CN104277160B - A kind of catalyst for producing Narrow Molecular Weight Distribution polyethylene - Google Patents
A kind of catalyst for producing Narrow Molecular Weight Distribution polyethylene Download PDFInfo
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Abstract
The present invention relates to a kind of catalytic component for producing Narrow Molecular Weight Distribution polyethylene, Catalysts and its preparation method, this catalytic component comprises magnesium halide/inorganic oxide carrier, alcohol compound, the product of titanium compound and halogen ether compounds.This catalyst has higher activity for vinyl polymerization or combined polymerization, it is possible to produce the polyvinyl resin that molecular weight distribution is narrower.
Description
Technical field
The present invention relates to a kind of for preparing the Ziegler-Natta catalyst component of Narrow Molecular Weight Distribution polyethylene, catalyst, its preparation method, and the application in olefinic polymerization.
Background technology
Molecular weight distribution (MWD) is an important indicator of resin, and serviceability and the processing characteristics of product are had certain impact by it.For improving the serviceability of polyethylene, expansive approach field, people constantly carry out the exploitation of the polyethylene new product of different molecular weight distribution, to meet the different field demand to polyvinyl resin.
There is the deformation in goods of the ethene polymers of Narrow Molecular Weight Distribution and contraction problem reduces, be therefore more suitable for film and injection moulding.
Metallocene catalyst is a kind of single site catalysts, it is possible to producing the polyethylene of Narrow Molecular Weight Distribution, its molecular weight distribution is 2.2-2.8.Owing to its oligomer substantially reduces, decrease the abnormal flavour produced in process of resin process, and material property significantly increases.But Methods for Immobilization of Metallocene Catalysts cost is costly, and the catalyst activity after load is on the low side, limits its range of application to a certain extent.
Compared with metallocene catalyst, the molecular weight distribution of polyethylene prepared by Ziegler-Natta catalyst is wider, molecular weight distribution is MWD > 7.2, and it has, and cost is low, catalyst activity advantages of higher, therefore prepares highly active supported Ziegler-Natta catalyst and obtain having the polyethylene of the Narrow Molecular Weight Distribution of elite clone performance and have a good application prospect.After deliberation by introducing suitable catalytic component, reducing the molecular weight distribution of polyvinyl resin prepared by existing Ziegler-Natta catalyst, namely molecular weight distribution is less than 7.2, is the effective way improved and improve Ziegler-Natta catalyst.
EP0373999 discloses a kind of catalyst for preparing ethylene (being total to) polymer with Narrow Molecular Weight Distribution, the ingredient of solid catalyst that this catalyst is made up of the titanium compound being carried on magnesium chloride, alkyl aluminum compound and the electronic donor compound capable in monoether.This catalyst by preparing the polymer with narrow MWD as the o-benzene butyl phthalate ester of internal electron donor, but the activity of this catalyst is quite weak in the industrial production.
CN101589068A discloses a kind of catalytic component for olefinic polyreaction, is (RO) (CR including Ti, Mg, halogen and formula1R2)n(OR) α, the ω represented-diether compounds, wherein n is the integer of 5-10.The catalyst prepared with this catalytic component can produce the polyethylene of narrower MWD, but catalyst prepared by its preferred 1,5-dimethoxy pentane is not enough in activity, and production capacity is relatively low.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of for producing the catalytic component of Narrow Molecular Weight Distribution polyethylene, Catalysts and its preparation method.
An object of the present invention is to provide a kind of catalytic component for producing Narrow Molecular Weight Distribution polyethylene, it is characterised in that comprise magnesium halide/inorganic oxide carrier, alcohol compound, the product of titanium compound and halogen ether compounds.
The detailed description of the present invention:
Described titanium compound is the Ti salt of tetravalence or trivalent, such as TiCl4、TiCl3、Ti(OH)4、Ti(OR)4Deng.
Described halogen ether compounds structure is as follows:
X-CHR1-OR2, R1It is hydrogen or carbon number is the alkyl of 1-4, R2Be carbon number being the alkyl of 1-4, X is halogen.It is specially chloro-3 methoxy propanes of 1-, chloro-3 ethoxy propanes of 1-, chloro-3 methyl butyl ethers of 1-, bromo-3 methoxy propanes of 1-, bromo-3 ethoxy butanes of 1-etc..Halogen ether compounds in the present invention enables to the molecular weight of polyethylene distribution narrow of preparation.
