CN101597347B - Main catalyst component for polymerizing ethylene and ethylene polymerizing catalyst containing the component - Google Patents
Main catalyst component for polymerizing ethylene and ethylene polymerizing catalyst containing the component Download PDFInfo
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- CN101597347B CN101597347B CN2009100534262A CN200910053426A CN101597347B CN 101597347 B CN101597347 B CN 101597347B CN 2009100534262 A CN2009100534262 A CN 2009100534262A CN 200910053426 A CN200910053426 A CN 200910053426A CN 101597347 B CN101597347 B CN 101597347B
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Abstract
The invention relates to a main catalyst component for polymerizing ethylene, a catalyst composed of the catalyst component and an auxiliary catalyst, and a preparation method of the catalyst. The main catalyst component is shaped by drying reaction product of components, such as nascent magnesium compound, titanium compound, alkyl aluminium compound, ether solvent and the like. The specific surface area of the primary pore structure of the obtained main catalyst particles is 20 to 160m<2>/g, and the single-point absorption pore volume is 0.3 to 0.9ml/g. The catalyst has high activity and stacking density of the polymer is high.
Description
Technical field
The present invention relates to a kind of main catalyst component that is used for vinyl polymerization, and the ethylene rolymerization catalyst that contains this component.
Background technology
The appearance of frozen state technology and super frozen state technology, make the production efficiency of gas phase polymerization technology improve 50～100% and 60～300% respectively, and traditional vapor phase process activity of such catalysts is generally at 3000～5000gPE/gCat, and the residence time is long, can not adapt to the requirement of novel technique.Therefore must study more highly active catalyzer is used for vapour phase polymerization.
Improving the most direct active way is to make catalyzer obtain higher active centre concentration.Can effectively improve the polymerization activity of catalyzer such as the content that improves transition metals Ti in the catalyzer.CN1223267A discloses and has adopted traditional impregnation drying method to produce the high-performance solid catalyzer, in actual fabrication process, when the Mg/Ti ratio reaches 3.0 when above, the sheet phenomenon will appear tying in catalyzer in drying process, though the catalyst junction sheet can be removed, can reduce the catalyzer yield.This small catalyst fragment can generate on the one hand fine polymer powder and cause and carry blocking pipe secretly in gas-phase polymerization processes, it forms hot localised points easily and makes the difficult control of temperature of reaction in gas-phase fluidized-bed on the other hand, also be subjected to electrostatic interaction powerful on the fluidized-bed inner-wall surface to cause adhering to the polymer scale sheet that the back forms easily, rupture after these knot sheets grow into certainweight or length, falling can the gas-phase fluidized-bed operational stability of influence on the fluidized bed gas grid distributor.
Among the EP0771820 traditional dipping method is improved.At first form a steeping fluid that contains magnesium, titanium and electron donor, this steeping fluid mixes with carrier, and solvent evaporated then is again with the same steeping fluid of forming impregnated carrier, solvent evaporated then once more.Dipping can repeat repeatedly by actual needs.Dipping can guarantee that components such as magnesium, titanium are evenly distributed in the carrier hole as much as possible repeatedly.Therefore obtain higher magnesium/titanium ratio, catalyst agglomeration is few, and active high.But this method is repeatedly flooded the electron donor consumption is increased greatly, has increased solvent recuperation purified load.Simultaneously, though catalyzer magnesium, titanium content that this method obtains increase, proportion is still more than 50wt% in catalyzer for inert support, and catalyst activity improves little.
Reduce inert support content in the catalyzer, the magnesium of catalyzer, titanium content are significantly improved, thereby catalyst activity is multiplied.In USP 4293673 and WO 01/05845, all mention the method that adopts spraying drying to prepare catalyzer.Adopting aerosil in these patents is carrier, with catalyst component one react form a gel material after, carry out spraying drying.Catalyst particle size can be controlled, and inert support content can drop to 30wt%, obtains the magnesium, the titanium content that double than pickling process, activity of such catalysts is increased substantially and sheet do not occur tying.But compare with pickling process, adopt spray-dired catalyzer initial apertures structure not controlled by inert support, so the catalyst pores structure control is relatively more difficult.
