80 liters of hexanes again, and the aluminium diethyl monochloride hexane solution reaction of 4.4 liters of volumetric concentrations 14% one hour obtains particulate solid thing B component through vacuum-drying.
2, slurry polymerization
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Comparative example 3
1, Preparation of catalysts
9.6 gram Magnesium Chloride Anhydrouss, 50 milliliters of toluene, 46.8 milliliters of 2-Ethyl Hexanols are joined in the reactor, are under 110 ℃ the condition, to react about 120 minutes in mixing speed 450rpm, temperature, add 2.22 gram Tetra hydro Phthalic anhydrides, continue about 60 minutes of reaction.Get above-mentioned homogeneous solution 50ml and fill in the reactor of 200ml titanium tetrachloride slow the adding, it is-20 ℃ of stirrings that do not stop that this process keeps still temperature, add the back and be warming up to 110 ℃ gradually with about 180 minutes, and constant temperature 2 hours, the elimination mother liquor obtains solid ingredient A.
In the reactor of solid ingredient A, add the 200ml titanium tetrachloride, be warming up to 110 ℃, constant temperature 2 hours.Remove mother liquor, solid residue is with 60 ℃ of hexane wash 3 times, slowly adds the 3.0ml tetrahydrofuran (THF) and reacted 1 hour in the 100ml hexane solvent, and after washing through twice hexane, evaporation drying obtains particulate solid composition B.
2, polymerization
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Table 1: polymerization result
Embodiment Condition 1 Condition 2
Active (gPE/gCat) BD (g/cm 3) MI (g/10min) Active (gPE/gCat) BD (g/cm 3) MI (g/10min)
1 8860 0.39 3.10 2700 0.40 170
2 7300 0.36 2.12 2540 0.37 154
3 7650 0.35 1.98 2630 0.36 164
4 6830 0.37 2.06 2400 0.38 162
5 6954 0.36 1.89 2510 0.37 152
6 7320 0.37 2.00 2581 0.38 148
7 4830 0.38 2.65 1980 0.38 172
8 5264 0.37 2.31 2140 0.38 165
9 4960 0.36 2.12 2050 0.37 168
10 4863 0.37 2.20 2020 0.37 159
11 5410 0.38 2.10 2189 0.39 158
12 5638 0.36 2.43 2250 0.37 169
13 4780 0.37 2.43 1988 0.38 170
14 5838 0.36 1.99 2310 0.38 145
15 6102 0.38 1.86 2380 0.38 143
16 5980 0.38 2.34 2356 0.39 166
Comparative example - - - - - -
1 6860 0.36 2.02 2300 0.37 72.6
2 6540 0.39 1.44 2210 0.40 71.0
3 4600 0.35 1.35 1834 0.36 63.5

Claims (11)

