CN103788247B - For the catalytic component of olefinic polymerization and application thereof with for catalyst and application and the olefine polymerizing process of olefinic polymerization - Google Patents
For the catalytic component of olefinic polymerization and application thereof with for catalyst and application and the olefine polymerizing process of olefinic polymerization Download PDFInfo
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Abstract
The invention provides a kind of catalytic component for olefinic polymerization and application thereof, this catalytic component contains and is reacted the product obtaining by carrier for olefin polymerization catalyst with titanium compound, and described carrier for olefin polymerization catalyst contains the magnesium halide that general formula is MgXY, the compound that general formula is ROH, compound, two oxyl hydrocarbon compounds, the oxirane compounds that general formula is R ' OH. The present invention also provides a kind of catalyst for olefinic polymerization and application thereof, and olefine polymerizing process. Catalyst for olefinic polymerization according to the present invention is in the time of the catalyst as olefinic polyreaction, and the bulk density of the polymer that polymerization obtains also can be improved.
Description
Technical field
The present invention relates to a kind of catalytic component for olefinic polymerization, the described catalysis for olefinic polymerizationAgent component is in the application of the catalyst for olefinic polymerization, and a kind of catalyst for olefinic polymerization, shouldBe used for the catalyst of olefinic polymerization at application and the olefine polymerizing process of olefinic polyreaction.
Background technology
As everyone knows, the Ziegler-Natta catalyst of magnesium chloride alcohol adduct load for alkene (particularlyPropylene) when polymerization, its performance is obviously better than the catalyst of other carrier institute load. Therefore, at present forThe catalyst of olefinic polymerization is mostly by being carried on halogenated titanium on magnesium chloride alcohol adduct and preparing.In order to obtain ball type carrier, can be dry by spraying, spray cooling, high pressure is extruded, high-speed stirred, breastThe method preparations such as change machine method and high-gravity rotating bed method, as open in WO99/44009 and US4399054 etc.Can form spherical alcohol adduct by quenching after high-speed stirred emulsification magnesium chloride alcohol adduct system under high temperature.
But, when by the catalyst of being prepared by above-mentioned published magnesium chloride alcohol adduct for olefinic polymerizationTime, in polymerization process, be easy to occur the Fragmentation Phenomena of polymer particle, thereby cause fine polymer powderMore. In order to overcome this shortcoming, people attempt again electron donor compound to be incorporated in advance magnesium chlorideFor example, in the carrier preparation of alcohol adduct: CN1169840C and CN1286863C are known by the industryInternal electron donor phthalate compound was incorporated in synthesizing of magnesium chloride alcohol adduct carrier, therebyObtain " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier, then by this carrier and titanium tetrachloride reactionTo form catalyst. But the spherical carrier of described compound is easily clamminess in preparation process, be difficult to formThe spheric granules that particle size is suitable.
In addition, above-mentioned magnesium chloride alcohol adduct is all to adopt cryogenic quenching to solidify the alcohol adduct melt system of high temperature, not only, complicated process of preparation large to the consumption of the energy, must combine preparation by multiple reactors, andThe particle diameter wider distribution of prepared alcohol adduct. In order to address this problem, CN102040683A disclosesReact to prepare a method for carrier by magnesium halide alcohol adduct and oxirane compounds, and concreteDisclose after magnesium halide alcohol adduct melting dispersion, added oxirane compounds; Or by halogenationMagnesium alcoholate melting directly joins in the reactor containing oxirane compounds after disperseing. But, adoptExist preparation process unstable with the method Kaolinite Preparation of Catalyst carrier, carrier adhesion easily occurs, and carrierThe shortcoming that molding effect is bad.
Summary of the invention
First object of the present invention is to lack in order to overcome the above-mentioned of existing carrier for olefin polymerization catalystFall into, and a kind of catalyst group for olefinic polymerization that contains new carrier for olefin polymerization catalyst is providedPoint.
Second object of the present invention be to provide the described catalytic component for olefinic polymerization forApplication in the catalyst of olefinic polymerization.
The 3rd object of the present invention is to provide a kind of catalyst for olefinic polymerization.
It is poly-at alkene that the 4th object of the present invention is to provide the catalyst for olefinic polymerization of the present inventionClose the application in reaction.
The 5th object of the present invention is to provide a kind of olefine polymerizing process.
For realizing aforementioned object, first aspect, the invention provides a kind of catalyst for olefinic polymerizationComponent, this catalytic component contains and is reacted the product obtaining by carrier for olefin polymerization catalyst with titanium compoundThing, wherein, described carrier for olefin polymerization catalyst contains magnesium halide, the general formula that general formula is MgXY and isThe compound of ROH, the compound that general formula is R ' OH, two oxyl hydrocarbon compounds, ethylene oxideCompound; In formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C1-C14AlkaneOxygen base, C6-C14Aryl or C6-C14Aryloxy group; In general formula R OH, R is C1-C8AlkylOr C3-C8Cycloalkyl; In general formula R ' OH, R ' is C16-C24Alkyl or aralkyl; Described twoThe structure of oxyl hydrocarbon compound as shown in the formula (I), the structure of described oxirane compounds suc as formulaShown in (II):
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl.
The present invention also provides a kind of catalytic component for olefinic polymerization, this catalytic component contain byCarrier for olefin polymerization catalyst reacts with titanium compound and internal electron donor the product obtaining, wherein, described inCarrier for olefin polymerization catalyst contain magnesium halide that general formula is MgXY, compound that general formula is ROH,General formula is compound, two oxyl hydrocarbon compounds, the oxirane compounds of R ' OH; At general formulaIn MgXY, X is halogen, and Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group; In general formula R OH, R is C1-C8Alkyl or C3-C8RingAlkyl; In general formula R ' OH, R ' is C16-C24Alkyl or aralkyl; Described two oxyl hydrocarbonylations are closedAs shown in the formula (I), the structure of described oxirane compounds is suc as formula shown in (II) for the structure of thing:
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl.
Second aspect, the invention provides a kind of catalytic component for olefinic polymerization of the present inventionIn the application of the catalyst for olefinic polymerization.
