CN101962417A - Catalyst for vinyl polymerization and preparation and application thereof - Google Patents
Catalyst for vinyl polymerization and preparation and application thereof Download PDFInfo
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- CN101962417A CN101962417A CN2009100895966A CN200910089596A CN101962417A CN 101962417 A CN101962417 A CN 101962417A CN 2009100895966 A CN2009100895966 A CN 2009100895966A CN 200910089596 A CN200910089596 A CN 200910089596A CN 101962417 A CN101962417 A CN 101962417A
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Abstract
The invention provides a solid catalyst component for vinyl polymerization and a preparation method thereof. The component is prepared by the following three continuous synthesis steps of: preparing a magnesium-containing solid from metal magnesium and alcohol in the presence of halogen or a compound containing halogen elements; treating the magnesium-containing solid to prepare a magnesium-containing catalyst carrier by using an organic metal compound or a mixture of the organic metal compound and an electron donor; and treating the magnesium-containing catalyst carrier to prepare the catalyst component by using a compound of transition metal titanium in the presence of an inert diluent. The solid catalyst component has the characteristics of simple technology, convenience of operation, low investment of industrial equipment, low production cost, easily controlled product quality, and the like. By catalyzing the vinyl polymerization together with alkyl aluminum, the solid catalyst component has the characteristics of higher catalyst activity and stacking density, less fine components of produced polyethylene powder and the like, and is applied to slurry polymerization or gas-phase polymerization of ethylene, particularly gas-phase fluidized bed ethylene polymerization technology in which catalysts are fed in a slurry form.
Description
Technical field
The present invention relates to a kind of titaniferous ingredient of solid catalyst of vinyl polymerization that is used for, method for making and application belong to field of olefin polymerisation.
Technical background
Along with the development of world's polyolefine industry, manufacture of polyolefins technology is updated and is innovated, and makes the polyolefine industry more and more higher to the requirement of catalyzer, has also occurred many different types of polyolefin catalysts simultaneously.
In the copolymerization of the equal polymerization of the polyreaction of alkene, particularly ethene or ethene and alpha-olefin, adopt with magnesium, titanium, halogen and electron donor catalyst component mostly as basal component.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.
In above-mentioned disclosed patent, in order to make catalyzer applicable to gas-phase fluidized bed polymerization process, employed carrier-silicon-dioxide median size, surface-area, aperture all there is strict requirement, and the price of this carrier is more expensive, need before use simultaneously silica supports is carried out strict activation, these all cause the increase of catalyst production cost; 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.
The Catalyst Production method that Chinese patent CN 1085915A is mentioned, although overcome foregoing some shortcomings, but need to use MAGNESIUM METAL in process of production as reductive agent, and still need use a large amount of silica supports materials, finally to obtain the catalyst particles granule product and also will adopt spray-dired method, facility investment is big, complicated operation, makes its overall manufacturing cost still higher.
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, organo phosphorous compounds formation homogeneous solution by magnesium halide, halogenide and derivative effect thereof with at least a precipitation additive, a kind of multi-carboxylate's electron donor and transition metals Ti prepares again, 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 hydrogen response is not ideal enough.
On the basis of above-mentioned Chinese patent CN85100997, Chinese patent CN1229092A discloses a kind of catalyzer that is used for vinyl polymerization or copolymerization, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor stimulator 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 in fact, this catalyst component that has added the alcohols stimulator is being used for ethene gas-phase polymerization technology, particularly during fluidized bed polymerization process, especially the starting stage of polyreaction, polyreaction is very fast, makes the polymkeric substance of generation broken easily, 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, the result is unsatisfactory.
On the basis of above-mentioned Chinese patent CN85100997, Chinese patent CN1463991A discloses a kind of catalyzer that is used for vinyl polymerization or copolymerization again, magnesium compound is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, mix with titanium compound after forming homogeneous solution, in the presence of precipitation additive, separate out solids; In the presence of the electron donor compound, resulting solids and titanium compound are reacted, adopt activator that reaction product is activated then, obtain catalyst component.Reactive behavior was higher when the catalyzer of this prepared was used for fluidized bed polymerization process, and the fine powder content of polymer powders also has substantial degradation, but this catalyst preparation process flow process is longer, and technology is comparatively complicated.
