CN101190953B - Process for preparing catalyst solid component of olefin polymerization - Google Patents
Process for preparing catalyst solid component of olefin polymerization Download PDFInfo
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- CN101190953B CN101190953B CN2006101442048A CN200610144204A CN101190953B CN 101190953 B CN101190953 B CN 101190953B CN 2006101442048 A CN2006101442048 A CN 2006101442048A CN 200610144204 A CN200610144204 A CN 200610144204A CN 101190953 B CN101190953 B CN 101190953B
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Abstract
The invention relates to a preparation of olefin polymerization catalyst solid constituent, and comprises the steps: magniferous composition with general formula C l Mg (OR) . n (ROH) reacts with electron donor compound and tetrahalogen titanium respectively in the presence of unreactive hydrocarbons; solid is collected, washed and dried. R in the general formula is selected from C1-C5 alkyl while n is 0.1-1.0. The method has simple preparation; the produced catalyst solid constituent is used for propylene polymerization and has relatively high activity and tacticity.
Description
Technical field
The present invention is a kind of preparation method of catalyst solid component of olefin polymerization, specifically, is a kind of by containing the method that magnesium complex prepares catalyst solid component of olefin polymerization.
Background technology
The Ziegler-Natta catalyst system comprises catalyst solid constituent and promotor, described catalyst solid constituent is made of the titanium compound that is carried on the carrier, carrier can be magnesium compound or other solid chemical compound, and as silica gel or aluminum oxide etc., carrier commonly used is a Magnesium Chloride Anhydrous.Promotor is an organo-aluminium compound.
When being the efficient Ziegler-Natta catalyst solid ingredient of preparing carriers, generally be titanium-containing compound such as load titanium tetrachloride again after Magnesium Chloride Anhydrous is activated, otherwise the catalyst activity of preparation is not high with the magnesium chloride.The method of activation Magnesium Chloride Anhydrous commonly used is with excessive alcohol or ether Magnesium Chloride Anhydrous to be handled, and then the load titanium-containing compound, makes catalyst solid constituent as titanium tetrachloride.For making carrier and catalyzer that good form be arranged, need to contain the more pure and mild thing carrier of spherical magnesium chloride of alcohol amount, further load TiCl again after the dealcoholysis halogenation
4Disclosing a kind of general formula as CN1226901A is MgCl
2MROHnH
2The magnesium dichloride-alcohol adducts of O (2≤m≤4) is used to prepare efficient Ziegler-Natta catalyst component.The preparation method of described adducts adds 2 moles alcohol at least in every mole of magnesium chloride, make magnesium chloride be melted into limpid adducts fully, adduct solution is added in the hexane of low temperature (＜12 ℃), makes and separates out the magnesium dichloride-alcohol adducts solid particulate.With the adducts solid particulate or after being heated dealcoholysis, adopt ordinary method load TiCl
4Make catalyst solid constituent.
CN1258684A discloses the catalyzer of a kind of propylene polymerization or copolymerization, the preparation method of the solid ingredient of this catalyzer is: magnesium halide is dissolved in the solvent system of organic epoxy compounds and organo phosphorous compounds and unreactive hydrocarbons solvent composition, formation contains the magnesium homogeneous solution, this solution mixes with the titanium tetrachloride or derivatives thereof, in the presence of precipitation additive, separate out solids, after the multicomponent hydroxy acid ester processing, obtain solid titanium catalyst component with titanium tetrachloride reaction again.Described organic epoxy compounds is that epoxy chloropropane, organo phosphorous compounds are tributyl phosphate.The catalyzer that makes is the catalyzing propone tactic polymerization efficiently.
The disclosed solid titanium catalyst component of CN96106647.4 is in the presence of the silicoorganic compound of non-activity hydrogen, a kind of magnesium compound of liquid state is contacted with a kind of liquid titanium compound to be made, the magnesium compound of described liquid state is magnesium halide and pure product of contact, described alcohol is methyl alcohol, ethanol, Virahol or butanols, liquid titanium compound is a titanium tetrahalide, and silicoorganic compound are tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane etc.Similarly, the disclosed olefin polymerization catalysis preparation method of CN1263895A is: earlier with magnesium compound at aliphatic hydrocarbon with contain at least in the presence of the unsaturated fatty acid ester of a hydroxyl and react generation alcohol adduct slurries with alcohol, then slurries are carried out carrying titanium after the esterification with organo-aluminium compound, make catalyzer through washing, drying.