And in the industrial application of reality, the initial pore Structure Control of catalyzer is extremely important.High-specific surface area and high pore volume make catalyzer easily cracked and expose more active site, therefore have higher activity.But catalyzer is easy more cracked, granule strength is just low more, because the granules of catalyst form is the template of final polymkeric substance, the polymkeric substance that the catalyzer that granule strength is high obtains has higher tap density, this is particularly important in gas fluidized-bed process, and it can the assurance device stable and high effective operation.Therefore catalyzer must have suitable initial apertures structure, makes the requirement of polymerization activity and the realistic production of granule strength.The invention provides a kind of ethylene polymerization catalysts that is used for, wherein main catalyst component has suitable specific surface area and pore volume, and catalyzer has the tap density height of highly active while polymkeric substance.
Summary of the invention
One of purpose of the present invention provides a kind of main catalyst component that is used for vinyl polymerization;
Two of purpose of the present invention provides a kind of ethylene rolymerization catalyst that contains this main catalyst component.
Three of purpose of the present invention provides a kind of preparation method who is used for the Primary Catalysts of vinyl polymerization;
Four of purpose of the present invention provides a kind of preparation method who contains the ethylene rolymerization catalyst of this main catalyst component.
A kind of main catalyst component that is used for vinyl polymerization, this main catalyst component is by following each component reaction after drying moulding, and the solid main catalyst particulate specific surface area that obtains is 20～160m
2/ g, single-point absorption pore volume is 0.3～0.9ml/g, described each component comprises:
(1) nascent state magnesium compound (MgRX)
y(MgX
2);
Wherein, R is the alkyl that contains 3～12 carbon atoms, and X is a halogen, y=0.02～1;
(2) titanium compound Ti (OR
2)
mCl
4-m
Wherein, R
2Be the alkyl that contains 1～10 carbon atom, m is 0～4;
(3) alkylaluminium cpd R
3 nAlCl
3-n
Wherein, R
3Be the alkyl that contains 1～14 carbon atom, n is 1～3;
(4) ether solvent R
4OR
5
Wherein, R
4And R
5Be to contain the alkyl of 1～8 identical or different carbon atom or form the ring that contains 4～12 carbon atoms together;
(5) polyoxyethylene glycol H (OCH
2CH
2)
nOH, n=4～450, molecular-weight average is 200～20000;
(6) aerosil.
A kind of ethylene polymerization catalysts that is used for, this catalyzer is made up of main catalyst component and promotor, it is characterized in that the BET surface-area 20～160m of Primary Catalysts particle initial apertures structure behind the drying and moulding
2/ g, single-point absorption pore volume 0.3～0.9ml/g.
Promotor is an organo-aluminium compound, comprises triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum etc. or its mixture, preferred triethyl aluminum.
Wherein, the nascent state magnesium compound is a feedstock production with the magnesium powder, and its structural formula is (RMgX)
y(MgX
2), y=0.02～1 wherein, preferred 0.05～0.43, R is the alkyl group that contains 3～12 carbon, X is a halogen, preferably chlorine.
The structural formula of titanium compound is Ti (OR
2)
mCl
4-m, R wherein
2Be the alkyl that contains 1～10 carbon atom, m is 0～4, as one or more the mixture in titanium tetrachloride, butyl (tetra) titanate, methoxyl group titanous chloride, the butoxy titanous chloride, and preferred titanium tetrachloride.
Alkylaluminium cpd is that structural formula is R
3 nAlCl
3-nMaterial, R wherein
3It is the alkyl that contains 1～14 carbon atom, n is 1～3, as a kind of or its mixture of triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-octylaluminium, three (2-ethylhexyl) aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium, preferred aluminium diethyl monochloride.
The structural formula of ether solvent is R
4OR
5, wherein, R
4And R
5Be the identical or different alkyl that contains 1～8 carbon atom or form the ring contain 4～12 carbon atoms together, preferred R
4And R
5Form ring, for example the ring of 4～6 carbon atoms.Preferred alkyl ether comprises ether, n-butyl ether, isobutyl ether, dicaprylyl ether; Preferred cyclic ethers comprises tetrahydropyrans, 3-methyl tetrahydropyrans, 2-methyltetrahydrofuran; Tetrahydrofuran (THF) most preferably.
The peg molecule formula is H (OCH
2CH
2)
nOH, repeated structural unit (OCH
2CH
2) number n=4～450, molecular-weight average 200～20000.Preferred 500～10000.