Be that the olefin polymerization catalysis of carrier has active high, advantage such as particle shape is good, degree of isotacticity is high, hydrogen regulation performance is good with the alkoxyl magnesium.
The method of the spherical alkoxyl magnesium carrier of conventional at present preparation comprises:
1. make catalyzer with iodine and make MAGNESIUM METAL and ethanol direct reaction, the weight ratio of ethanol and MAGNESIUM METAL was 7～9 when control reaction solution viscosity sharply rose (reactivity 70.85%), becoming sticky rapidly, the back changes ethanol and the MAGNESIUM METAL weight ratio is 15.20, prepares spherical magnesium ethylate carrier (spy opens flat 8-73388);
With the ratio control of ethanol and magnesium powder in 9/1～15/1 scope, ethanol and MAGNESIUM METAL be intermittent or method (spy opens flat 3-74341) that successive reacts when alcohol reflux;
3. the preparation method (special public clear 63.4815) that under stable hydrocarbon coexistence, reacts of MAGNESIUM METAL and ethanol.
Chinese patent CN101173015A discloses a kind of catalyst component that is used for vinyl polymerization or copolymerization, it is characterized in that, 1) preparation of titaniferous solids: dialkoxy magnesium under the situation that has inert diluent or inertialess thinner to exist, is obtained with the transition metals Ti compound effects; 2) in the presence of described electron donor compound, after titaniferous solids and the reaction of transition metal titanium compound.In every mole of dialkoxy magnesium, inert diluent is 0～100 mole in the step 1), and the transition metal titanium compound is 2～20 moles; Step 2) in every mole of dialkoxy magnesium compound, titanium compound is 0.3～20 mole in, is preferably 0.5～10 mole; Electron donor is 0.01～10 mole, is preferably 0.01～1 mole; 0.1～10 mole in activator is preferably 0.1～5 mole.The size-grade distribution of the polymer powders that is obtained by catalyst component polymerization of the present invention is very concentrated, and fine powder content is few, the tap density height.But because the alkoxyl magnesium preparing carriers ingredient of solid catalyst that is to use prepared beforehand to go out, this making method resulting Catalyst Production cost in the industrial realization process is higher, and gained catalyst spherical degree is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of ingredient of solid catalyst that is used for vinyl polymerization, and the Preparation of catalysts method that contains this ingredient of solid catalyst, this method is by metal magnesium powder continuous uninterrupted synthesizing ethylene polymerization solid catalyst, have technology simple, be convenient to operation, the industrial equipment investment is low, production cost is low, quality product characteristics such as control easily.This catalyst component has catalyst activity and tap density is higher, generates characteristics such as the polyethylene powder segmentation is few, is suitable for the slurry polymerization or the vapour phase polymerization of ethene, is specially adapted to the gas-phase fluidized bed polymerization process of catalyzer with the ethene of slurries form charging.
A kind of titanium-containing catalyst component that is used for vinyl polymerization of the present invention, it is to obtain by following three successive synthesis steps: (1) is at halogen or contain in the presence of the compound of halogen element, uses MAGNESIUM METAL and alcohol preparation to contain the magnesium solids; (2) this magniferous solids of mixture process that re-uses one or more organometallic compounds or one or more organometallic compounds and one or more electron donors obtains magniferous support of the catalyst; (3) in the presence of inert diluent, use this magniferous support of the catalyst of compound treatment of one or more transition metals Ti to obtain catalyst component.
Described alcohol is that carbonatoms is 1～6 low-carbon alcohol, preferred alcohol.Water-content generally is controlled at below the 2000ppm in the alcohol, and preferably water content is controlled at below the 200ppm.
Described MAGNESIUM METAL is the magnesium powder of activated carbon content＞98%, and magnesium powder footpath is below 350 microns, preferably between 80～350 microns.Described halogen is chlorine, bromine, iodine, preferred iodine.In containing the compound of halogen element, described halogen atom is chlorine, bromine, iodine.In containing the compound of halogen element, the metallic compound that wherein contains halogen element is preferred, as MgCl
2, MgI
2, Mg (OEt) Cl, Mg (OEt) I, MgBr
2, CaCl
2, NaCl, KBr etc., preferred MgCl
2
The general formula of described organometallic compound is AlR '
cX '
dH
e, R ' is C in the formula
1～C
14Saturated hydrocarbyl, X ' is a halogen atom, c is 1～3 integer, d is 0～2 integer, e is 0 or 1, c+d+e=3; Specifically can select AlMe for use
3, AlEt
3, AlEt
2H, AlEt
2Cl, AlEtCl
2, Al (n-Bu)
3, Al (i-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3In one or more.With AlMe
3Or AlEt
3For excellent.