Also having with the alkoxyl magnesium is the method for feedstock production activation magnesium chloride support, a kind of preparation method of Ziegler-Natta type catalyst solid constituent is disclosed as CN1016422B, this method is in the presence of transition metal alkoxide, make the reaction of solubility dialkoxy magnesium and transition metal halide, the reusable liquid hydrocarbon is settled out solid ingredient, can obtain the very narrow spherical catalyst solid ingredient of size distribution.Alkoxyl group in the dialkoxy magnesium that it adopts is the branched alkoxy that contains the line style alkoxyl group of 6～12 carbon atoms or 5～12 carbon atoms are arranged, so that can form the pure magnesium solution that is dissolved in liquid hydrocarbon, yet this alkoxyl magnesium often is difficult to obtain.
CN1358202A discloses a kind of preparation method and catalyzer prepared therefrom of magnesium/magnesium/transition metal alkoxide complexes.This method makes the alkoxide complexes that contains magnesium/transition metal and is selected from alkyl aluminum halide, TiX
4, SiX
4, BX
3And Br
2Halogenating agent contact, from slurries, isolate solid then and be catalyzer.Described transition metal is selected from titanium, zirconium, hafnium, chromium, iron or vanadium.This catalyzer can be used for vinyl polymerization.
USP5034361 discloses a kind of catalyst precursor, is a kind of alcoholic solution that contains the adducts of alkoxyl magnesium and the formation of Lewis acidic substance, and the highest carbon number in the described alkoxyl group is 4, and alcohol is methyl alcohol or ethanol; Acidic substance are selected from sulfurous gas, formaldehyde, aluminum alkoxide or tri-alkoxy boron, and the maximum carbon number of wherein said alkyl also is 4.This solution can be used for spraying drying, lyophilize or floods silica containing carrier making support of the catalyst, uses ordinary method load titanium tetrachloride and internal electron donor compound again, promptly can be made into the catalyst solid constituent of better activity and stereoselective.
USP5849655 forms metal alkoxides halogenide with the reaction of alkoxyl magnesium and halogenating agent, again it is carried a titanium after with diethyl or the acid treatment of diisobutyl O-phthalic and makes solid ingredient.CN1359394A discloses a kind of magnesium/titanium alkoxide complexes and catalyzer prepared therefrom, and this method is blocked in the presence of the agent pure and mild, alkoxyl magnesium is contacted with titan-alkoxide make catalyzer solid precursor slurries, then solid precursor is separated from slip.Because alkoxyl magnesium forms the chain macromolecular structure, utmost point indissoluble is separated, and in order to obtain good carrier of form or catalyzer, must make it fragment into small molecules with blocking agent.Describedly block agent and be selected from CO
2, CO
3 2-, (O
2COC
2H
5)
-Etc. a large amount of materials that can dissolve alkoxyl magnesium when excessive.
It is the preparing carriers catalyst solid constituent that USP5817591 adopts the chlorination magnesium ethylate, need during preparation with the slurry dissolved formation solution of 2-Ethylhexyl Alcohol chlorination magnesium ethylate and varsol formation, and then go out solid with the titanium tetrachloride contact precipitation, this solid is contacted with n-butyl phthalate with titanium tetrachloride, handle obtaining catalyst solid constituent again with titanium tetrachloride.If do not use 2-Ethylhexyl Alcohol with the dissolving of chlorination magnesium ethylate in the preparing carriers process, the catalyst activity that then makes declines to a great extent.
CN1590415A discloses a kind of preparation method of catalyst solid component of olefin polymerization, in the presence of methyl halide, makes C
2～C
4Low-carbon alcohol and magnesium powder make even magnesium complex solution by 2.0～4.0 molar ratio reaction, but this method does not prepare single magnesium complex carrier, make complex carrier but the magnesium complex solution that forms loaded on the preparing spherical SiO 2 carrier, the load titanium compound makes catalyst solid constituent again.
USP4469648 discloses a kind of method with crystalline alkoxyl magnesium compound and titanium tetrachloride contact preparation catalyst solid constituent, and the general formula of described alkoxyl magnesium compound is [Mg
4(OR)
6(R ' OH)
10] X, wherein R and R ' are selected from C
1～C
4Alkyl.