Aerosil (fumed silica) is a kind of have minimum particle diameter, bigger serface, highly purified silica gel, and its average particle size range (state of aggregation) is 0.1～0.9 μ m; Specific surface area is 100～500m
2/ g, preferred 150～400m
2/ g.As commercially available Cabot company
TS-610, EH5, M5 etc.
A kind of preparation method who is used for ethylene polymerization catalysts, this method comprises following reactions steps:
(1) preparation of nascent state magnesium compound:
Under nitrogen protection; the magnesium powder reacts with halogenated alkane in alkane solvents; temperature of reaction is controlled at 10～100 ℃; preferably 20～80 ℃; in 0.5～10 hour reaction times, preferably 1～8 hour, after finishing, reaction makes the nascent state magnesium compound; with the nascent state magnesium compound of the alkane solvents washing gained of cleaning several times, drying makes it into solid-state standby.The mol ratio of described magnesium powder and halogenated alkane is 1: (1～3),
Contain a certain amount of alkyl halide magnesium RMgX in the nascent state magnesium compound, its structural formula is (RMgX)
y(MgX
2), y=0.02～1 wherein, preferred 0.05～0.43, R is the alkyl group that contains 3～12 carbon, X is a halogen, preferably chlorine.
Alkane solvents is aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon, and as Skellysolve A, iso-pentane, normal hexane, octane, pentamethylene, hexanaphthene, benzene, 1,2-ethylene dichloride etc. or its mixture preferably contain the aliphatic hydrocarbon compounds of 5～10 carbon.
The structural formula of described halogenated alkane is RX, and R is the alkyl that contains 3～12 carbon atoms, and X is a halogen, and preferably chlorine can be chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, chloro iso-pentane etc.
(2) preparation of titaniferous main catalyst component:
The nascent state magnesium compound that will make by above-mentioned steps is dissolved in the ether solvent, adds stirring reaction behind titanium compound, alkylaluminium cpd and the polyoxyethylene glycol.20～80 ℃ of temperature of reaction, 0.5～10 hour reaction times, preferably 1～8 hour.
After finishing, reaction reduces to normal temperature, aerosil joined in the above-mentioned reactant while stirring mix, aerosil is dispersed in fully forms a uniform thickness attitude mixture in the liquid system, be warmed up to 30～65 ℃, keep reaction 0.5～3.0 hour.
The above-mentioned titanium compound that adds and the mol ratio of alkylaluminium cpd and nascent state magnesium compound are Mg: Ti: Al=(2～10): 1: (0.5～5), preferred (3～6): 1: (1～2).
The consumption of polyoxyethylene glycol is to guarantee to account for 0.5～10wt% in final main catalyst component.Preferred 2～9wt%.
The ether solvent consumption is that every gram aerosil adds 10～20ml.
The moisture on surface can be removed before aerosil uses, this purpose can be reached by the method that at room temperature vacuumizes or heat.The consumption of aerosil is to guarantee that it accounts for 10～40wt%, preferred 20～35wt% in final main catalyst component.
(3) moulding of main catalyst component and drying
The uniform thickness attitude mixture that step (2) is obtained carries out moulding and drying, the BET surface-area 20～160m of the Primary Catalysts particulate initial apertures structure that makes
2/ g, single-point absorption pore volume 0.3～0.9ml/g.
The moulding of main catalyst component and drying can adopt various known method, and slightly cooling of the even thickness attitude mixture that for example step (2) is obtained is to wherein adding alkane solvents such as iso-pentane or normal hexane.Along with the adding of solvent, solid particulate begins sedimentation separates out, and aerosil is not only carrier here, also helps the moulding of main catalyst component to separate out as the crystal seed component.Solvent adds the back and keeps reaction for some time, and the intensification drying obtains the main catalyst component particle.For example in the even thickness attitude mixture that step (2) obtains, add inert mineral oil again and under agitation carry out emulsification with a small amount of polyhydric alcohol fatty acid ester class nonionogenic tenside, then emulsion is transferred in advance in the refrigerative alkane, main catalyst component therein rapidly condensation cured become particle.Obtain the main catalyst component particle then behind the cleaning-drying.
The present invention preferably adopts spray drying process.The moulding and a dry step that can make main catalyst component are in this way finished.Its device is divided into air-flowing type, pressure type and rotary three kinds usually according to the type of spraying gun.The preferred rotary atomizer of the present invention.Owing to need to recycle as the tetrahydrofuran (THF) of solvent and electron donor, so the present invention adopts the closed circuit circulatory system spray drying unit, with nitrogen as drying medium.