Described electron donor compound is selected from carboxylicesters, aliphatic ether, cyclic aliphatic ether or aliphatic ketone, is preferably C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8The alkyl ester of aromatic carboxylic acid, C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers, C
3～C
6Saturated fatty ketone.Be specially methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone and methyl iso-butyl ketone (MIBK) etc., this class electron donor can use separately or several being used.Preferred tetrahydrofuran (THF).
The compound of transition metals Ti is that titanium tetrahalide or general formula are TiX
n(OR)
4-nCompound, 0≤n≤3 wherein, X is a halogen, R is C
1～C
10Alkyl.Comprise in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, trichlorine methoxyl group titanium, trichlorine ethanolato-titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide, dichloro dimethoxy titanium, dichloro diethoxy titanium, dichloro dipropoxy titanium, dichloro two titanium n-butoxide, a chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine tripropoxy titanium or a chlorine three titanium n-butoxide one or more, wherein with the titanium tetrachloride best results.
The preparation method of the titanium-containing catalyst component that is used for vinyl polymerization of the present invention is as follows:
1) earlier with alcohol and metal magnesium powder at halogen or contain reaction generation magnesium compound in the presence of the compound of halogen element, alcohol is 3.5～4.7 with the mol ratio of magnesium powder, halogen or contain the compound of halogen element and the mol ratio of magnesium powder is 0.002～0.01, above three's contact temperature is 30 ℃～90 ℃, preferred 40 ℃～80 ℃.
2) when reaction solution viscosity sharply rises, add alcohol, or the mixed solution of inert organic solvents or alcohol and inert organic solvents, the mol ratio of amount of adding and magnesium powder is 2～7; After reacting completely, directly remove for 1～5 time promptly to get behind the excessive alcohol with the inert organic solvents washing and contain the magnesium solids, the temperature of adding liquid is 30 ℃～90 ℃, preferred 40 ℃～80 ℃.
3) with inert organic solvents the magnesium solids that contains of gained is configured to suspension, uses the magniferous solids of mixture process of one or more organometallic compounds or one or more organometallic compounds and one or more electron donors to obtain support of the catalyst; In every mole of magnesium compound, the amount of organometallic compound is 0.01～1 mole, and the amount of electron donor is 0.1～1 mole;
4) use the compound of one or more transition metals Ti to handle support of the catalyst in the presence of inert diluent, after washing, drying, get ingredient of solid catalyst, the titanium compound consumption is 0.005～0.5 mole.
In step 1), alcohol can be earlier contacts with halogen or the compound that contains halogen element, and then contacts with metal magnesium powder; Alcohol and halogen or contain the compound of halogen element and metal magnesium powder can add reactor separately or the three once adds reactor simultaneously, also can adopt mode that in batches adds or the mode that adds continuously, wherein preferred mode that in batches adds or the mode that adds continuously.
In step 2) in, described inert organic solvents is at room temperature being liquid aromatic hydrocarbons or alkane, as pentane, hexane, heptane, octane, decane, benzene, toluene or dimethylbenzene, aromatic hydrocarbons and alkane can use separately also can mix use.When containing the magnesium solids with the inert organic solvents washing, the mol ratio of the consumption of the consumption of inert organic solvents and magnesium powder is 3～20, preferred 5～10; Wash temperature is 10 ℃～150 ℃, preferred 20 ℃～80 ℃.
In step 3), treatment temp is 0 ℃～60 ℃ during with organometallic compound or with the magniferous solids of mixture process of organometallic compound and electron donor, preferred 40 ℃～60 ℃.Be advisable with about 0.5 hour in treatment time 10min～1 hour.
In step 4), when handling support of the catalyst with the compound of transition metals Ti in the presence of inert diluent, treatment temp is 40 ℃～80 ℃, preferred 50 ℃～60 ℃.In 1～3 hour treatment time, with about 2 hours, be advisable.
In the resulting catalyst component of the present invention, titanium: 1～10%, aluminium: 0.1～2%, electron donor: 1～60%, (weight content).