Summary of the invention
It is carrier that the preparation method who the purpose of this invention is to provide a kind of catalyst solid component of olefin polymerization, this method adopt a kind of magniferous title complex, and the catalyst solid constituent that makes has the better polymerization reactivity worth.
The preparation method of catalyst solid component of olefin polymerization provided by the invention, comprise with general formula being the magnesium complex that contains of ClMg (OR) n (ROH), in the presence of unreactive hydrocarbons, react with electron donor compound and titanium tetrahalide respectively, collect solid then, washing is also dry, and R is selected from C in the described general formula
1～C
5Alkyl, n is 0.1～1.0.
The inventive method is that to contain magnesium complex be carrier to the raw material synthetic with magnesium powder and low-carbon alcohol, this carrier need not use excessive alcohol activation to get final product direct load titanium tetrahalide and internal electron donor compound, the preparing carriers raw material is cheap and easy to get, the preparation method is simple, the Preparation of catalysts method is also simplified more simultaneously, thereby reduced the Preparation of catalysts cost, and had advantages of high catalytic activity and stereospecificity preferably with the catalyst solid constituent of this preparing carriers.
Embodiment
The present invention in the presence of methyl halide, uniformly contains magnesium complex solution with what the reaction of suitable proportioning generated with magnesium powder and alcohol, and described methyl halide should be not and magnesium powder direct reaction, but magnesium powder, alcohol and methyl halide are reacted jointly.The described magnesium complex solution that contains can be directly adds solid carrier and is prepared into the carrier that contains magnesium complex in this solution, load olefin polymerizating activity component prepares catalyst solid constituent again; Also available stable hydrocarbon is separated out the title complex that contains in the magnesium complex solution, after super-dry, makes to contain magnesium complex, and be carrier directly to contain magnesium complex, further load olefin polymerizating activity component makes catalyst solid constituent.The used magnesium complex carrier that contains of the present invention need not activate with alcohol, the load efficiency height, and the catalyst solid constituent catalytic activity height, the stereospecificity that make are good.
The carrier that uses in the described method has the general expression of ClMg (OR) n (ROH) for containing magnesium complex, and ROH is the alcohol with magnesium powder reaction in the general formula, (OR) group from the alcohol of magnesium powder reaction in alkoxyl group.The preferred C of R in the general formula
2～C
4Alkyl, more preferably C
2～C
3Alkyl, n is preferred 0.5～1.0 in the described magnesium-containing carrier, the magnesium complex that contains that forms in this scope because of n is a crystalline material, and when n less than 0.5 the time, containing magnesium complex is noncrystalline thing.
The preparation method who contains magnesium complex of the present invention is included in methyl halide and exists down, makes C
1～C
5Alcohol and the magnesium powder by 1.5～4.0: 1 mol ratio 20～200 ℃ of reactions, add stable hydrocarbon then, collect solid particulate and dry, the mass ratio of described methyl halide and magnesium powder is 10～500: 1.
The preferred methylene dichloride of described methyl halide, trichloromethane or tetrachloromethane, C
1～C
5Pure particular methanol, ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol, more preferably ethanol.The mass ratio of described methyl halide and magnesium powder preferred 10～500: 1, more preferably 50～120: 1.
Preferred 40～100 ℃ of the temperature of reaction of described alcohol and magnesium powder, alcohol during reaction/magnesium mol ratio should be controlled at 1.5～4.0: 1, if ratio is too low, then pure dosage is less, the flowability of gained carrier is not good, the catalyst reaction poor activity that makes with this carrier; If alcohol/magnesium mol ratio is too high during reaction, then understand the generation that produces dialkoxy magnesium by product and influence carrier of the present invention in the reaction process.When alcohol reacts with the magnesium powder, in reactant, add the initiator such as the I of small quantities of usual
2, mercury chloride etc. can impel reaction to carry out with fast speeds.Alcohol is 1～20 hour with the reaction times that the reaction of magnesium powder suits, preferred 4～10 hours.Alcohol/magnesium mol ratio preferred 2.0～3.0: 1.
Above-mentioned containing in the magnesium complex preparation process, use stable hydrocarbon to make to contain magnesium complex and from reaction soln, separate out, precipitation process preferably under agitation carries out, separate out the temperature that contains the magnesium complex solid particulate and be-10～100 ℃, preferred 0～60 ℃, preferred 10～500 minutes of churning time, more preferably 30～120 minutes.After treating that solid particulate is separated out, it is separated with saturated hydrocarbon solvent, gained solid particulate drying promptly obtains containing magnesium complex.The described preferred C of stable hydrocarbon that is used to separate out carrier
5～C
8Aliphatic hydrocarbon, as pentane, iso-pentane, hexane, heptane or octane.