The even thickness attitude mixture that above-mentioned steps (2) is obtained injects in the spray-dryer, feeds nitrogen as drying medium, and making particle diameter is the main catalyst component of 10～50 μ m.The volumetric flow rate of nitrogen will be higher than the flow of the mixture of injection, and controlled temperature will be higher than the boiling point of ether solvent (the preferred tetrahydrofuran (THF) of the present invention), controls the content of ether solvent in the Primary Catalysts component by control nitrogen flow and temperature.Making the residual weight percentage of ether solvent in the Primary Catalysts component is 15～35%, preferred 17～30%.
The dry temperature in of spray drying unit is 130～190 ℃ among the present invention, and dry temperature out is 100～120 ℃, and nitrogen flow is 300～600Nm
3/ hr.Mainly control the size and the form of the catalyst particle of final formation by the speed of rotation of adjusting rotary atomizer.The rotating speed of rotary atomizer is 10000～25000r/min among the present invention.The main catalyst component particle median size that forms is at 10～50 μ m, preferred 15～30 μ m; BET surface-area 20～160m
2/ g, single-point absorption pore volume 0.3～0.9ml/g.
The main catalyst component that obtains by above-mentioned preparation method can with activator join respectively by a certain percentage carry out in the polymerisation medium main catalyst component with regard to activatable.Also main catalyst component can be activated in advance with activator before introducing polymerisation medium.The activator that adopts is the aluminum alkyls compounds, as one or more the mixture in aluminium diethyl monochloride, triethyl aluminum, tri-n-hexyl aluminum, dichloro one aluminium triethyl.Activator level is controlled by ether solvent remaining in the main catalyst component, and general add-on is 60～70% (moles) of ether solvent residual volume.
(4) contact reacts of main catalyst component and promotor
The body of catalyst component that drying and moulding is obtained contacts the formation ethylene rolymerization catalyst with promotor, described promotor is an organo-aluminium compound, the mol ratio of described promotor and body of catalyst component is Al in the promotor: Ti=in the body of catalyst component (30～300): 1, preferred (50～250): 1.
Promotor among the present invention is an organo-aluminium compound, as triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, tri-n-hexyl aluminum or its mixture, and preferred triethyl aluminum.
The solid main catalyst component that forms by (3) method can directly apply to polymerization, also can be dispersed in to form slurry in alkane solvents or the inert mineral oil and be applied to polymerization again.The present invention preferably is dispersed in the solid main catalyst component in alkane solvents or the mineral oil and forms slurry and be applied to the polymeric method again.
Described alkane solvents can be a paraffinic hydrocarbons, a kind of as in iso-pentane, hexane, normal heptane, octane, nonane or the decane etc.Since the existence of alkane solvents to be used to pack, the resin of foodstuff is unfavorable, the present invention preferably is suspended in main catalyst component in the inert mineral oil and forms slurry, main catalyst component shared weight percentage in slurry is 10～50wt%.
The above-mentioned ethylene polymerization catalysts that is used for can be used for slurry polymerization or vapour phase polymerization, preferred gas phase polymerization.
The mentioned catalyzer of the present invention directly is applied in and is used to produce polyethylene in gas-phase fluidized-bed, and polymerization temperature is 80～115 ℃, preferably 85～100 ℃; Polymerization pressure is 1.0～2.0MPa.
As need production of linear new LDPE (film grade), then can add the density that comonomer is regulated product.Common comonomer is the aliphatics alpha-olefin that contains 3～8 carbon atoms.The alpha-olefin that is suitable for has propylene, butene-1, amylene-1, hexene-1,4-methylpentene-1, heptene-1 and octene-1.Preferred alpha-olefin is butene-1 and hexene-1.After adding comonomer, can make density is 0.915～0.958 gram per centimeter
3Polyethylene product.
Be the melting index of telomerized polymer, can add chain-transfer agent and regulate.The chain-transfer agent that is suitable for is a hydrogen, or adds zinc ethyl in catalyzer.The hydrogen partial pressure that feeds can make melting index MI 10%～50% adjusting
2.16At 0～60 polyethylene product that restrains between/10 minutes.