The present invention relates to a kind of ethylene polymerization catalysts that is used for, it comprises the reaction product of following component:
(1) the titanium-containing catalyst component that is used for vinyl polymerization of the present invention;
(2) alkylaluminium cpd;
The general formula of wherein used alkylaluminium cpd is AlR " 3, R " be the alkyl of C1～C8 identical or inequality, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls to mix and use preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc.Ratio between catalyst component and the alkylaluminium cpd, in every gram catalyst component, the alkylaluminium cpd consumption is: 0.1mmol～10mmol is preferably 0.5mmol～3mmol.
The above-mentioned ethylene polymerization catalysts that is used for is closed or ethene and C at ethylene homo
3～C
8Alpha-olefin copolymer can both well be used in closing.` wherein alpha-olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation particularly gas-phase fluidized-bed condensation technology.Simultaneously, 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, and charging is even, stable operation.
The invention provides a kind of ingredient of solid catalyst that is used for vinyl polymerization or copolymerization, and the Preparation of catalysts method that contains this ingredient of solid catalyst, this method have technology simple, be convenient to operation, the industrial equipment investment is low, production cost is low, quality product characteristics such as control easily.This catalyst component has catalyst activity and tap density is higher, generates characteristics such as the polyethylene powder segmentation is few, is suitable for the slurry polymerization or the vapour phase polymerization of ethene, is specially adapted to the gas-phase fluidized bed polymerization process of catalyzer with the ethene of slurries form charging.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
1, melting index (MI) is to measure according to ASTM D1238-99;
2, flow index (FI) is to measure according to ASTM D1238-99;
3, melt flow ratio (MFR) is a melting index and the ratio of flow index;
4, density polymer is to measure according to GB-1033;
5, size-grade distribution: according to method, with " Malvern Instr.2600 " tester based on the optical diffraction principle of one-wavelength laser.
Embodiment 1:
1, the preparation of catalyst component
In the four-hole boiling flask of agitator is housed, install back flow condenser and on reflux exchanger, connect accumulation moulded coal gas meter, the entire reaction device adds dehydrated alcohol 70.8ml in container after fully replacing through nitrogen, and iodine 1.26g makes it dissolving.Add the 6g MAGNESIUM METAL inside, under agitation condition, be warming up to the alcoholic acid reflux temperature, added dehydrated alcohol 47ml, magnesium powder 6g, totally 3 times every 10 minutes from the beginning that refluxes.About 1～2 hour liquid viscosity begins rapid rising (can calculate reactivity by the amount of the hydrogen of generation this moment is about 85%) after adding is finished for the third time, at this moment in reactive system, add ethanol 259ml again, continue reaction till the reaction termination no longer produces hydrogen, about about 6 hours of entire reaction time.Obtain containing the magnesium solids three times with 150ml hexane wash solids.
With hexane 120mL, and the 1.3 moles of AlEt that contain magnesium solids 6g and the other preparation of 27mL that prepare above
3The mixture of/THF adds a 350mL down at 0 ℃ to be furnished with in the glass reactor of agitator, is incubated 30 minutes with the mixture heating up intensification and at 50 ℃ under agitation condition.Stop then stirring, remove liquid with the method for siphon.Begin repetition from room temperature under the same conditions and use AlEt twice
3/ THF mixture process process.Obtain the support of the catalyst component three times with hexane wash.Further use 0.4mlTiCl 60 ℃ of 100mL hexanes and under stirring at last
4(being diluted in the 20ml hexane) handled this support of the catalyst 2 hours.
With 120ml hexane wash solids, obtain solids containing titanium catalyst component 7.1 grams through evaporation drying, wherein Ti 1.8%, Mg16.8%, THF14.2% (weight).
2, polymerization
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, be 1mmol/ml triethyl aluminum-hexane solution 2ml with the syringe implantation concentration, add a certain amount of above-mentioned solids containing titanium catalyst component under stirring again, replenish the hexane total amount and be about 1 liter.
Heat up and successively feed hydrogen and ethene in the reinforced back that finishes, and wherein 2.8 * 10
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 dry, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 2:
Method for preparing catalyst is with embodiment 1.
The polymerization appreciation condition: 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 is 1mmol/ml triethyl aluminum-hexane solution 2ml, add a certain amount of solids containing titanium catalyst component under stirring again, replenish the hexane total amount and be about 1 liter.