Described magnesium halide/inorganic oxide carrier is magnesium chloride/silica supports, and the preparation of this carrier is according to the preparation of magnesium chloride/silica-gel carrier in Chinese patent application 200710176589, and concrete grammar is as follows:
By anhydrous magnesium chloride carrier under noble gas such as nitrogen protection; join in reactor; add a certain amount of solvent; adding silica gel Deng anhydrous magnesium chloride after dissolving, after stirring, heating steams solvent; and make the solid that obtains keep good mobility; then heat evacuation, remove solvent, obtain magnesium chloride/silica-gel carrier.
Above-mentioned solvent can be oxolane, it is possible to be alcohols solvent or the mixed alcohol solvents such as ethanol, methanol, propanol, butanol, 2-Ethylhexyl Alcohol, ethylene glycol, glycerol, it is possible to be water, it is also possible to the mixed solvent being made up of above several solvents.
Silica gel is carrier conventional in polyolefin catalyst preparation, and it mainly comprises as silicon dioxide, and particle diameter is 0.1 μm～120 μm, and general specific surface area is > 100m2/ g.With front 50～800 DEG C of roasting temperatures 1～24 hour.
Above-mentioned magnesium chloride/silica-gel carrier has good particle shape and mobility, is completely removed by solvent as far as possible in preparation process, it is ensured that in magnesium chloride/silica-gel carrier, weight of solvent content is not higher than 0.1%.
In above-mentioned magnesium chloride/silica-gel carrier, the weight content of magnesium chloride is 0.1%～60%, it is preferred to 0.5%～45%.
The preparation method that it is a further object to provide a kind of catalytic component for producing Narrow Molecular Weight Distribution polyethylene, by the above-mentioned magnesium chloride/silica-gel carrier prepared, under noble gas such as nitrogen protection, join and varsol is made serosity, heat to 50～90 DEG C of stirring reactions 10～90 minutes, it is proportionally added into quantitative alcohol compound, stirring reaction 0.5 hour, pump the supernatant, varsol is rejoined in reaction bulb, quantitative Ti compound it is proportionally added under stirring, heat to 50～90 DEG C of stirring reactions 1～3 hour, drop to room temperature, it is proportionally added into quantitative halogen ether compounds, it is raised to 30～70 DEG C to react 1～4 hour, then the supernatant is pumped, solids varsol wash 3 times colourless to upper strata mother solution, dry up in flow regime with nitrogen in 50 DEG C, obtain solid catalyst.
Above-mentioned varsol often selects heptane, hexane, pentane, iso-butane etc..
Alcohol compound is R-CH2(OH), R is hydrogen or carbon number is the alkyl of 2～8, and particular compound is ethanol, normal propyl alcohol, n-butyl alcohol, 2-Ethylhexyl Alcohol, isopropanol, isobutanol etc..
Ti compound is the Ti salt of tetravalence or trivalent, such as TiCl4、TiCl3、Ti(OR)4Deng.
Halogen ether compounds in said method is 0.1～10 with the molar ratio of magnesium chloride in carrier, it is preferable that 0.2～5.
Alcohol compound in said method is 0.1～10 with the molar ratio of magnesium chloride in carrier, it is preferable that 0.3～3.
Ti compound in said method is 0.1～10 with the molar ratio of magnesium chloride in carrier, it is preferable that 0.5～8.
Present invention also offers the catalyst of the copolymerization of a kind of equal polyreaction for ethylene or ethylene and other alpha-olefin, alpha-olefin therein includes propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, styrene, methyl styrene etc.；The catalytic component that this catalyst comprises (1) above-mentioned present invention and (2) formula are AlRnX3-nThe product of organo-aluminum compound, in formula, R can be hydrogen, carbon number be the alkyl of 1～20, particularly alkyl, aralkyl, aryl；X is halogen, particularly chlorine and bromine；N is the integer of 0 < n≤3.Particular compound such as organo-aluminum compounds such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminum, ethyl aluminum dichlorides, wherein preferably triethyl aluminum, triisobutyl aluminium.Wherein in component (2), aluminum is 5～500 with the mol ratio of titanium in component (1), it is preferable that 20～200.
Ziegler-Natta catalyst of the present invention is usable on different polymerizations, such as gas-phase polymerization and slurry polymerization etc..