1. catalyst component that is used for vinyl polymerization or copolymerization, it is characterized in that, it is included on a kind of solids of titaniferous/magnesium, the compound of at least a transition metals Ti of load, at least a electron donor and at least a hydrogen regulation performance improving agent and the catalyst component that obtains;
Described electron donor(ED) is aliphatic ether, aromatic oxide, mixed ether, cyclic aliphatic ether and aliphatic ketone;
The general formula of described transition metal titanium compound is Ti (OR) aX b, R is C in the formula 1～C 14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen atom, a is 0 to 2 integer, b is 0 to 4 integer, a+b=3 or 4;
Described hydrogen regulation performance improving agent is the silicon compounds, and its general formula is Si (OR) aX b, R is C in the formula 1～C 14Alkyl or aralkyl, X is a halogen, a is 0 to 4 integer, b is 0 to 4 integer, a+b=4.
2. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that, the solids of described titaniferous/magnesium prepares by following method: form homogeneous solution after magnesium compound is dissolved in organic epoxy compounds, organo phosphorous compounds and inert solvent, obtain with the compound effects of transition metals Ti in the presence of analysing helping.
3. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, described electron donor(ED) is C 2～C 6Aliphatic ether, C 3～C 4Cyclic ethers, C 3～C 6Aliphatic ketone.
4. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, described electron donor(ED) is preferably tetrahydrofuran (THF), butanone, pimelinketone, 2,4 hexanediones, 4-methyl-3 amylene-2 ketone, n-butyl ether, phenyl ethyl ether.
5. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, described hydrogen regulation performance improving agent is preferably silicon tetrachloride, tetraethoxy-silicane, four butoxy silicon, a chlorine triethoxysilicane, dichloro diethoxy silicon.
6. according to the described catalyst component that is used for vinyl polymerization or copolymerization of claim 1, it is characterized in that the transition metal titanium compound is preferably titanium tetrachloride, trichlorine ethanolato-titanium, titanous chloride.
7. the preparation method of the described catalyst component that is used for vinyl polymerization or copolymerization of one of claim 1～6 is as follows: magnesium compound is dissolved in organic epoxy compounds, organo phosphorous compounds and inert solvent, form behind the homogeneous solution and the transition metals Ti compound, in the presence of precipitation additive, separate out the solids that contains magnesium/titanium; In the presence of the electron donor compound, will contain the solids and the reaction of transition metal titanium compound of magnesium/titanium, the product that obtains is handled with the hydrogen regulation performance improving agent and is obtained catalyst component.
8. the preparation method who is used for the catalyst component of vinyl polymerization or copolymerization according to claim 7, it is characterized in that, each component is in every mole of magnesium compound, 0.2～10 mole of organic epoxy compounds, 0.1～3 mole of organo phosphorous compounds, 0.03～1.0 mole of precipitation additive, 0.01～10 mole of electron donor compound, 0.5～150 mole of transition metal titanium compound, 0.01～10 mole of hydrogen regulation performance improving agent.
9. catalyzer that is used for vinyl polymerization or copolymerization comprises following two kinds of component reaction products:
(1) the described catalyst component that is used for vinyl polymerization or copolymerization of one of claim 1～6,
(2) alkylaluminium cpd.
10. the catalyzer that is used for vinyl polymerization or copolymerization of claim 9 is in the application of the a-alpha-olefinic copolymerization of vinyl polymerization or ethene and C3～C8.
11. the catalyzer that is used for vinyl polymerization or copolymerization of claim 9 is in the application of ethene gas phase or slurry polymerization or copolymerization.
CNB2004100782791A 2004-09-23 2004-09-23 Catalyst used for ethylene polymerization or copolymerization, its preparation method and application Expired - Lifetime CN100389134C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101565476B (en) * 2008-04-25 2011-01-26 中国石油化工股份有限公司 Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof
CN104974283A (en) * 2014-04-11 2015-10-14 中国石油化工股份有限公司 Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN105482002A (en) * 2014-10-10 2016-04-13 中国石油化工股份有限公司 Catalyst component for polymerization of ethylene, catalyst and preparation method of catalyst component

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CN1137155C (en) * 1999-12-06 2004-02-04 中国石油化工集团公司 Catalyst system for polymerization or copolymerization of olefine
KR100389962B1 (en) * 2000-11-10 2003-07-02 삼성종합화학주식회사 Preparation method of catalyst for ethylene polymeration or copolymeration

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101565476B (en) * 2008-04-25 2011-01-26 中国石油化工股份有限公司 Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof
CN104974283A (en) * 2014-04-11 2015-10-14 中国石油化工股份有限公司 Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN104974283B (en) * 2014-04-11 2017-03-22 中国石油化工股份有限公司 Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN105482002A (en) * 2014-10-10 2016-04-13 中国石油化工股份有限公司 Catalyst component for polymerization of ethylene, catalyst and preparation method of catalyst component
CN105482002B (en) * 2014-10-10 2018-03-02 中国石油化工股份有限公司 Catalytic component, catalyst for vinyl polymerization and preparation method thereof

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