Heat up and successively feed hydrogen and ethene in the reinforced back that finishes, and wherein 6.8 * 10
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 dry, obtains polyethylene powder, the results are shown in Table 1.
Embodiment 3:
Contain magnesium solids preparation method with embodiment 1.
6 grams are contained the magnesium solids to join in another reactor, add the 120ml hexane, drip 2mlTHF under 0 ℃ the condition stirring 320rpm, temperature, be under 10 ℃ the condition in mixing speed 320rpm, temperature, reaction half an hour is with 120ml hexane wash solids.Add the 120ml hexane, drip 2mlAlEt under 0 ℃ the condition stirring 320rpm, temperature
2Cl, wherein AlEt
2The concentration of Cl is 14wt%, is being under 10 ℃ the condition in mixing speed 320rpm, temperature, and reaction half an hour is with 120ml hexane wash solids.Further use 0.4ml TiCl 60 ℃ of 100mL hexanes and under stirring at last
4(being diluted in the 20ml hexane) handled this support of the catalyst 2 hours.
Obtain particulate state solids containing titanium catalyst component 7.74 gram, wherein Ti 1.61%, tetrahydrofuran (THF)s 21.4% (weight) through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 4:
Contain magnesium solids preparation method with embodiment 1.
6 gram solidss are joined in another reactor, add the 120ml hexane, drip 2mlAlEt under 0 ℃ the condition stirring 320rpm, temperature
2Cl, wherein AlEt
2The concentration of Cl is 14wt%, is under 10 ℃ the condition in mixing speed 320rpm, temperature, and reaction half an hour is with 120ml hexane wash solids.Adding the 120ml hexane, drip 2mlTHF under 0 ℃ the condition stirring 320rpm, temperature, is being under 10 ℃ the condition in mixing speed 320rpm, temperature, and reaction half an hour is with 120ml hexane wash solids.Further use 0.4ml TiCl 60 ℃ of 100mL hexanes and under stirring at last
4(being diluted in the 20ml hexane) handled this support of the catalyst 2 hours.
Obtain particulate state solids containing titanium catalyst component 7.27 gram, wherein Ti 1.87%, tetrahydrofuran (THF)s 18.9% (weight) through evaporation drying.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 5:
The Preparation of catalysts method only changes added 1.26 gram iodine into 2.5 gram magnesium chlorides substantially with embodiment 1 when preparation contains the magnesium solids.Particulate state solids containing titanium catalyst component 8.0 gram, wherein Ti 1.46%, the THF20.3% (weight) that finally obtain.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 6:
The Preparation of catalysts method is substantially with embodiment 1, only added ethanol changed into methyl alcohol, ethanol, Virahol volume ratio when preparation contains the magnesium solids and be 1: 7.5: 1.5 alcohol mixture solution.Particulate state solids containing titanium catalyst component 7.2 gram, wherein Ti 1.79%, the THF21.4% (weight) that finally obtain.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Embodiment 7:
Contain magnesium solids preparation method with embodiment 1.
6 gram solidss are joined in another reactor, add the 120ml hexane, drip 2mlAlEt under 0 ℃ the condition stirring 320rpm, temperature
2Cl, wherein AlEt
2The concentration of Cl is 28wt%, in mixing speed 320rpm, temperature is under 10 ℃ the condition, to react 2 hours, with 120ml hexane wash solids.Further use 0.4ml TiCl 60 ℃ of 100mL hexanes and under stirring at last
4(being diluted in the 20ml hexane) handled this support of the catalyst 2 hours.Obtain particulate state solids containing titanium catalyst component 6.77 grams through evaporation drying, wherein Ti 2.17%, THF19.4% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Comparative example 1:
Prepare catalyst component according to the disclosed method of Chinese patent ZL02120861.1:
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 is separated out solids, the elimination mother liquor gradually in temperature-rise period, 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:
According to US4,302,565, US4,379,759 and disclosed composition of 93117628.X and content, adopt the method for pickling process to prepare catalyst component:
The activation of silica gel: 948# spherical silica gel (U.S. Grace company) is activated 4 hours at 600 ℃,
In reactor, add 100mlTHF, titanous chloride 0.74g, magnesium chloride 1.13g, be warming up to 70 ℃, reacted 1 hour, standby as masterbatch.Add iso-pentane 60ml to another reactor, add silica gel 10g, triethyl aluminum 4.3ml after the above-mentioned activation, normal-temperature reaction 30min, iso-pentane in 55 ℃ of following still kettles content of aluminium to the material in reactor is 1.65%, then ready masterbatch is transferred in this reactor, being warming up to refluxes produces constant temperature 1 hour.THF in distillation reactor material THF content to the still is 12.6%, adds iso-pentane 86ml, aluminium diethyl monochloride 5.3ml normal temperature reaction 30min down, adds tri-n-hexyl aluminum 3.3ml normal temperature reaction 30min down.Obtain particulate solid through vacuum-drying.Contain Ti 0.78%, Mg 1.58%, tetrahydrofuran (THF) 10.9% (weight) in the final catalyst component.