The ethylene polymerization catalysts that is used for of the present invention reduces greatly owing to inert support one aerosil content, so polymerization activity height, activity can reach 10000～15000 gram polyethylene/gram catalyzer (ethylene partial pressure is 0.5～0.6Mpa, polymerization time 2 hours).
Simultaneously, the ethylene polymerization catalysts that is used for of the present invention is owing to have rational initial apertures structure, so granules of catalyst intensity height, and the polyvinyl resin powder that polymerization obtains has high-bulk-density.
In addition, the ethylene polymerization catalysts that is used for of the present invention has regular particle form, and size-grade distribution is concentrated.Therefore reduce the generation of polyethylene fine powder, and helped gas-phase fluidized-bed stable operation.Find out that from accompanying drawing 1 and accompanying drawing 2 Primary Catalysts particulate median size can be regulated and control as required, and the Primary Catalysts particle size distribution that obtains is concentrated in spray-drying process.Find out that from accompanying drawing 3 the Primary Catalysts particle presents ganoid sphere, and almost can't see the ground grains appearance.
Description of drawings
Fig. 1 is the Primary Catalysts size distribution situation of embodiment 1 preparation.
Fig. 2 is the Primary Catalysts size distribution situation of embodiment 3 preparations.
Fig. 3 is Primary Catalysts particulate scan Electronic Speculum (SEM) photo of embodiment 1 preparation.
Embodiment
Further specify the present invention below by detailed description to specific embodiments of the invention, but embodiment and do not mean that limitation of the present invention.
The analysis that catalyzer is formed among the embodiment is carried out in accordance with the following methods:
Mg, Ti, Al ion content adopt plasma emission spectrum to measure;
The Cl ion content adopts potentiometric determination;
The THF residual volume is solid phase prod to be extracted the extraction liquid that obtains adopt gas chromatographic analysis to obtain in acetone;
The initial apertures structural analysis of Primary Catalysts adopts ASAP2000 specific surface pore volume high speed tester to measure among the embodiment; The size-grade distribution of granules of catalyst then adopts MasterSizer 2000 laser particle analyzers to measure; Primary Catalysts particulate stereoscan photograph adopts the X-650 scanning electron microscope to measure.
Each polymer properties index is measured as follows among the embodiment:
The mensuration of melting index MI: according to ASTM-D1238, condition E, 190 ℃ of following mensuration;
The mensuration of density polymer: measure according to ASTM-1050;
The mensuration of polymer stacks density: measure according to ASTM-D1895;
Embodiment 1:
(1) preparation of nascent state magnesium chloride
In reactor, add 1000l hexane and 24.81kg magnesium powder, be warmed up to 60 ℃, the 217l n-propylcarbinyl chloride is slowly joined in the reactor, add the back and continue reaction 4 hours down, obtain the nascent state magnesium chloride solids suspension of black at 60 ℃ with 3.0 hours.Steam hexane solvent under 70 ℃, the cooling back adds the 800l tetrahydrofuran (THF) in reactor, stirs and obtains dark solution.After the analysis as can be known, Cl/Mg=1.89, (BuMgCl)
0.12(MgCl
2);
(2) preparation of main catalyst component
Make adding 29.6kg titanium tetrachloride in the solution in step (1), 22.56kg aluminium diethyl monochloride and molecular-weight average are 6000 polyoxyethylene glycol (Acros company product) 7.80kg, be warmed up to 60 ℃ and under this temperature, keep reaction 3 hours, after being cooled to room temperature, add 130kg while stirring through heat treated aerosil (EH-5 of CABOT company type), under the effect of stirring, form a uniform thickness attitude mixture.Be warming up to 55 ℃, keep reaction 1.5 hours.
(3) to the main catalyst component spraying drying
The aforesaid liquid mixture is carried out spraying drying.Use closed cycle formula spray drying unit, the temperature in of nitrogen in spray-dryer is 160 ℃, and dry temperature out is 110 ℃, and the circulating nitrogen gas flow is 450Nm
3/ h, the rotating speed of rotary atomizer are 13500r/min, and forming volume average particle size is the main catalyst component particle of 28 μ m, and it is collected in
Form slurry in 550 water-white mineral oils, solid constituent accounts for 25wt% in the maintenance slurry.
The content of each principal element is in the Primary Catalysts component:
Ti:2.23wt%, Mg:3.88wt%, Cl:20.1wt%, polyoxyethylene glycol: 2wt%, tetrahydrofuran (THF): 23.2wt%.