The inventive method in the presence of unreactive hydrocarbons, with titanium tetrahalide and the reaction of electron donor compound, prepares catalyst solid constituent with the described magnesium complex that contains respectively.Preferable methods is earlier once carried titanium with the titanium tetrahalide reaction for making the described magnesium complex that contains, and uses the electron donor compound treatment again, and then carries out secondary with the titanium tetrahalide reaction and carry titanium.
Describedly once carry the used titanium tetrahalide of titanium and contain the mol ratio of magnesium preferred 2～10: 1 in the magnesium complex, more preferably 2～7: 1, the temperature of reaction of once carrying titanium is 10～100 ℃, preferred 20～80 ℃.Described secondary carries the used titanium tetrahalide of titanium and contains the mol ratio of magnesium preferred 1～5: 1 in the magnesium complex, and more preferably 1～3.5: 1, the temperature of reaction that secondary carries titanium is 80～150 ℃, preferred 90～120 ℃.The preferred titanium tetrachloride of described titanium tetrahalide.
Electron donor compound in the described catalyst solid constituent was preferably introduced carrier at twice year between the titanium, and the temperature of described carrier and the reaction of electron donor compound is 30～130 ℃, preferred 60～100 ℃.Described electron donor compound is selected from phthalic ester, 1, the mixture of 3-diether, succinate or above-mentioned substance, as diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, ethyl succinate or 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal.Contain during reaction that the mol ratio of magnesium and electron donor is 2～20 in the magnesium complex, preferred 4～10.
The described magnesium complex that contains is preferably used SiX earlier
4Carry out halogenation treatment, and then react with titanium tetrahalide and electron donor compound.Used SiX during halogenation treatment
4With the mol ratio that contains magnesium in the magnesium complex be 0.1～1.0, preferred 0.1～0.5.The temperature of halogenation treatment is 0～100 ℃, preferred 20～50 ℃.Time is 20～300 minutes, preferred 30～120 minutes.Described SiX
4Preferred SiCl
4
The described preferred C of unreactive hydrocarbons that is used to prepare catalyst solid constituent
6～C
8Aromatic hydrocarbons or C
5～C
8Aliphatic hydrocarbon, as benzene, toluene, hexane or heptane.Described unreactive hydrocarbons are 10～200: 1 with the mass ratio that contains magnesium complex, preferred 20～100: 1.
The catalyst solid constituent of the inventive method preparation is applicable to alpha-olefin homopolymerization or copolyreaction, must be used with the promotor alkylaluminium cpd during polymerization.The preferred triethyl aluminum of described promotor, three n-butylaluminum or triisobutyl aluminium.Al/Ti mol ratio suitable during polyreaction is 20～800, preferred 20～300.In order to obtain to have high normal polypropylene product, also need add the external electron donor compound during polyreaction, as dimethoxydiphenylsilane, dicyclohexyl dimethoxy silane etc., suitable Al/Si ratio is 10～40.Polymeric reaction temperature is 60～120 ℃, and preferred 80～100 ℃, pressure is 0.1～6.0MPa, preferred 0.4～2.0MPa.
The preferred C of described alpha-olefin
2～C
12Alkene, as ethene, third rare, butylene, hexene or octene.That the used monomer of copolymerization can be is third rare, butylene, hexene or octene.Be the molecular weight of telomerized polymer, can add chain-transfer agent during polymerization, preferred chain-transfer agent is a hydrogen.
Further specify the present invention below by example, but the present invention is not limited to this.
The element of sample or alkoxy group content and physico-chemical parameter adopt following method to measure in the example:
Cl, Mg-chemical titration.
Alkoxyl group-SHIMAD2U-8A type gas chromatograph (chromatographic column: GDX-401 2.5 * 3mm, FID: hydrogen flame) measure.
Ti-adds 1 30% hydrogen peroxide with the mass ratio dissolving by 1: 17 of sample and sulfuric acid, uses 721 spectrophotometer colorimetrics then, surveys absorbancy, looks into standard curve determination.