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
Comparative example 3:
Prepare catalyst component according to Chinese patent 200710163321.3 disclosed methods:
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml, add 10g magnesium ethylate (tap density 0.279/cm3) and the prepare suspension of 80ml toluene, maintain 0 ℃ then and drip titanium tetrachloride 20ml.After dropwising system was warming up to 110 ℃ of constant temperature 2 hours, then that the liquid press filtration is clean, elimination liquid, the solid of gained obtains titaniferous solids A with toluene and twice washing of hexane after drying.
10 gram solids A are joined in another reactor, add 100ml iso-pentane, 0.4 gram titanous chloride and 30 milliliters of tetrahydrofuran (THF)s, normal temperature reacted 1 hour down, filter solution, add the 100ml iso-pentane again, the aluminium diethyl monochloride solution reaction of 4 ml volumes concentration 26.43% 1 hour, evaporation drying obtain particulate solid thing component 12.6 grams, wherein contain Ti 1.98%, Mg 13.51%, tetrahydrofuran (THF) 46.8% (weight).
The polymerization appreciation condition the results are shown in Table 1 with embodiment 1.
The polymerization result of table 1: embodiment and comparative example
Claims (12)
1. a titanium-containing catalyst component that is used for vinyl polymerization is characterized in that, it is to obtain by following three successive synthesis steps: (1) is at halogen or contain in the presence of the compound of halogen element, uses MAGNESIUM METAL and alcohol preparation to contain the magnesium solids; (2) this magniferous solids of mixture process that re-uses one or more organometallic compounds or one or more organometallic compounds and one or more electron donors obtains magniferous support of the catalyst; (3) in the presence of inert organic solvents, use this magniferous support of the catalyst of compound treatment of one or more transition metals Ti to obtain catalyst component;
Described alcohol is that carbonatoms is 1～6 low-carbon alcohol; The general formula of described organometallic compound is AlR '
cX '
dH
e, R ' is C in the formula
1～C
14Saturated hydrocarbyl, X ' is a halogen atom, c is 1～3 integer, d is 0～2 integer, e is 0 or 1, c+d+e=3; Described electron donor compound is selected from carboxylicesters, aliphatic ether, cyclic aliphatic ether or aliphatic ketone; The compound of transition metals Ti is that titanium tetrahalide or general formula are TiX
n(OR)
4-nCompound, 0≤n≤3 wherein, X is a halogen, R is C
1～C
10Alkyl.
2. the titanium-containing catalyst component that is used for vinyl polymerization according to claim 1 is characterized in that the compound of described transition metals Ti is a titanium tetrachloride.
3. the preparation method of the described titanium-containing catalyst component that is used for vinyl polymerization of one of claim 1～2 is as follows:
1) earlier with alcohol and metal magnesium powder at halogen or contain reaction generation magnesium compound in the presence of the compound of halogen element, alcohol is 3.5～4.7 with the mol ratio of magnesium powder, halogen or contain the compound of halogen element and the mol ratio of magnesium powder is 0.002～0.01, above three's contact temperature is 30 ℃～90 ℃;
2) when reaction solution viscosity sharply rises, add alcohol or inert organic solvents, perhaps add the mixed solution of alcohol and inert organic solvents, the mol ratio of amount of adding and magnesium powder is 2～7; After reacting completely, directly with inert organic solvents washing 1～5 time, remove excessive pure promptly getting later and contain the magnesium solids, the temperature of adding liquid is 30 ℃～90 ℃;
3) with inert organic solvents the magnesium solids that contains of gained is mixed with suspension, uses the magniferous solids of mixture process of one or more organometallic compounds or one or more organometallic compounds and one or more electron donors to obtain support of the catalyst; In every mole of magnesium compound, the amount of organometallic compound is 0.01～1 mole, and the amount of electron donor is 0.1～1 mole;
4) in the presence of inert organic solvents, use the compound treatment support of the catalyst of one or more transition metals Ti, after washing, drying, get ingredient of solid catalyst, in every mole of magnesium compound, the titanium compound consumption is 0.005～0.5 mole.