The third aspect, the invention provides a kind of catalyst for olefinic polymerization, and this catalyst contains:
(1) catalytic component for olefinic polymerization of the present invention;
(2) alkyl aluminum compound; And
(3) optional external donor compound.
Fourth aspect, the invention provides the catalyst for olefinic polymerization of the present invention poly-at alkeneClose the application in reaction.
The 5th aspect, the invention provides a kind of olefine polymerizing process, and the method comprises: in olefinic polymerizationUnder condition, by one or more alkene and the catalytic component for olefinic polymerization of the present invention, alkaneBase aluminium compound and optional external donor compound contact.
The present inventor is surprised to find that, on the one hand, and in the system of described carrier for olefin polymerization catalystIn standby process, adding general formula is the compound of R ' OH, not only can reduce the interparticle collider of not mouldingAdhesion between rate, minimizing carrier particle, thus significantly improve stability and dispersiveness prepared by described carrier,Make that the carrier granular form that obtains is good, smooth surface, substantially there will not be irregular particle, and by instituteWhile stating catalyst prepared by carrier for alkene (particularly propylene) polymerization, can also effectively improve polymerizationThe bulk density of product; On the other hand, the use of structure two hydrocarbon oxy compounds as shown in the formula (I),Not only can make to carry out emulsification under low stir speed (S.S.) time, also can obtain the good carrier of pattern, raisingThe stability of product preparation process, can also significantly shorten time, the raising of subsequent wash operation and produce effectRate.
Catalyst for olefinic polymerization according to the present invention has used according to the present invention containing originallyThe catalytic component for olefinic polymerization of the carrier for olefin polymerization catalyst described in invention. Therefore according to thisThe described catalyst for olefinic polymerization of invention is in the time of the catalyst as olefinic polyreaction, and polymerization obtainsTo the bulk density of polymer also can be improved.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 1;
Fig. 2 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 2;
Fig. 3 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by contrast preparation example 1;
Fig. 4 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by contrast preparation example 2.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
According to a first aspect of the invention, the invention provides a kind of catalyst group for olefinic polymerizationPoint, this catalytic component contains and is reacted the product obtaining by carrier for olefin polymerization catalyst with titanium compound,Wherein, to contain magnesium halide, general formula that general formula is MgXY be ROH to described carrier for olefin polymerization catalystCompound, compound, two oxyl hydrocarbon compounds, the oxirane compounds that general formula is R ' OH;In formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl,C6-C14Aryl or C6-C14Aryloxy group; In general formula R OH, R is C1-C8Alkyl or C3-C8Cycloalkyl; In general formula R ' OH, R ' is C16-C24Alkyl or aralkyl; Described two oxyl hydrocarbonAs shown in the formula (I), the structure of described oxirane compounds is suc as formula (II) institute for the structure of compoundShow:
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl.
According to the present invention, preferably described catalytic component of the present invention contains by olefin polymerization catalysis and carriesBody, titanium compound and internal electron donor compound react the product obtaining. Be that the present invention also provides oneFor the catalytic component of olefinic polymerization, this catalytic component contains by carrier for olefin polymerization catalyst and titaniumCompound and internal electron donor react the product obtaining, and wherein, described carrier for olefin polymerization catalyst containsCompound that general formula is the magnesium halide of MgXY, compound that general formula is ROH, general formula is R ' OH,Two oxyl hydrocarbon compounds, oxirane compounds; In formula M gXY, X is halogen, and Y isHalogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group;In general formula R OH, R is C1-C8Alkyl or C3-C8Cycloalkyl; In general formula R ' OH, R 'For C16-C24Alkyl or aralkyl; The structure of described two oxyl hydrocarbon compounds as shown in the formula (I),The structure of described oxirane compounds is suc as formula shown in (II):
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl.
In the present invention, described internal electron donor compound can be for the preparation of the catalyst of olefinic polymerizationThe conventional various internal electron donor compounds that use in process, can be for example carboxylate, alcohol ester, ether,One or more in ketone, nitrile, amine and silane, are preferably monobasic or polyhydric aliphatic family carboxylate, monobasicOr one or more in polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether. In the present invention, described inMonobasic or polyhydric aliphatic family carboxylate, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and binary etherThe selection of concrete kind all can be selected with reference to prior art, and the present invention retouches no longer in detail at thisState.
In the present invention, at the described catalytic component for olefinic polymerization, titanium elements, magnesium elements and inThe weight ratio of electron donor compound can be 1:5-15:2-15, is preferably 1:6-13:3-12.
In the present invention, described carrier for olefin polymerization catalyst, titanium compound and internal electron donor compoundThere is no particular limitation for the condition of reaction, and under preferable case, the condition of this reaction can comprise: reaction temperatureDegree is 80-130 DEG C, and the reaction time is 0.5-10 hour.
According to the present invention, the content of the above-mentioned each component in described carrier for olefin polymerization catalyst can beIn large scope, select and change, for example, the magnesium halide taking 1mol general formula as MgXY is benchmark,General formula is that the content of the compound of ROH can be 4-30mol, the content of the compound that general formula is R ' OHCan be 0.001-1.5mol, the content of structure two oxyl hydrocarbon compounds as shown in the formula (I) can be0.001-1.5mol, structure suc as formula the content of the oxirane compounds shown in (II) can be1-10mol; Preferably, the magnesium halide taking 1mol general formula as MgXY is benchmark, and general formula is ROHThe content of compound is 6-20mol, and the content of the compound that general formula is R ' OH is 0.01-1mol, structureThe content of two oxyl hydrocarbon compounds is as shown in the formula (I) 0.01-1mol, and structure is suc as formula (II) instituteThe content of the oxirane compounds showing is 2-6mol.