Infrared spectra (IR)-measure on Nicolet MAGNA-IR 560 infrared spectrometers grinds compressing tablet with KBr.
Fusing point-dsc (DSC) is measured on the T5000-DSC2910 instrument, during mensuration with sample in N
2In under the condition of 10 ℃/min, heat up and record.
Example 1
Prepare the magnesium complex carrier that contains of the present invention.
Get 1.0g (41.7mmol) magnesium powder, under nitrogen protection, put into there-necked flask, add 0.1g I again
2, and 60ml (80g) CH
2Cl
2, at 41 ℃ of (CH
2Cl
2Boiling point) oil bath was stirred 5 minutes down, dropwise slowly added 5ml (86.1mmol) ethanol, and reaction is acutely carried out and produced a large amount of bubbles.Dropwise, under this temperature, stirred 10 hours magnesium powder complete reaction.Reaction product is cooled to 25 ℃, obtains colourless transparent solution.Add the 60ml hexane under stirring in colourless transparent solution, promptly the adularescent crystal is separated out, and continues to stir 60min, filters, and with 25 ℃ of dry white powder crystal that get of solids, is carrier a, and its expression formula is ClMg (OC
2H
5) 0.63 (C
2H
5OH).
Each component concentration of carrier a is: Mg, 17.52 quality %; Cl, 27.71 quality %; (OC
2H
5), 53.40 quality %.It is 142.7 ℃ that the DSC method is measured its fusing point, and its alcoholic extract hydroxyl group characteristic peak of infrared measurement appears at 3400cm
-1Near.
Example 2
Method by example 1 prepares carrier, and different is with 60ml (89g) CHCl
3Replaced C H
2Cl
2, and at 61 ℃ of (CHCl
3Boiling point) magnesium powder and ethanol are reacted, the expression formula of the carrier b that makes is ClMg (OC
2H
5) 0.81 (C
2H
5OH).
Each component concentration of carrier b is: Mg, 16.67 quality %; Cl, 20.92 quality %; (OC
2H
5), 56.40 quality %.It is 142.9 ℃ that the DSC method is measured its fusing point, and the characteristic peak of its alcoholic extract hydroxyl group of infrared measurement appears at 3400cm
-1Near.
Example 3
Following examples preparation catalyst solid constituent of the present invention.
With three mouthfuls of reaction flask N that have a mechanical stirring device
2Fully displacement, and at N
2Under the air-flow the Powdered magnesium-containing carrier a of 2.0 grams is added reaction flask, add 20ml toluene again and be uniformly dispersed, 25 ℃ add 0.4ml (3.5mmol) SiCl
4Stirring reaction 0.5 hour.0.5 be warming up to 40 ℃ in hour, reduce to 20 ℃ again and add 8ml (72.05mmol) TiCl
4React and once carried titanium in 0.5 hour, 80 ℃ add 0.4ml (1.5mmol) diisobutyl phthalate, are warming up to 110 ℃ of reactions 2 hours, sedimentation, filtration, and the gained solid adds 4ml (36.61mmol) TiCl again with the hot washed twice of 20ml toluene difference
4Carry out secondary in 1 hour with 20ml toluene 110 ℃ of reactions and carry titanium, sedimentation, filtration, solid hexane wash 6 times obtain catalyst solid constituent C after 67 ℃ of dryings, and wherein each component concentration sees Table 1.
Example 4
Method by example 3 prepares catalyst solid constituent, and different is once to carry titanium to add 12ml (109.84mmol) TiCl
4, secondary carries titanium and adds 6ml (54.92mmol) TiCl
4, each component concentration of the catalyst solid constituent D that makes sees Table 1.
Example 5
Method by example 3 prepares catalyst solid constituent, and different is once to carry titanium to add 4ml (36.61mmol) TiCl
4, secondary carries titanium and adds 2ml (18.30mmol) TiCl
4, each component concentration of the catalyst solid constituent E that makes sees Table 1.