Ziegler-Natta catalyst of the present invention can be used for polymerization or the copolymerization of alkene, being particularly well-suited to the copolymerization of ethylene homo conjunction or ethylene and other alpha-olefin, wherein alpha-olefin adopts propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc..
Wherein it is polymerized the solvent used selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.A kind of in preferred hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, it is most preferred that for a kind of in hexane, pentane, toluene, heptane or their mixture.
Polymerization temperature is 30 DEG C-100 DEG C, it is preferred to 60 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, it is preferable that 0.1-2.0MPa.
Relative to prior art, the catalyst for producing Narrow Molecular Weight Distribution polyethylene of the present invention has the advantage that
1, Ziegler-Natta catalyst component of the present invention, comprises Ti compound, MgCl2, silica gel and halogen ether compounds, for vinyl polymerization, it is possible to substantially reduce the molecular weight distribution of polyethylene；
2, Ziegler-Natta catalyst of the present invention has high ethylene copolymerization catalysis activity；
3, the resin powder that Ziegler-Natta catalyst of the present invention obtains for olefinic polymerization has good particle shape, and bulk density is high, it is possible to suitable in slurry process and vapor phase method polymerization technique.
Detailed description of the invention
Method of testing:
1, Ti content: record by ICP method, the P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, polymerization activity=polymer weight/catalyst weight
3, molecular weight of polyethylene distribution MI21.6/MI2.16Represent, MI2.16For the melt index under load 2.16 kilograms, MI21.6For the melt index under load 21.6 kilograms, method test, instrument selection Germany GOTTFERTMI-2 type fusion index instrument described in employing GB GB/T3682-2000.
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
1) preparation (preparing according to Chinese patent application 200710176589 method) of magnesium chloride/silica-gel carrier
Under nitrogen protection, in glass reactor, under room temperature, add 1.04 grams of anhydrous magnesium chlorides; it is subsequently adding 700 milliliters of dried oxolanes, after starting stirring, by 2.42 grams of silica gel (GRACESylopol2485; under nitrogen; 150 DEG C of roastings 2.5 hours, are warming up to 300 DEG C of roastings 2 hours, then 600 DEG C of roastings 5 hours) join in reactor; it is warming up to 65 DEG C; stirring and dissolving 2 hours, then evaporation of solvent at 80 DEG C, obtains white solid powder.By white solid powder vacuum drying 2 hours at 100 DEG C, then at 300 DEG C vacuum drying 10 hours, obtain the pressed powder 3.40 grams of good fluidity, through gas chromatographic analysis, fail oxolane to be detected.
2), the preparation of catalyst A
0.686 gram of (2.16mmolMgCl of magnesium chloride/silica-gel carrier that said method is prepared2), under noble gas such as nitrogen protection, join in 30 milliliters of hexanes, under stirring; heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.20 milliliter, stirring reaction 0.5 hour; pumping the supernatant, 30 milliliters of hexanes again in reaction bulb, stirring is lower adds 1.0 milliliters of TiCl4Heat to 70 DEG C of stirring reactions 1 hour, drop to room temperature, add 0.06 milliliter of chloro-3 methoxy propane of (0.54mmol) 1-, be warmed up to 50.0 DEG C react 2 hours, then pump the supernatant, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the A catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 4.35wt%.
Embodiment 2
The preparation of catalyst B
With magnesium chloride/silica-gel carrier 0.717 gram (2.26mmo1) that preparation method in embodiment 1 obtains; under noble gas such as nitrogen protection; join in 30 milliliters of hexanes; under stirring, heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.20 milliliter; stirring reaction 0.5 hour; pumping the supernatant, rejoin 30 milliliters of hexanes in reaction bulb, stirring is lower adds 1.0 milliliters of TiCl4Heat to 70 DEG C of stirring reactions 1 hour, drop to room temperature, add 0.13 milliliter of chloro-3 methoxy propane of (1.13mmol) 1-, be raised to 50.0 DEG C react 2 hours, then pump the supernatant, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the B catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 3.77wt%.
Embodiment 3
The preparation of catalyst C
With magnesium chloride/silica-gel carrier 0.737 gram (2.33mmol) that preparation method in embodiment 1 obtains; under noble gas such as nitrogen protection; join in 30 milliliters of hexanes; under stirring, heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.21 milliliter; stirring reaction 0.5 hour; pumping the supernatant, 30 milliliters of hexanes again in reaction bulb, stirring is lower adds 1.11 milliliters of TiCl4Heat to 70 DEG C of stirring reactions 1 hour, drop to room temperature, add 0.26 milliliter of chloro-3 methoxy propane of (2.33mmol) 1-, be raised to 50.0 DEG C react 2 hours, then pump the supernatant, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the C catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 4.1wt%.