According to the present invention, in described carrier for olefin polymerization catalyst, in formula M gXY, X is preferredFor chlorine or bromine, Y is preferably chlorine, bromine, C1-C5Alkyl, C1-C5Alkoxyl, C6-C10ArylOr C6-C10Aryloxy group. Described C1-C5Alkyl can be for example methyl, ethyl, n-pro-pyl, differentPropyl group, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl or new pentaBase, described C1-C5Alkoxyl can be for example methoxyl group, ethyoxyl, propoxyl group, isopropoxy,Butoxy or isobutoxy, described C6-C10Aryl can be for example phenyl, o-tolyl, a tolueneBase, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, described C6-C10Fragrant oxygenBase can be for example phenoxy group or naphthoxy. General formula is that the magnesium halide of MgXY can be a kind of magnesium halide,Or the mixture of multiple magnesium halide. General formula be MgXY magnesium halide instantiation can for butBe not limited to: magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxyOne or more in magnesium. From the angle of being easy to get property of raw material, be preferably magnesium chloride.
According to the present invention, in described carrier for olefin polymerization catalyst, in general formula R OH, R is preferablyC1-C8Alkyl. Described C1-C8Alkyl can be for example methyl, ethyl, n-pro-pyl, isopropyl,Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, ownBase, isohesyl, heptyl, different heptyl, octyl group or iso-octyl. General formula is compound concrete of ROHExample can be but be not limited to: ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, amylalcohol, isoamylOne or more in alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
According to the present invention, in described carrier for olefin polymerization catalyst, in general formula R ' OH, R ' is preferablyC16-C20Alkyl or aralkyl. General formula is that the instantiation of the compound of R ' OH can be but be not limited to:Hexadecanol and 18 alcohol.
According to the present invention, in structure two oxyl hydrocarbon compounds as shown in the formula (I), R1、R2、R3And R4Be preferably hydrogen, C independently of one another1-C3Alkyl, C6-C8Aryl; Described C1-C3AlkylCan be for example methyl, ethyl, propyl group or isopropyl; Described C6-C8Aryl can be for example phenyl,O-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene or to ethylbenzene; Described twoThe instantiation of oxyl hydrocarbon compound can be but be not limited to: 2,2-dimethoxypropane, 2,2-dimethoxyBase butane, 2,2-dimethoxy pentane, 3,3-dimethoxy pentane, 2,2-di ethyl propyl ether and 2,2-bis-One or more in phenoxypropane.
According to the present invention, structure suc as formula the oxirane compounds shown in (II) in, R5And R6Be preferably hydrogen, C independently of one another1-C3Alkyl or haloalkyl. Described oxirane compoundsInstantiation can for but be not limited to: oxirane, expoxy propane, epoxy butane, epoxychloropropane,One or more in epoxy chlorobutane, epoxy bromopropane and epoxy NBB.
A preferred embodiment of the invention, the average grain of described carrier for olefin polymerization catalystDiameter can be 10-100 micron, is preferably 40-60 micron; Particle diameter distributes and is less than 1.2, is preferably0.6-0.8. In this preferred embodiment, the catalyst of being prepared by this carrier for olefin polymerization catalyst canObtain having the more olefin polymer of high-bulk-density. In the present invention, described olefin polymerization catalysis carriesThe average particulate diameter of body and particle diameter distribute can adopt MasterSizer2000 laser particle analyzer (byMalvernInstrumentsLtd manufactures) record.
According to the present invention, the water containing in described carrier for olefin polymerization catalyst comes from synthesis material and anti-Answer medium with minor amount of water.
In the present invention, described titanium compound can be for the preparation of normal in the process of the catalyst of olefinic polymerizationThe various titanium compounds that rule are used. Conventionally, described titanium compound is general formula Ti (ORa)4-mXmCompound,Wherein, RaFor C1-C14Aliphatic group, X is F, Cl or Br, the integer that m is 1-4; Described titaniumCompound is preferably titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, three butoxy titanium chlorides, dibutoxyTitanium chloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy titanium chloride and ethyoxylOne or more in titanium trichloride.
In the present invention, can realize this as long as ensure to contain carrier for olefin polymerization catalyst of the present inventionInvention object, particularly to the preparation method of described carrier for olefin polymerization catalyst without particular/special requirement, pinTo the present invention, particularly preferably carrier for olefin polymerization catalyst of the present invention prepares in accordance with the following steps:
(1) compound, general formula that the magnesium halide that is MgXY by general formula, general formula are ROH are R ' OHCompound, two oxyl hydrocarbon compounds mix with inert liquid medium and heat, obtain liquefied mixture;
(2) liquefied mixture emulsification step (1) being obtained, and by emulsification product and ethylene oxideCompound haptoreaction;
In formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C1-C14AlcoxylBase, C6-C14Aryl or C6-C14Aryloxy group; In general formula R OH, R is C1-C8Alkyl orC3-C8Cycloalkyl; In general formula R ' OH, R ' is C16-C24Alkyl or aralkyl; Described two hydrocarbonAs shown in the formula (I), the structure of described oxirane compounds is suc as formula (II) for the structure of oxygen base hydrocarbon compoundShown in:
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl.
Wherein, the magnesium halide that general formula is MgXY, compound, the general formula that general formula is ROH are R ' OHCompound, two oxyl hydrocarbon compounds, the kind of oxirane compounds describe hereinbefore,To repeat no more at this.
According to the present invention, the magnesium halide that general formula is MgXY, compound, the general formula that general formula is ROH areTwo oxyl hydrocarbon compounds as shown in the formula (I) of the compound of R ' OH, structure, structure are suc as formula (II)The consumption of shown oxirane compounds can be according to the group of the carrier for olefin polymerization catalyst of expectionBecome to carry out suitable selection, preferably, the magnesium halide taking 1mol general formula as MgXY is benchmark, general formulaFor the consumption of the compound of ROH is 4-30mol, the consumption of the compound that general formula is R ' OH is0.001-1.5mol, the consumption of structure two oxyl hydrocarbon compounds is as shown in the formula (I) 0.001-1.5mol,Structure is 1-10mol suc as formula the consumption of the oxirane compounds shown in (II); More preferably, with1mol general formula is that the magnesium halide of MgXY is benchmark, and the consumption of the compound that general formula is ROH is6-20mol, the consumption of the compound that general formula is R ' OH is 0.01-1mol, structure is as shown in the formula (I)The consumption of two oxyl hydrocarbon compounds is 0.01-1mol, and structure is suc as formula the ethylene oxide shown in (II)The consumption of compound is 2-6mol.