Example 6
With three mouthfuls of reaction flask N that have a mechanical stirring device
2Fully displacement, and at N
2Under the air-flow the Powdered magnesium-containing carrier a of 2.0 grams is added reaction flask, add 20ml toluene again and be uniformly dispersed, 25 ℃ add 4ml (36.61mmol) TiCl
4React and once carried titanium in 0.5 hour, 80 ℃ add 0.4ml (1.5mmol) diisobutyl phthalate, are warming up to 110 ℃ of reactions 2 hours, sedimentation, filtration, and the gained solid adds 2ml (18.30mmol) TiCl again with the hot washed twice of 20ml toluene difference
4Carry out secondary in 1 hour with 20ml toluene 110 ℃ of reactions and carry titanium, sedimentation, filtration, solid hexane wash 6 times obtain catalyst solid constituent F after 67 ℃ of dryings, and wherein each component concentration sees Table 1.
Example 7
Method by example 6 prepares catalyst solid constituent, and different is once to carry titanium to add 8ml (73.22mmol) TiCl
4, secondary carries titanium and adds 4ml (36.61mmol) TiCl
4, each component concentration of the catalyst solid constituent G that makes sees Table 1.
Example 8
Method by example 6 prepares catalyst solid constituent, and different is once to carry titanium to add 12ml (109.84mmol) TiCl
4, secondary carries titanium and adds 6ml (54.92mmol) TiCl
4, each component concentration of the catalyst solid constituent H that makes sees Table 1.
Example 9
Method by example 3 prepares catalyst solid constituent, and different is after described carrier disperses with toluene, to add 0.6ml (5.3mmol) SiCl
4React and carried titanium in 0.5 hour again, each component concentration of the catalyst solid constituent K that makes sees Table 1.
Example 10
Method by example 3 prepares catalyst solid constituent, and different is that the diisobutyl phthalate that adds is 0.6ml (2.25mmol), and each component concentration of the catalyst solid constituent L that makes sees Table 1.
Example 11
Method by example 3 prepares catalyst solid constituent, and different is once to carry titanium to add 12ml (109.84mmol) TiCl
4, 80 ℃ add 0.8ml (3.0mmol) diisobutyl phthalate, are warming up to 110 ℃ of reactions 2 hours, sedimentation, filtration, and solid washes twice with toluene heat, and each toluene consumption is 20ml, and secondary carries titanium and adds 6ml (54.9mmol) TiCl
4With 20ml toluene reaction 1 hour, sedimentation, filtration, solid hexane wash 6 times get catalyst solid constituent J after 67 ℃ of dryings, and wherein each component concentration sees Table 1.
Example 12
Method by example 3 prepares catalyst solid constituent, and the different carrier b that are to use replace carrier a, and each component concentration of the catalyst solid constituent Q that makes sees Table 1.
Comparative Examples 1
(1) preparation carrier
Get 1.0g (41.7mmol) magnesium powder, under nitrogen protection, put into there-necked flask, add 0.1g I again
2, and 60ml (80g) CH
2Cl
2, at 41 ℃ of (CH
2Cl
2Boiling point) oil bath was stirred 5 minutes down, dropwise slowly added 2.43ml (41.7mmol) ethanol, and reaction is acutely carried out and produced a large amount of bubbles.Dropwise, under this temperature, stirred 12 hours magnesium powder complete reaction.Reaction product is cooled to 25 ℃, obtains white soup compound, the dry white powder that gets is carrier c, and its expression formula is ClMg (OC
2H
5).
Each component concentration of carrier c is: Mg, 23.1 quality %; Cl, 34.2 quality %; (OC
2H
5), 42.8 quality %.The DSC method is measured its no sharp melting point.
(2) preparation catalyst solid constituent
Get 2.0 gram carrier c, prepare catalyst solid constituent N by the method for example 3, wherein each component concentration sees Table 1.
Example 13～23
Following example is estimated the polymerization catalyzed performance of the catalyst solid constituent of the present invention's preparation.
5L stainless steel polymermaking autoclave is fully replaced with nitrogen, add 1600mL exsiccant hexane, add the 100mg catalyst solid constituent again, add triethyl aluminum and O-phthalic TMOS, making Al/Ti is 300, and Al/Si is 15.Be warming up to 70 ℃, feed hydrogen and propylene, keeping the hydrogen dividing potential drop is 0.2MPa, feeds propylene continuously and carries out polyreaction in 2 hours, and total pressure is controlled to be 0.7MPa during reaction.Reaction finishes, and isolates polymkeric substance and dry from hexane, obtains runny spherical polypropylene GRANULES.The polyacrylic character data of each example catalyst system therefor, catalyst activity and preparation sees Table 2.
As shown in Table 2, the catalyst solid constituent of the inventive method preparation has advantages of high catalytic activity than Comparative Examples.