Primary Catalysts particle initial apertures structure is:
BET surface-area: 140.68m
2/ g, single-point absorption pore volume: 0.589ml/g.
(4) polyreaction:
Take out 70g catalyst slurry liquid, before carrying out polymerization, in the main catalyst component slurry, add the 3.7ml aluminium diethyl monochloride, mix at normal temperatures and stirred 2 hours.
In 2 liters reactor, carry out slurry polymerization, pressure 0.8MPa, nitrogen partial pressure 0.2Mpa, 80 ℃ of temperature, 2 hours time, triethyl aluminum 1.4ml, catalyzer add-on 0.2042g (solids content 0.0504g) obtains white polyethylene 650g, the bulk density 0.40g/cm of product
3, density 0.952g/cm
3
Embodiment 2:
(1) preparation of nascent state magnesium chloride is with embodiment 1;
(2) preparation of main catalyst component
The preparation method is TiCl with embodiment 1
4Add-on 26.1kg, AlEt
2Cl add-on 18.42kg, the polyoxyethylene glycol 19.0Kg of molecular-weight average 1450, SiO
2: 133kg;
(3) to the main catalyst component spraying drying: method is with embodiment 1.
The content of each principal element is in the Primary Catalysts component:
Ti:2.03wt%, Mg:4.38wt%, Cl:20.3wt%, polyoxyethylene glycol: 4.9wt%, tetrahydrofuran (THF): 26.0wt%.
Primary Catalysts particle initial apertures structure is:
BET surface-area: 104.38m
2/ g, single-point absorption pore volume: 0.328ml/g.
(4) polyreaction:
Take out 70g catalyst slurry liquid, add aluminium diethyl monochloride 3.1ml and tri-n-hexyl aluminum 3.2ml respectively before the polymerization in the main catalyst component slurry, all the other are with embodiment 1.
In 2 liters reactor, carry out slurry polymerization, pressure 0.8MPa, hydrogen partial pressure 0.1MPa wherein, nitrogen partial pressure 0.1Mpa, all the other polymerizing conditions are with embodiment 1, and polymerization result sees Table 1.
Embodiment 3:
(1) preparation of nascent state magnesium chloride is with embodiment 1;
(2) preparation of main catalyst component: the preparation method is TiCl with embodiment 1
4Add-on 32.18kg, Et
2AlCl add-on 21.56kg, the polyoxyethylene glycol of molecular-weight average 4000 (Alfa Aesar company product) 5.1kg.Aerosil adopts CABOT company's T S610 type, and consumption is 128kg.
(3) to the main catalyst component spraying drying: method is with embodiment 1, and just the circumferential speed with rotary atomizer is adjusted into 25000r/min.The Primary Catalysts particulate volume average particle size that obtains is 12.48 μ m.
Each components contents is in the catalyzer:
Ti:2.41wt%, Mg:6.27wt%, Cl:27.9wt%, polyoxyethylene glycol: 1.3wt%, tetrahydrofuran (THF): 25.7wt%.
Primary Catalysts particle initial apertures structure is:
BET surface-area: 71.77m
2/ g, single-point absorption pore volume: 0.731ml/g.
(4) polyreaction
Take out 70g catalyst slurry liquid, add aluminium diethyl monochloride 2.3ml before the polymerization in the main catalyst component slurry, all the other are with embodiment 1.
In 2 liters reactor, carry out slurry polymerization, pressure 0.8MPa, hydrogen partial pressure 0.15MPa wherein, nitrogen partial pressure 0.15MPa, hexene 150ml, all the other polymerizing conditions are with embodiment 1, and polymerization result sees Table 1.
Embodiment 4:
(1) preparation of nascent state magnesium chloride
In reactor, add 1000l hexane and 25.31kg magnesium powder, with 3.0 hours the 220l chloro-butane is added dropwise in the reaction flask down, after dropwising, under 65 ℃, keep reaction 4 hours, obtain the nascent state magnesium chloride solids suspension of black at 65 ℃.Steam hexane solvent under 70 ℃, the cooling back adds the 800l tetrahydrofuran (THF) in reaction flask, stir, and obtains dark solution.Analyze Cl/Mg=1.84, (BuMgCl)
0.19(MgCl
2);
(2) preparation of main catalyst component
Make adding 25.7kg TiCl in the solution in step (1)
4, 20.3kg AlEt
2Cl, molecular-weight average are 6000 polyoxyethylene glycol (Acros company product) 11.5kg.Be warmed up to 63 ℃ and under this temperature, keep reaction 3 hours, be cooled to room temperature after, add 135kg while stirring through heat treated aerosil (CABOT company's T S-610 type), under the effect of stirring, form a uniform thickness attitude mixture.Be warming up to 50 ℃, keep reaction 1.0 hours.