According to invention, the minor amount of water in above-mentioned each reactant also can participate in forming olefin polymerization catalysis and carryThe reaction of body.
According to the present invention, in step (1), be ROH for the magnesium halide that is MgXY by general formula, general formulaCompound, compound, two oxyl hydrocarbon compounds and inert liquid medium that general formula is R ' OH mixedThe condition of compound heating is not particularly limited, and is MgXY as long as the condition of described heating can make general formulaMagnesium halide melting the compound that is ROH with general formula, the compound and two that general formula is R ' OHOxyl hydrocarbon compound reacts. Usually, the condition of described heating comprises: temperature can be80-120 DEG C, the time can be 0.5-5 hour; Preferably, described temperature is 80-100 DEG C, and the time is0.5-3 hour.
According to the present invention, the halogenation that the consumption of described inert liquid medium can be MgXY according to general formulaThe consumption of magnesium is selected. Usually, the magnesium halide taking 1mol general formula as MgXY is benchmark, described lazyThe consumption of property liquid medium can be 0.8-10L, is preferably 2-8L. Described inert liquid medium can beThis area not there is not chemically interactive liquid medium with reactant and product in conventional various. ExampleAs: as described in inert liquid medium can be silicone oil and/or inert fluid varsol. Particularly, described lazyProperty liquid medium can be kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil,One or more in Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil. Inertia of the present inventionLiquid medium is particularly preferably white oil.
According to the present invention, can adopt and well known to a person skilled in the art that the whole bag of tricks obtains step (1)The liquefied mixture emulsification of arriving. For example, described liquefied mixture can be carried out to low velocity shear or cut at a high speedCut, thereby by its emulsification. The stir speed (S.S.) of described low velocity shear is generally 400-800 rev/min. DescribedThe method of high speed shear is conventionally known to one of skill in the art, high-speed stirred as disclosed in CN1151183CMethod (, is stirred the solution that contains liquid adduct of magnesium halides with the speed of 2000-5000 rev/minMix). In addition, can also be with reference to following patent disclosed method by described liquefied mixture emulsification:CN1267508C is disclosed to be rotated the solution that contains liquid adduct of magnesium halides in hypergravity bedDisperse (speed of rotation can be 100-3000 rev/min); CN1463990A is disclosed will contain liquidThe solution of state adduct of magnesium halides speed with 1500-8000 rev/min in mulser is exported;US6020279 is disclosed will contain the emulsifying soln of liquid adduct of magnesium halides by spray-on process.
According to the present invention, in step (2), by emulsification product and oxirane compounds haptoreactionCondition can be for the existing various conditions that can form carrier for olefin polymerization catalyst, for example, described inCatalytic condition comprises that temperature can be 80-120 DEG C, and the time can be 20-60 minute; Preferably,Described temperature is 80-100 DEG C, and the time is 20-50 minute.
According to the present invention, the method for preparing described carrier for olefin polymerization catalyst can also comprise contact anti-In the product that should obtain, carry out Separation of Solid and Liquid, solid product is washed and is dried. Described Separation of Solid and LiquidCan be the existing various method that can realize solid phase and liquid phase separation, for example suction filtration, press filtration or centrifugalSeparate, under preferable case, the method for described Separation of Solid and Liquid is filter press technique. The present invention does not have the condition of press filtrationHave especially and limit, be as the criterion with separating of liquid phase to realize as far as possible fully solid phase. Described washing is passableEmploying well known to a person skilled in the art that method washs the solid product obtaining, for example, can adoptInert hydrocarbon solvent (for example: pentane, hexane, heptane, benzinum and gasoline) produces the solid phase obtainingThing washs. The present invention is not particularly limited for described dry condition, for example: described dryTemperature can be 20-70 DEG C, and the described dry time can be 0.5-10 hour. According to the present invention, instituteState dry can carrying out under normal pressure or reduced pressure.
According to a second aspect of the invention, the invention provides urging for olefinic polymerization of the present inventionAgent component is in the application of the catalyst for olefinic polymerization.
According to a third aspect of the invention we, the invention provides a kind of catalyst for olefinic polymerization, shouldCatalyst contains:
(1) catalytic component for olefinic polymerization of the present invention;
(2) alkyl aluminum compound; And
(3) optional external donor compound.
The composition of the described catalytic component for olefinic polymerization has carried out detailed retouching in the preceding articleState, do not repeat them here.
Catalyst for olefinic polymerization according to the present invention has used according to the present invention for alkeneThe catalytic component of polymerized hydrocarbon, therefore the catalyst for olefinic polymerization according to the present invention is being used asWhen the catalyst of olefinic polyreaction, the bulk density of the polymer that polymerization obtains is also improved. Therefore,Catalyst for olefinic polymerization according to the present invention is for alkyl aluminum compound and external electron donorKind and the consumption of compound are all not particularly limited.
Usually, at the described catalyst for olefinic polymerization, in the alkyl aluminum compound of aluminium and withThe mol ratio of the catalytic component for olefinic polymerization of titanium meter can be 1-2000:1, is preferably20-500:1; The mol ratio of described external donor compound and alkyl aluminum compound can be0.005-0.5:1, is preferably 0.01-0.4:1.
According to the catalyst for olefinic polymerization of the present invention, described alkyl aluminum compound can be this areaConventional various alkyl aluminum compounds. For example, described alkyl aluminum compound can be triethyl aluminum, three differentButyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorineDi-n-butyl aluminium, a chlorine di-n-hexyl aluminium, dichloro one aluminium ethide, dichloro one aluminium isobutyl, dichloro one are justOne or more in butyl aluminium and dichloro one n-hexyl aluminium.