Table 1
Table 2
Claims (16)
1. the preparation method of a catalyst solid component of olefin polymerization, being included in unreactive hydrocarbons exists down, with general formula is that titanium is once carried in magnesium complex and the titanium tetrahalide reaction that contains of ClMg (OR) n (ROH), use the electron donor compound treatment again, carry out secondary with the titanium tetrahalide reaction again and carry titanium, collect solid then, washing is also dry, and R is selected from C in the described general formula
2～C
4Alkyl, n is 0.1～1.0, described electron donor compound is selected from phthalic ester, 1, the mixture of 3-diether, succinate or above-mentioned substance.
2. in accordance with the method for claim 1, it is characterized in that describedly containing that R is selected from C in the magnesium complex general formula
2～C
3Alkyl, n is 0.5～1.0.
3. in accordance with the method for claim 1, it is characterized in that once carrying the used titanium tetrahalide of titanium is 2～10: 1 with the mol ratio that contains magnesium in the magnesium complex, and it is 1～5: 1 with the mol ratio that contains magnesium in the magnesium complex that secondary carries the used titanium tetrahalide of titanium.
4. in accordance with the method for claim 1, it is characterized in that described titanium tetrahalide is a titanium tetrachloride.
5. in accordance with the method for claim 1, it is characterized in that the described magnesium complex SiCl that contains
4React with titanium tetrahalide and electron donor compound again after the processing.
6. in accordance with the method for claim 5, it is characterized in that described SiCl
4With the mol ratio that contains magnesium in the magnesium complex be 0.1～1.0.
7. in accordance with the method for claim 1, it is characterized in that describedly containing that the mol ratio of magnesium and electron donor compound is 2～20 in the magnesium complex.
8. in accordance with the method for claim 1, it is characterized in that described unreactive hydrocarbons are C
6～C
8Aromatic hydrocarbons or C
5～C
8Aliphatic hydrocarbon.
9. in accordance with the method for claim 1, it is characterized in that the described preparation method who contains magnesium complex is included in methyl halide and exists down, make ethanol, propyl alcohol or butanols and magnesium powder by 1.5～4.0: 1 mol ratio is 20～200 ℃ of reactions, add stable hydrocarbon then, collect solid particulate and dry, the mass ratio of described methyl halide and magnesium powder is 10～500: 1.
10. in accordance with the method for claim 9, it is characterized in that described propyl alcohol is that Virahol, butanols are isopropylcarbinol.
11. in accordance with the method for claim 9, it is characterized in that described methyl halide is methylene dichloride, trichloromethane or tetrachloromethane.
12. it is characterized in that in accordance with the method for claim 9, the mol ratio of described ethanol, propyl alcohol or butanols and magnesium powder is 2.0～3.0: 1.
13. in accordance with the method for claim 12, it is characterized in that described propyl alcohol is that Virahol, butanols are isopropylcarbinol.
14. in accordance with the method for claim 9, the temperature of reaction that it is characterized in that described alcohol and magnesium powder is 40～100 ℃, and stable hydrocarbon is C
5～C
8Aliphatic hydrocarbon.
15. in accordance with the method for claim 9, the mass ratio that it is characterized in that described methyl halide and magnesium powder is 20～200: 1, and stable hydrocarbon is pentane, hexane, heptane or octane.
16. in accordance with the method for claim 15, it is characterized in that described pentane is an iso-pentane.
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| SA3686B1 (en) | 2009-10-16 | 2014-10-22 | China Petroleum& Chemical Corp | Catalyst component for olefin polymerization and catalyst comprising the same |
| CN102079796B (en) * | 2009-11-26 | 2012-07-25 | 中国石油化工股份有限公司 | Load type olefin polymerization solid catalyst as well as preparation method and application of load type olefin polymerization solid catalyst |
| CN102718897B (en) * | 2011-03-31 | 2015-01-14 | 中国石油化工股份有限公司 | Loaded olefin polymerization solid catalyst ingredient, and preparation method and application thereof |
| CN109201117B (en) * | 2017-07-06 | 2021-11-16 | 中国石油化工股份有限公司 | Supported ethylene oligomerization catalyst, and preparation method and application thereof |
| KR20230097111A (en) | 2020-10-26 | 2023-06-30 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Solid component for preparing olefin polymerization catalyst, method for preparing the same and application thereof |
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