4. the preparation method who is used for the titanium-containing catalyst component of vinyl polymerization according to claim 3, described alcohol is that carbonatoms is 1～6 low-carbon alcohol, MAGNESIUM METAL is the magnesium powder of activated carbon content＞98%, and magnesium powder footpath is below 350 microns, and described halogen is an iodine.
5. the preparation method who is used for the titanium-containing catalyst component of vinyl polymerization according to claim 4, described alcohol is ethanol, magnesium powder footpath is between 80～350 microns.
6. the preparation method who is used for the titanium-containing catalyst component of vinyl polymerization according to claim 3 is characterized in that described organometallic compound is selected from AlMe
3, AlEt
3, AlEt
2H, AlEt
2Cl, AlEtCl
2, Al (n-Bu)
3, Al (i-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3In one or more.
7. the preparation method who is used for the titanium-containing catalyst component of vinyl polymerization according to claim 6 is characterized in that described organometallic compound is selected from AlMe
3Or AlEt
3
8. the preparation method who is used for the titanium-containing catalyst component of vinyl polymerization according to claim 3, described electron donor compound is a tetrahydrofuran (THF).
9. the preparation method who is used for the titanium-containing catalyst component of vinyl polymerization according to claim 1 is characterized in that described inert organic solvents is pentane, hexane, heptane, octane, decane, benzene, toluene or dimethylbenzene.
10. one kind is used for ethylene polymerization catalysts, it is characterized in that, comprises following component:
(1) the described titanium-containing catalyst component that is used for vinyl polymerization of one of claim 1～2;
(2) alkylaluminium cpd, its general formula are AlR " 3, R wherein " be identical or different C
1～C
8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls to mix use, the ratio between catalyst component and the alkylaluminium cpd, in every gram catalyst component, the alkylaluminium cpd consumption is: 0.1mmol～10mmol.
11. the described ethylene polymerization catalysts that is used for of claim 10 is closed or ethene and C at ethylene homo
3～C
8The application of alpha-olefin copolymer in closing.`
12. the described application that is used for ethylene polymerization catalysts at ethene slurry polymerization or gas-phase polymerization process of claim 10.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807634A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst of catalyst component |
| CN102952222A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Ultra-high molecular weight polyethylene resin and preparation method thereof |
| WO2013093930A1 (en) * | 2011-12-21 | 2013-06-27 | Reliance Industries Limited | A high surface area silicon derivative free magnesium- titanium catalyst system for ethylene polymerization and process of preparation thereof |
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| US4464518A (en) * | 1981-06-24 | 1984-08-07 | Nissan Chemical Industries, Ltd. | Process for the polymerization or copolymerization of ethylene |
| JP3204688B2 (en) * | 1991-06-25 | 2001-09-04 | 出光石油化学株式会社 | Method for producing ethylene polymer |
| FR2691970B1 (en) * | 1992-06-04 | 1995-08-25 | Bp Chemicals Snc | PROCESS FOR THE PREPARATION OF A POLYMERIZATION CATALYST. |
| CN1281636C (en) * | 2003-11-28 | 2006-10-25 | 中国石油化工股份有限公司 | Preparation method for solid catalyst component for olefin polymerization |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102807634A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst of catalyst component |
| CN102807634B (en) * | 2011-06-03 | 2014-04-02 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst of catalyst component |
| CN102952222A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Ultra-high molecular weight polyethylene resin and preparation method thereof |
| CN102952222B (en) * | 2011-08-30 | 2015-02-25 | 中国石油化工股份有限公司 | Ultra-high molecular weight polyethylene resin and preparation method thereof |
| WO2013093930A1 (en) * | 2011-12-21 | 2013-06-27 | Reliance Industries Limited | A high surface area silicon derivative free magnesium- titanium catalyst system for ethylene polymerization and process of preparation thereof |
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