According to the catalyst for olefinic polymerization of the present invention, described external donor compound can be thisThe various external donor compounds that field is conventional, for example, described external electron donor can be carboxylic acid, acidOne or more in acid anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and silicon compound; Preferably,Described external electron donor is for having general formula R8 aR9 bSi(OR10)cSilicon compound, wherein, a and b are separatelyBe 0,1 or 2 integer, the integer that c is 1-3, and a+b+c's and be 4, R8、R9、R10SeparatelyBe C independently1-C18Replacement or unsubstituted alkyl; More preferably, a and b 1, the c that respectively does for oneself is 2,R8、R9Be C independently of one another3-C10Replacement or unsubstituted alkyl, R10For C1-C10Replacement orUnsubstituted alkyl. Particularly, the example of described organo-silicon compound can be but be not limited to: cyclohexylMethyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, two differentButyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, two ringsAmyl group dimethoxy silane, 2-ethyl piperidine base-2-tert-butyl group dimethoxy silane and (the fluoro-2-third of 1,1,1-tri-Base)-2-ethyl piperidine base dimethoxy silane and (the fluoro-2-propyl group of 1,1,1-tri-)-methyl dimethoxysilane.
According to a forth aspect of the invention, the invention provides urging for olefinic polymerization of the present inventionThe application of agent in olefinic polyreaction.
According to a fifth aspect of the invention, the invention provides a kind of olefine polymerizing process, the method comprises:Under olefinic polymerization condition, by one or more alkene and the catalysis for olefinic polymerization of the present inventionAgent component, alkyl aluminum compound and optional external donor compound contact.
Olefine polymerizing process according to the present invention is according to the present invention for alkene by usingThe catalyst of polymerization, can prepare the polymer that particle shape is good, bulk density is high. Described in of the present inventionOlefine polymerizing process is not particularly limited for olefinic polymerization condition and the alkene using.
Described alkene can be for example ethene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-A kind of in methyl isophthalic acid-butylene, 2-methyl-2-butene, 1-amylene, 2-amylene, 1-hexene and styrene orMultiple, be preferably one or more in ethene, propylene, 1-butylene, 2-butylene and styrene.
According to olefine polymerizing process of the present invention, described olefinic polymerization can be according to the conventional method of this areaCarry out. For example, described olefinic polymerization can be polymerisation in bulk, gas-phase polymerization or slurry polymerization. According to thisThe olefine polymerizing process of invention, described olefinic polymerization condition can be the normal condition of this area, for example,Polymerization temperature can be 0-150 DEG C, is preferably 60-90 DEG C; Polymerization pressure can be normal pressure or pressurization.
The invention will be further described by the following examples. But, should be understood that, these are realExecute example only for description and interpretation the present invention, be not limited to the present invention.
Below will describe the present invention by embodiment.
In embodiment and comparative example:
1, the average particulate diameter of carrier for olefin polymerization catalyst and particle diameter distribute and adopt MastersSizer2000 particle size analyzers (being manufactured by MalvernInstrumentsLtd) are measured;
2, the apparent pattern of carrier for olefin polymerization catalyst by being purchased from the model of Nikon company isThe light microscope of EclipseE200 is observed;
3, the method that the bulk density of polyolefine powder adopts GB/T1636-2008 to specify is measured.
Preparation example 1
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 8.0g(0.08mol) magnesium chloride, 3g(0.01mol) 18 alcohol, 95mL(1.6mol) ethanol, 9.8mL(0.08mol) 2,2-dimethoxyPropane, is under agitation warming up to 90 DEG C. After isothermal reaction 1 hour, mixture stirring at low speed (is stirredSpeed is 400 revs/min) disperse 30 minutes, to carry out emulsification. And add in above-mentioned emulsification product35mL(0.45mol) epoxychloropropane, press filtration after reaction half an hour, time of filter pressing is 9 minutes.By hexane washing 5 times for press filtration product, washed rear press filtration at every turn, press filtration operation total time is 20 pointsClock. Finally, by product vacuum drying, obtain carrier for olefin polymerization catalyst Z1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z1 is 57 microns, particle diameterDistribution ((D90-D10)/D50) is 0.6. Adopt the particle morphology of observation by light microscope as Fig. 1 instituteShow. As can be seen from the figure, the particle shape of carrier for olefin polymerization catalyst Z1 is more regular, surfaceSmooth, be all spherical substantially, particle size distribution is more concentrated, and there is no irregular particleExist.
Preparation example 2
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 300mL white oil, 8.0g(0.08mol) magnesium chloride, 10.8g(0.04mol) 18 alcohol, 28mL(0.48mol) ethanol, 1mL(0.008mol) 2,2-dimethoxyPropane, is under agitation warming up to 100 DEG C. After isothermal reaction 0.5 hour, mixture stirring at low speed (is stirredMixing speed is 800 revs/min) disperse 30 minutes, to carry out emulsification. And add in above-mentioned emulsification productEnter 12.5mL(0.16mol) epoxychloropropane, react press filtration after 20 minutes, time of filter pressing is 10 pointsClock. By hexane washing 5 times for press filtration product, washed rear press filtration at every turn, press filtration operation total time is 25Minute. Finally, by product vacuum drying, obtain carrier for olefin polymerization catalyst Z2.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z2 is 48 microns, particle diameterDistribution ((D90-D10)/D50) is 0.7. Adopt the particle morphology of observation by light microscope as Fig. 2 instituteShow. As can be seen from the figure, the particle shape of carrier for olefin polymerization catalyst Z2 is more regular, surfaceSmooth, be all spherical substantially, particle size distribution is more concentrated, and there is no irregular particleExist.