Embodiment 4
The preparation of catalyst D
Use magnesium chloride/silica-gel carrier 0.701 gram (2.21mmol) that in embodiment 1, the preparation method of magnesium chloride/silica-gel carrier obtains; under noble gas such as nitrogen protection; join in 30 milliliters of hexanes; under stirring, heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.20 milliliter; stirring reaction 0.5 hour; pumping the supernatant, 30 milliliters of hexanes again in reaction bulb, stirring is lower adds 1.08 milliliters of TiCl4Heat to 70 DEG C of stirring reactions 1 hour, drop to room temperature, add 0.48 milliliter of chloro-3 methoxy propane of (4.42mmol) 1-, be raised to 50.0 DEG C react 2 hours, then pump the supernatant, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the D catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 4.37wt%.
Comparative example 1
The preparation of catalyst E
Use magnesium chloride/silica-gel carrier 0.701 gram (2.21mmol) that in embodiment 1, the preparation method of magnesium chloride/silica-gel carrier obtains; under noble gas such as nitrogen protection; join in 30 milliliters of hexanes; under stirring, heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.20 milliliter; stirring reaction 0.5 hour; pumping the supernatant, 30 milliliters of hexanes again in reaction bulb, stirring is lower adds 1.08 milliliters of TiCl4Heat to 70 DEG C of stirring reactions 1 hour, drop to room temperature, add 0.18 milliliter (1.10mmol) 1,5-dimethoxy pentane, be raised to 50.0 DEG C and react 2 hours, then the supernatant is pumped, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the D catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 5.99%wt.
Comparative example 2
The preparation of catalyst F
Use magnesium chloride/silica-gel carrier 0.701 gram (2.21mmol) that in embodiment 1, the preparation method of magnesium chloride/silica-gel carrier obtains; under noble gas such as nitrogen protection; join in 30 milliliters of hexanes; under stirring, heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.20 milliliter; stirring reaction 0.5 hour; pumping the supernatant, 30 milliliters of hexanes again in reaction bulb, stirring is lower adds 1.08 milliliters of TiCl4Heat to 70 DEG C of stirring reactions 1 hour, drop to room temperature, add 0.37 milliliter (2.21mmol) 1,5-dimethoxy pentane, be raised to 50.0 DEG C and react 2 hours, then the supernatant is pumped, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the D catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 9.6%wt.
Comparative example 3
The preparation of catalyst G
Use magnesium chloride/silica-gel carrier 0.713 gram (2.25mmol) that in embodiment 1, the preparation method of magnesium chloride/silica-gel carrier obtains; under noble gas such as nitrogen protection; join in 30 milliliters of hexanes; under stirring, heat to 70 DEG C of reactions 0.5 hour, be subsequently adding the n-butyl alcohol of 0.20 milliliter; stirring reaction 0.5 hour; pumping the supernatant, 30 milliliters of hexanes again in reaction bulb, stirring is lower adds 1.06 milliliters of TiCl4, heat to 70 DEG C of stirring reactions 1 hour, then pump the supernatant, solids hexane solvent wash 3 times colourless to upper strata mother solution, dry up in flow regime, obtaining the G catalyst of solid with nitrogen in 50 DEG C.By analysis, Ti content is 3.30wt%.
Embodiment 5～13 vinyl polymerization is tested
Vinyl polymerization experimentation is as follows:
In the rustless steel polymerization autoclave of 2 liters, three times are respectively replaced with nitrogen and hydrogen, it is subsequently adding 1000 milliliters of hexane solvents, addition along with hexane, (if copolymerization experiments, 30 milliliters of hexenes need to be added at this moment,) triethyl aluminum (TEA) hexane solution of 1 milliliter of 1 mol/L is added, it is subsequently added into the Ziegler-Natta catalyst 20-30 milligram that above-described embodiment prepares, is warming up to 70 DEG C, add hydrogen 0.28MPa, temperature rises to 80 DEG C, add ethylene to 0.73MPa, and maintain pressure at 0.73MPa with ethylene, react 2 hours.After polyreaction terminates, cooling, collect polyethylene particle powder, weigh.