(3) to the main catalyst component spraying drying
The aforesaid liquid mixture is carried out spraying drying, and method is with embodiment 1.
Content in the catalyzer in the main body component is:
Ti:2.02wt%, Mg:4.09wt%, Cl:19.28wt%, polyoxyethylene glycol: 2.9wt% tetrahydrofuran (THF): 32.1wt%.
Primary Catalysts particle initial apertures structure is:
BET surface-area: 137.77m
2/ g, single-point absorption pore volume: 0.431ml/g.
(4) polyreaction:
Take out 70g catalyst slurry liquid, add aluminium diethyl monochloride 5.8ml before the polymerization in the main catalyst component slurry, all the other are with embodiment 1.
In 2 liters reactor, carry out slurry polymerization, pressure 0.8MPa, hydrogen partial pressure 0.15Mpa wherein, nitrogen partial pressure 0.10Mpa, hexene 100ml, all the other polymerizing conditions are with embodiment 1, and polymerization result sees Table 1.
Embodiment 5:
Body of catalyst component 10g with spraying drying among the embodiment 1 makes stirs into slurry with the 60ml hexane, adds the 0.6ml aluminium diethyl monochloride under the room temperature and stirs 1 hour, then evaporate to dryness.Obtain carrying out vapour phase polymerization through preactivated solid main catalyst component.
Polyreaction:
In being 100 millimeters, high 1500 millimeters fluidized-bed, diameter carries out polyreaction.In fluidized-bed reactor, add earlier through exsiccant 100g polyethylene base-material, promotor triethyl aluminum 0.8ml adds a certain amount of solid main catalyst component, and other polymerizing condition sees Table 2, test number is respectively 1,2,3,4,5,6, and polymerization result sees Table 2.
The comparative example 1
(1) preparation of nascent state magnesium chloride is with embodiment 1;
(2) preparation of main catalyst component and spray-drying process are with embodiment 1, except not adding polyoxyethylene glycol.
Each components contents is in the catalyzer:
Ti:2.21wt%, Mg:3.97wt%, Cl:22.9wt%, tetrahydrofuran (THF): 25.5wt%.
Primary Catalysts particle initial apertures structure is:
BET surface-area: 270.18m
2/ g, single-point absorption pore volume: 1.214ml/g.
(4) polyreaction
Take out 70g catalyst slurry liquid, add aluminium diethyl monochloride 3.5ml before the polymerization in the main catalyst component slurry, all the other are with embodiment 1.
Slurry polymerization conditions is with embodiment 1.
Gas phase polymerization process is with embodiment 7, and polymerizing condition and polymerization result see Table 2.
Table 1
From the table data as can be seen, the tap density of polymkeric substance is significantly improved.
Claims (11)
1. main catalyst component that is used for vinyl polymerization, this main catalyst component is by following each component reaction after drying moulding, and the specific surface area of the solid main catalyst particulate initial apertures structure that obtains is 20～160m
2/ g, single-point absorption pore volume is 0.3～0.9ml/g, described each component comprises:
(1) nascent state magnesium compound (MgRX)
y(MgX
2)
Wherein, R is the alkyl that contains 3～12 carbon atoms, and X is a halogen, y=0.02～1;
(2) titanium compound Ti (OR
2)
mCl
4-m
Wherein, R
2Be the alkyl that contains 1～10 carbon atom, m is 0～4;
(3) alkylaluminium cpd R
3 nAlCl
3-n
Wherein, R
3Be the alkyl that contains 1～14 carbon atom, n is 1～3;
(4) ether solvent R
4OR
5
Wherein, R
4And R
5Be to contain the alkyl of 1～8 identical or different carbon atom or form the ring that contains 4～12 carbon atoms together;
(5) polyoxyethylene glycol H (OCH
2CH
2)
nOH, n=4～450, molecular-weight average is 200～20000;
(6) aerosil.