Preparation example 3
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 500mL white oil, 8.0g(0.08mol) magnesium chloride, 21.6g(0.08mol) 18 alcohol, 58mL(1mol) ethanol, 3.5mL(0.04mol) 2,2-dimethoxy thirdAlkane, is under agitation warming up to 80 DEG C. After isothermal reaction 3 hours, mixture stirring at low speed (is stirred to speedRate is 800 revs/min) disperse 30 minutes, to carry out emulsification. And add in above-mentioned emulsification product23.5mL(0.3mol) epoxychloropropane, reacts press filtration after 50 minutes, and time of filter pressing is 8 minutes.By hexane washing 5 times for press filtration product, washed rear press filtration at every turn, press filtration operation total time is 22 pointsClock. Finally, by product vacuum drying, obtain carrier for olefin polymerization catalyst Z3.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z3 is 50 microns, particle diameterDistribution ((D90-D10)/D50) is 0.65. Adopt the pattern of observation by light microscope particle to find, alkeneThe particle shape of polymerized hydrocarbon catalyst carrier Z3 is more regular, and smooth surface is all spherical substantially,Particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 4
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 600mL methyl-silicone oil, 8.0g(0.08mol) magnesium bromide,29.1g(0.12mol) hexadecanol, 13mL(0.32mol) methyl alcohol, 19.3mL(0.12mol) 2,2-Di ethyl propyl ether, is under agitation warming up to 110 DEG C. After isothermal reaction 0.3 hour, mixture is lowSpeed stirs (stir speed (S.S.) is 800 revs/min) disperses 30 minutes, to carry out emulsification. And at above-mentioned breastChange in product and add 4mL(0.08mol) oxirane, press filtration after reaction half an hour, time of filter pressingIt is 11 minutes. By hexane washing 5 times for press filtration product, washed rear press filtration at every turn, press filtration operation is totalTime is 27 minutes. Finally, by product vacuum drying, obtain carrier for olefin polymerization catalyst Z4.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z4 is 45 microns, particle diameterDistribution ((D90-D10)/D50) is 0.75. Adopt the pattern of observation by light microscope particle to find, alkeneThe particle shape of polymerized hydrocarbon catalyst carrier Z4 is more regular, and surface is comparatively smooth, is all ball substantiallyShape, particle size distribution is more concentrated, and there is no that irregular particle exists.
Contrast preparation example 1
This contrast preparation example is used for illustrating reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to preparation example 1 is prepared carrier for olefin polymerization catalyst, different, does not add 2,2-Dimethoxy propane. Emulsification product is carried out to press filtration, and time of filter pressing is 22 minutes. Press filtration product is usedRear press filtration has been washed in hexane washing 5 times at every turn, and press filtration operation total time is 50 minutes. Finally will produceThing vacuum drying, obtains carrier for olefin polymerization catalyst DZ1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst DZ1 is 52 microns, grainFootpath distribution ((D90-D10)/D50) is 1.0. Adopt the particle morphology of observation by light microscope as Fig. 3Shown in. As can be seen from the figure, in carrier for olefin polymerization catalyst DZ1, Fragmentation Phenomena is comparatively serious,And the surface of particle is comparatively coarse.
Contrast preparation example 2
This contrast preparation example is used for illustrating reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to embodiment 1 is prepared carrier for olefin polymerization catalyst, different, and 18 alcohol are usedThe ethanol of identical weight part substitutes. In emulsification product, add 35mL(0.45mol) epoxychloropropane,Press filtration after reaction half an hour, time of filter pressing is 18 minutes. By hexane washing 5 times for press filtration product,Washed rear press filtration, press filtration operation total time is 36 minutes at every turn. Finally, by product vacuum drying, obtainTo carrier for olefin polymerization catalyst DZ2.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst DZ2 is 54 microns, grainFootpath distribution ((D90-D10)/D50) is 1.2. Adopt the particle morphology of observation by light microscope as Fig. 4Shown in. As can be seen from the figure, in carrier for olefin polymerization catalyst DZ2, there is a large amount of irregular particles,And surface is comparatively coarse.
Embodiment 1
This embodiment is for illustrating the preparation of alkene provided by the invention.
(1) preparation of olefin polymerization catalysis
In the glass reaction bottle of 300mL, add the titanium tetrachloride of 100mL, be cooled to-20 DEG C, willThe described carrier for olefin polymerization catalyst Z1 being obtained by preparation example 1 of 40 grams adds wherein, and at-20 DEG CLower stirring 30min. Afterwards, start to be slowly warming up to 110 DEG C, in temperature-rise period, add 1.5mL'sDiisobutyl phthalate, at 110 DEG C, maintain 30min after elimination liquid. Then, add tetrachloroChange titanium washing 2 times, finally wash 3 times with hexane, after being dried, obtain olefin polymerization catalysis C1.
(3) propylene polymerization
In the stainless steel autoclave of a 5L, adopt stream of nitrogen gas to purge, then at nitrogen(concentration of triethyl aluminum is in entraining air stream, to introduce the hexane solution of the triethyl aluminum of 1mmol0.5mmol/mL), the anhydrous hexane of the Cyclohexylmethyldimethoxysilane of 0.05mmol, 10mL andThe olefin polymerization catalysis C1 being obtained by step (1) of 10mg, 1.5L(normal volume) hydrogenLiquid propene with 2.5L. Be warming up to 70 DEG C, and at this temperature, react 1 hour, cooling, bleeds off pressure,The dry polypropylene powder that obtains of discharging. The bulk density of this polypropylene powder is 0.45g/cm3, in addition, shouldPolypropylene powder particle shape is good, does not substantially have abnormity material.
Embodiment 2
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, described olefin polymerization catalysis carriesThe described carrier for olefin polymerization catalyst Z2 that body Z1 obtains by preparation example 2 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.44g/cm3, in addition, this polypropylene powder particle shape is good,Substantially there is not abnormity material.
Embodiment 3
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, described olefin polymerization catalysis carriesThe described carrier for olefin polymerization catalyst Z3 that body Z1 obtains by preparation example 3 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.44g/cm3, in addition, this polypropylene powder particle shape is good,Substantially there is not abnormity material.
Embodiment 4
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, described olefin polymerization catalysis carriesThe described carrier for olefin polymerization catalyst Z4 that body Z1 obtains by preparation example 4 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.44g/cm3, in addition, this polypropylene powder particle shape is good,Substantially there is not abnormity material.
Comparative example 1
This comparative example is for illustrating the reference preparation of alkene.
Carry out propylene polymerization according to the method for embodiment 1, different, described olefin polymerization catalysis carriesBody Z1 substitutes with the described carrier for olefin polymerization catalyst DZ1 that contrast preparation example 1 obtains, and obtains poly-thirdAlkene powder. The bulk density of this polypropylene powder is 0.43g/cm3, in addition, in this polypropylene powder particleThere is more abnormity material.
Comparative example 2
This comparative example is for illustrating the reference preparation of alkene.