The molecular weight distribution (Mw/Mn) of concrete polymerization result and polymer is listed in table 1.
Table 1, polymerization result
Polymerizing condition: 1000ml hexane, 1.0mmolTEA, 0.28MPa hydrogen, 0.45MPa ethylene, 80 DEG C, time 2h
As can be seen from Table 1, the catalyst E that contrast Halogen adds for ether compound, the distribution of the molecular weight of polyethylene prepared by catalyst adding chloro-3 methoxy propanes of 1-increases with the addition of chloro-3 methoxy propanes of 1-and reduces, it is reduced to 5.70 by 7.23, is then reduced to 4.78 by 5.95 with the molecular weight distribution of hervene copolymer.
Claims (9)
1. the catalytic component being used for producing Narrow Molecular Weight Distribution polyethylene, it is characterised in that comprise magnesium halide/inorganic oxide carrier, alcohol compound, the product of titanium compound and halogen ether compounds；The formula of described halogen ether compounds is X-CHR1-OR2, R1It is hydrogen, R2Be carbon number being the alkyl of 1～4, X is halogen；Or described halogen ether compounds is 1 chlorine 3 methoxy propane, 1 chlorine 3 ethoxy propane, 1 chlorine 3 methyl butyl ether, 1 bromine 3 methoxy propane, 1 bromine 3 ethoxy butane.
2. the catalytic component for producing Narrow Molecular Weight Distribution polyethylene according to claim 1; it is characterized in that described magnesium halide/inorganic oxide carrier is magnesium chloride/silica-gel carrier; it is prepared by following method: by anhydrous magnesium chloride under inert gas shielding, joins in reactor, adds a certain amount of solvent; silica gel is added after anhydrous magnesium chloride dissolves; after stirring, heating steams solvent, then heats evacuation; remove solvent, obtain magnesium chloride/silica-gel carrier.
3. the catalytic component for producing Narrow Molecular Weight Distribution polyethylene according to claim 1, it is characterised in that described titanium compound is TiCl4、TiCl3Or Ti (OR)4。
4. the catalytic component for producing Narrow Molecular Weight Distribution polyethylene according to claim 1, it is characterised in that alcohol compound is carbon number be 1～10 straight or branched alcohol.
5. the catalytic component for producing Narrow Molecular Weight Distribution polyethylene according to claim 1, it is characterised in that alcohol compound at least one in ethanol, normal propyl alcohol, n-butyl alcohol, 2-Ethylhexyl Alcohol, isopropanol, isobutanol.
6. the catalytic component for producing Narrow Molecular Weight Distribution polyethylene according to claim 1, it is characterized in that the molar ratio of described halogen ether compounds and magnesium halide is 0.1～10, the molar ratio of described alcohol compound and magnesium halide is 0.1～10, and the molar ratio of described titanium compound and magnesium halide is 0.1～10.
7. for producing a catalyst for Narrow Molecular Weight Distribution polyethylene, comprise the product of following components: the catalytic component that one of (1) claim 1-6 is described；(2) formula is AlRnX3-nOrgano-aluminum compound, in formula, R is hydrogen or carbon number is the alkyl of l～20, and X is halogen, the integer of 0 < n≤3；In component (2), aluminum is 5～500 with the mol ratio of titanium in component (1).
8. the preparation method of the catalytic component for producing Narrow Molecular Weight Distribution polyethylene described for one of claim 1-6, comprise the following steps: under the protection of noble gas, magnesium halide/inorganic oxide carrier is added in solvent and makes serosity, heat to 50～90 DEG C of stirrings, add alcohol compound, stirring reaction 10～90 minutes, pump the supernatant, rejoin solvent, add titanium compound, heating is to 50～90 DEG C, stirring reaction 1～3 hour, drop to room temperature, add halogen ether compounds, it is raised to 30～70 DEG C to react 1～4 hour, filter, washing, dry, obtain ingredient of solid catalyst.
9. the preparation method of the catalytic component for producing Narrow Molecular Weight Distribution polyethylene according to claim 8, it is characterized in that the molar ratio of described halogen ether compounds and magnesium halide is 0.1～10, the molar ratio of described alcohol compound and magnesium halide is 0.1～10, and the molar ratio of described titanium compound and magnesium halide is 0.1～10.
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