2. a kind of main catalyst component that is used for vinyl polymerization according to claim 1 is characterized in that described titanium compound is selected from one or more the mixture in titanium tetrachloride, butyl (tetra) titanate, methoxyl group titanous chloride, the butoxy titanous chloride.
3. a kind of main catalyst component that is used for vinyl polymerization according to claim 1 is characterized in that described alkylaluminium cpd is selected from a kind of or its mixture of triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-octylaluminium, three (2-ethylhexyl) aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium.
4. a kind of main catalyst component that is used for vinyl polymerization according to claim 1, it is characterized in that described ether solvent is selected from ether, n-butyl ether, isobutyl ether or dicaprylyl ether at interior alkyl oxide, or be selected from tetrahydropyrans, 3-methyl tetrahydropyrans or 2-methyltetrahydrofuran at interior cyclic ethers.
5. a kind of main catalyst component that is used for vinyl polymerization according to claim 1, the molecular-weight average that it is characterized in that described polyoxyethylene glycol is 500-10000.
6. one kind is used for ethylene polymerization catalysts, and this catalyzer is made up of main catalyst component and promotor, it is characterized in that described main catalyst component according to claim 1, and described promotor is an organo-aluminium compound.
7. preparation method who is used for the Primary Catalysts of vinyl polymerization, the preparation method of this Primary Catalysts comprises:
(1) preparation of nascent state magnesium compound:
Under nitrogen protection, the magnesium powder reacts with halogenated alkane RX in alkane solvents, and temperature of reaction is controlled at 10～100 ℃, in 0.5～10 hour reaction times, makes nascent state magnesium compound (RMgX) after reaction is finished
y(MgX
2), y=0.02～1 wherein, the mol ratio of described magnesium powder and halogenated alkane is 1: (1～3), and R is the alkyl that contains 3～twelve carbon atom, X is a halogen;
(2) preparation of titaniferous main catalyst component:
The nascent state magnesium compound that will make by above-mentioned steps is dissolved in the ether solvent, adds stirring reaction behind titanium compound, alkylaluminium cpd and the polyoxyethylene glycol; 20～80 ℃ of temperature of reaction, 0.5～10 hour reaction times, after finishing, reaction reduces to normal temperature, and aerosil is joined in the above-mentioned reactant mix, be warmed up to 30～65 ℃, keep reaction 0.5～3.0 hour;
The above-mentioned titanium compound that adds and the mol ratio of alkylaluminium cpd and nascent state magnesium compound are Mg: Ti: Al=(2～10): 1: (0.5～5), the consumption of polyoxyethylene glycol accounts for 0.5～10wt% in final main catalyst component, the ether solvent consumption is that every gram aerosil adds 10～20ml, and the consumption of aerosil accounts for 10～40wt% in final main catalyst component;
(3) moulding of main catalyst component and drying:
The mixture that above-mentioned steps is obtained carries out moulding and drying, the Primary Catalysts particulate initial apertures structure BET surface-area 20～160m that makes
2/ g, single-point absorption pore volume 0.3～0.9ml/g.
8. a kind of preparation method who is used for the Primary Catalysts of vinyl polymerization according to claim 7 is characterized in that described moulding and exsiccant method are spraying drying.
9. a preparation method who is used for ethylene polymerization catalysts is characterized in that the main catalyst component that described claim 7 drying and moulding is obtained contacts the formation ethylene rolymerization catalyst with promotor, and described promotor is an organo-aluminium compound; The mol ratio of described promotor and main catalyst component is Al in the promotor: Ti=in the main catalyst component (30～300): 1.
10. a kind of preparation method who is used for ethylene polymerization catalysts according to claim 9, before it is characterized in that main catalyst component that described claim 7 drying and moulding is obtained and promotor contacting, activate in advance with activator earlier, described activator is the aluminum alkyls compounds, and activator level is 60～70% moles of ethers residual volume in the main catalyst component.
11. a kind of preparation method who is used for ethylene polymerization catalysts according to claim 10 is characterized in that described aluminum alkyls compounds is selected from one or more the mixture in aluminium diethyl monochloride, triethyl aluminum, tri-n-hexyl aluminum or dichloro one aluminium triethyl.
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| CN101235109A (en) * | 2007-02-01 | 2008-08-06 | 上海化工研究院 | Method for preparing superhigh molecular weight polythene catalyst and application thereof |
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