Carry out propylene polymerization according to the method for embodiment 1, different, described olefin polymerization catalysis carriesBody Z1 substitutes with the described carrier for olefin polymerization catalyst DZ2 that contrast preparation example 2 obtains, and obtains poly-thirdAlkene powder. The bulk density of this polypropylene powder is 0.41g/cm3, in addition, in this polypropylene powder particleThere is more abnormity material.
As can be seen from the above results, the olefin polymerization catalysis that adopts method of the present invention to prepare carriesThe particle shape of body is good, smooth surface, substantially there will not be irregular particle, and with the carrier of gainedWhen the catalyst of preparation is used for alkene (particularly propylene) polymerization, the heap that can also improve polymerizate is closeThe appearance of spending, substantially expecting without the opposite sex. In addition, can from the contrast of preparation example 1 and contrast preparation example 1Go out, the use of structure two hydrocarbon oxy compounds as shown in the formula (I), not only can make in low stirringWhile carrying out emulsification under speed, also can obtain the good carrier of pattern, improve the stable of product preparation processProperty, can also significantly shorten subsequent wash operation time, enhance productivity, have before commercial ApplicationScape.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentioned realityExecute the detail in mode, within the scope of technical conceive of the present invention, can be to technical side of the present inventionCase is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode. For fear of needn'tThe repetition of wanting, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (33)
1. for a catalytic component for olefinic polymerization, this catalytic component contains by olefinic polymerization urgesAgent carrier reacts the product obtaining with titanium compound, it is characterized in that, described olefin polymerization catalysis carriesBody contains the magnesium halide that general formula is MgXY, the compound that general formula is ROH, the change that general formula is R'OHCompound, two oxyl hydrocarbon compounds, oxirane compounds; In formula M gXY, X is halogenElement, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14'sAryloxy group; In general formula R OH, R is C1-C8Alkyl or C3-C8Cycloalkyl; General formula R ' OHIn, R' is C16-C24Alkyl or aralkyl; The structure of described two oxyl hydrocarbon compounds is suc as formula (I)Shown in, the structure of described oxirane compounds is suc as formula shown in (II):
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl,
In described carrier for olefin polymerization catalyst, the magnesium halide taking 1mol general formula as MgXY is benchmark,General formula is that the content of the compound of ROH is 4-30mol, and the content of the compound that general formula is R'OH is0.001-1.5mol, structure is 0.001-1.5mol suc as formula the content of two oxyl hydrocarbon compounds shown in (I),Structure is 1-10mol suc as formula the content of the oxirane compounds shown in (II).
2. for a catalytic component for olefinic polymerization, this catalytic component contains by olefinic polymerization urgesAgent carrier reacts with titanium compound and internal electron donor the product obtaining, and it is characterized in that described alkenePolymerizing catalyst carrier contains the magnesium halide that general formula is MgXY, compound, the general formula that general formula is ROHFor compound, two oxyl hydrocarbon compounds, the oxirane compounds of R'OH; At formula M gXYIn, X is halogen, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14ArylOr C6-C14Aryloxy group; In general formula R OH, R is C1-C8Alkyl or C3-C8Cycloalkyl;General formula R ' in OH, R' is C16-C24Alkyl or aralkyl; The knot of described two oxyl hydrocarbon compoundsStructure is suc as formula shown in (I), and the structure of described oxirane compounds is suc as formula shown in (II):
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl,
In described carrier for olefin polymerization catalyst, the magnesium halide taking 1mol general formula as MgXY is benchmark,General formula is that the content of the compound of ROH is 4-30mol, and the content of the compound that general formula is R'OH is0.001-1.5mol, structure is 0.001-1.5mol suc as formula the content of two oxyl hydrocarbon compounds shown in (I),Structure is 1-10mol suc as formula the content of the oxirane compounds shown in (II).
3. catalytic component according to claim 2, wherein, described internal electron donor compoundFor one or more in carboxylate, alcohol ester, ether, ketone, nitrile, amine and silane.
4. catalytic component according to claim 3, wherein, described internal electron donor compoundFor monobasic or polyhydric aliphatic family carboxylate, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and binary etherIn one or more.
5. catalytic component according to claim 2, wherein, described for olefinic polymerizationIn catalytic component, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1:5-15:2-15.
6. catalytic component according to claim 5, wherein, described for olefinic polymerizationIn catalytic component, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1:6-13:3-12.
7. according to the catalytic component described in any one in claim 1-6, wherein, described alkeneIn polymerizing catalyst carrier, the magnesium halide taking 1mol general formula as MgXY is benchmark, and general formula is ROHThe content of compound be 6-20mol, the content of the compound that general formula is R'OH is 0.01-1mol, knotStructure is 0.01-1mol suc as formula the content of two oxyl hydrocarbon compounds shown in (I), and structure is suc as formula (II)The content of shown oxirane compounds is 2-6mol.
8. according to the catalytic component described in any one in claim 1-6, wherein, described alkeneIn polymerizing catalyst carrier, in formula M gXY, X is chlorine or bromine, and Y is chlorine, bromine, C1-C5'sAlkyl, C1-C5Alkoxyl, C6-C10Aryl or C6-C10Aryloxy group.
9. catalytic component according to claim 8, wherein, described olefin polymerization catalysis carriesIn body, the magnesium halide that general formula is MgXY is selected from magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorinationOne or more in isopropoxy magnesium and chlorination n-butoxy magnesium.
10. according to the catalytic component described in any one in claim 1-6, wherein, described alkeneIn polymerizing catalyst carrier, in general formula R OH, R is C1-C8Alkyl.
11. catalytic components according to claim 10, wherein, described olefin polymerization catalysisIn carrier, the compound that general formula is ROH be selected from ethanol, propyl alcohol, isopropyl alcohol, n-butanol, isobutanol,One or more in amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
12. according to the catalytic component described in any one in claim 1-6, wherein, and described alkeneIn polymerizing catalyst carrier, general formula R ' in OH, R' is C16-C20Alkyl or aralkyl.
13. catalytic components according to claim 12, wherein, described olefin polymerization catalysisIn carrier, the compound that general formula is R'OH is hexadecanol and/or 18 alcohol.
14. according to the catalytic component described in any one in claim 1-6, wherein, and described alkeneIn polymerizing catalyst carrier, structure is suc as formula in two oxyl hydrocarbon compounds shown in (I), R1、R2、R3And R4Be hydrogen, C independently of one another1-C3Alkyl, C6-C8Aryl.
15. catalytic components according to claim 14, wherein, described olefin polymerization catalysisIn carrier, described two oxyl hydrocarbon compounds are selected from 2,2-dimethoxypropane, 2,2-dimethoxy-butane,2,2-dimethoxy pentane, 3,3-dimethoxy pentane, 2,2-di ethyl propyl ether and 2,2-, bis-phenoxy groups thirdOne or more in alkane.
16. according to the catalytic component described in any one in claim 1-6, wherein, and described alkeneIn polymerizing catalyst carrier, structure suc as formula the oxirane compounds shown in (II) in, R5WithR6Be hydrogen, C independently of one another1-C3Alkyl or haloalkyl.
17. catalytic components according to claim 16, wherein, described olefin polymerization catalysisIn carrier, described oxirane compounds is selected from oxirane, expoxy propane, epoxy butane, epoxyOne or more in chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy NBB.
18. according to the catalytic component described in any one in claim 1-6, wherein, and described alkeneThe average particulate diameter of polymerizing catalyst carrier is 10-100 micron, and particle diameter distributes and is less than 1.2.
19. catalytic components according to claim 18, wherein, described olefin polymerization catalysisThe average particulate diameter of carrier is 40-60 micron, and particle diameter is distributed as 0.6-0.8.
20. according to the catalytic component described in any one in claim 1-6, wherein, and described titanizingCompound is general formula Ti (ORa)4-mXmCompound, wherein, RaFor C1-C14Aliphatic group, X be F,Cl or Br, the integer that m is 1-4.
21. catalytic components according to claim 20, wherein, described titanium compound is tetrachloroChange titanium, titanium tetrabromide, titanium tetrafluoride, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxyOne in titanium trichloride, triethoxy titanium chloride, diethoxy titanium chloride and ethyoxyl titanium trichlorideOr multiple.
22. according to the catalytic component described in any one in claim 1-6, wherein, and described alkeneThe preparation method of polymerizing catalyst carrier comprises the following steps:
(1) compound, general formula that the magnesium halide that is MgXY by general formula, general formula are ROH are R'OHCompound, two oxyl hydrocarbon compounds mix with inert liquid medium and heat, obtain liquefied mixture;
(2) liquefied mixture emulsification step (1) being obtained, and by emulsification product and ethylene oxideCompound haptoreaction;
In formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C1-C14AlcoxylBase, C6-C14Aryl or C6-C14Aryloxy group; In general formula R OH, R is C1-C8Alkyl orC3-C8Cycloalkyl; General formula R ' in OH, R' is C16-C24Alkyl or aralkyl; Described two hydrocarbonThe structure of oxygen base hydrocarbon compound is suc as formula shown in (I), and the structure of described oxirane compounds is suc as formula (II)Shown in:
Wherein, R1、R2、R3And R4Be hydrogen, C independently of one another1-C10Alkyl or haloalkyl,C3-C10Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl orAlkyl halide aryl, C7-C10Aralkyl or halo aralkyl; R5And R6Be hydrogen, C independently of one another1-C5Alkyl or haloalkyl,
Magnesium halide taking 1mol general formula as MgXY is benchmark, the consumption of the compound that general formula is ROHFor 4-30mol, the consumption of the compound that general formula is R'OH is 0.001-1.5mol, and structure is suc as formula (I)The consumption of two shown oxyl hydrocarbon compounds is 0.001-1.5mol, and structure is suc as formula the ring shown in (II)The consumption of oxidative ethane compounds is 1-10mol.
23. catalytic components according to claim 22, wherein, taking 1mol general formula as MgXYMagnesium halide be benchmark, the consumption of the compound that general formula is ROH is 6-20mol, general formula is R'OHThe consumption of compound is 0.01-1mol, and structure is suc as formula the consumption of two oxyl hydrocarbon compounds shown in (I)For 0.01-1mol, structure is 2-6mol suc as formula the consumption of the oxirane compounds shown in (II).
24. catalytic components according to claim 22, wherein, in step (1), described in addThe temperature of heat is 80-120 DEG C, and the time is 0.5-5 hour.
25. catalytic components according to claim 24, wherein, in step (1), described in addThe temperature of heat is 80-100 DEG C, and the time is 0.5-3 hour.
26. catalytic components according to claim 22, wherein, in step (2), described in connectThe condition of touching reaction comprises that temperature is 80-120 DEG C, and the time is 20-60 minute.
27. catalytic components according to claim 26, wherein, in step (2), described in connectThe condition of touching reaction comprises that temperature is 80-100 DEG C, and the time is 20-50 minute.
28. catalytic components according to claim 22, wherein, taking 1mol general formula as MgXYMagnesium halide be benchmark, the consumption of described inert liquid medium is 0.8-10L; Described inert liquid mediumFor silicone oil and/or inert fluid varsol.
29. catalytic components according to claim 28, wherein, described inert liquid medium isKerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, benzeneOne or more in base silicone oil and methyl phenyl silicone oil.
The catalytic component for olefinic polymerization described in 30. claim 1-29 any one forApplication in the catalyst of olefinic polymerization.
31. 1 kinds of catalyst for olefinic polymerization, this catalyst contains:
(1) catalytic component for olefinic polymerization described in any one in claim 1-29;
(2) alkyl aluminum compound; And
(3) optional external donor compound.
The catalyst for olefinic polymerization described in 32. claims 31 should olefinic polyreactionWith.
33. 1 kinds of olefine polymerizing process, the method comprises: under olefinic polymerization condition, by one or manyPlant the catalytic component for olefinic polymerization, alkane described in any one in alkene and claim 1-29Base aluminium compound and optional external donor compound contact.
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| CN102040683A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Spherical carriers for olefin polymerization catalyst and preparation method |
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