CN106608940B - The preparation method of catalytic component for olefinic polymerization - Google Patents
The preparation method of catalytic component for olefinic polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of catalytic component for olefinic polymerization, in the preparation process of catalytic component, certain synergistic effect is shown collectively as precipitation additive by using logical formula (I) compound represented and organic acid compound anhydride, the catalyst good fluidity of preparation, particle shape is good, even particle size distribution, catalyst high comprehensive performance；Especially when being used for propylene polymerization, the activity of catalyst is high, and capacity of orientation is good, and resulting polymers isotacticity is high, is conducive to industrial applications；
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of preparation side of the catalytic component for olefinic polymerization
Method.
Background technique
The usually first chemically activated magnesium chloride of the preparation of magnesium chloride supported catalyst, is then handled with titanium compound high
Active magnesium chloride.Magnesium chloride is generally first dissolved in dicyandiamide solution by chemical method activated magnesium chloride, then molten with heat treatment removing
Agent adds the technologies such as precipitation agent that magnesium chloride is precipitated again from solution.And it uses and the technologies such as precipitation agent is added to make magnesium chloride from solution
In be precipitated again method when, generally require be added precipitation additive can just obtain even-grained solids.
Show that using phthalic anhydride as precipitation additive be preferred example in the prior art, but what is thus prepared urges
Agent activity is not high.In order to improve the activity of catalyst, have been reported that using malonate as precipitation additive, but such catalyst exists
While improving catalyst activity, the capacity of orientation of catalyst is reduced, the industrial application of catalyst is limited.
Therefore, it is badly in need of researching and developing a kind of preparation method of catalytic component for olefinic polymerization at present, thus method
The catalyst good fluidity of preparation, particle shape is good, even particle size distribution, the high comprehensive performance of catalyst, by the catalyst
When for propylene polymerization, the catalyst activity is high, and capacity of orientation is good.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide one kind to be used for olefinic polymerization
Catalytic component preparation method, by using logical formula (I) compound represented and organic acid compound anhydride collectively as
The catalyst good fluidity of precipitation additive preparation, particle shape is good, even particle size distribution, the high comprehensive performance of catalyst.With
When olefinic polymerization, especially propylene polymerization, the catalyst activity is high, and resulting polymers isotacticity is high.
For this purpose, first aspect present invention provides a kind of preparation method of catalytic component for olefinic polymerization, packet
It includes:
Magnesium compound is dissolved in containing organic epoxide, organic phosphorus compound, logical formula (I) compound represented by step A
In the dicyandiamide solution of organic acid compound anhydride, under precipitation agent effect, solids is made；
Step B is filtered, washed with obtained solid object in titanium compound processing step A, and catalytic component is made；
In logical formula (I), R1And R2It is identical or different, it is each independently selected from C1-C20Substituted or unsubstituted straight chain or
Branched alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substitution or
Alkaryl, the C of unsubstituted linear chain or branched chain7-C20Substituted or unsubstituted linear chain or branched chain aralkyl, C2-C20Take
Generation or unsubstituted alkylene and C10-C20Substituted or unsubstituted fused ring aryl.It is preferred that R1And R2It is each independently selected from C1-
C10Substituted or unsubstituted linear or branched alkyl group, C3-C10Substituted or unsubstituted naphthenic base, C6-C10Substitution or not
Substituted aryl, C7-C10Substituted or unsubstituted linear chain or branched chain alkaryl, C7-C10Substituted or unsubstituted straight chain
Or the aralkyl and C of branch2-C10Substituted or unsubstituted alkylene.
In logical formula (I), R3And R4It is identical or different, it is each independently selected from hydrogen, C1-C20It is substituted or unsubstituted straight
The alkyl of chain or branch, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20's
Alkaryl, the C of substituted or unsubstituted linear chain or branched chain7-C20Substituted or unsubstituted linear chain or branched chain aralkyl, C2-
C20Substituted or unsubstituted alkylene and C10-C20Substituted or unsubstituted fused ring aryl；R3And R4Optionally it is keyed to
Ring is not cyclic.In certain specific embodiments of the invention, R3And R4When bonded cyclization, in ring can also containing double bond or
Hetero atom.
In the present invention, the substituted alkyl (linear chain or branched chain), naphthenic base, aryl, alkaryl (linear chain or branched chain), virtue
Alkyl (linear chain or branched chain) or alkylene, such as alkyl (linear chain or branched chain), naphthenic base, aryl, alkaryl (linear chain or branched chain), virtue
The carbon or hydrogen atom of alkyl (linear chain or branched chain) or alkylene are optionally replaced by one or several hetero atoms, the hetero atom
Selected from one of nitrogen, oxygen, sulphur, silicon, phosphorus and halogen atom or a variety of.
The inventors of the present invention discovered through researches that by using logical formula (I) compound represented and organic acid compound anhydride
Collectively as the catalyst good fluidity of precipitation additive preparation, particle shape is good, even particle size distribution, the comprehensive performance of catalyst
It is excellent.When the catalyst is used for olefinic polymerization, especially propylene polymerization, the catalyst activity is high, resulting polymers etc.
Normality is high.
Magnesium compound " is dissolved in containing organic epoxide, organic phosphorus compound, logical formula (I) institute by term of the present invention
In the dicyandiamide solution of the compound and organic acid compound anhydride that show " comprising first magnesium compound is dissolved in containing organic epoxide
In the mixed solution of organic phosphorus compound, logical formula (I) compound represented and organic acid compound anhydride are added；Also include
By magnesium compound be dissolved in containing logical formula (I) compound represented, organic acid compound anhydride and containing organic epoxide with have
In the dicyandiamide solution that the mixed solution of machine phosphorus compound collectively constitutes.According to the present invention, lead to formula (I) compound represented and organic
Anhydride compound can be added simultaneously, can also be added in the different phase of reaction.
Some specific embodiments according to the present invention use and magnesium compound are dissolved in containing organic in step
In the mixed solution of epoxide and organic phosphorus compound again with logical formula (I) compound represented and organic acid compound anhydride
Mixing.
In some preferred embodiments of the invention, during handling solids with titanium compound and/or handle
Internal electron donor compound is added before.
In the present invention, the internal electron donor compound is selected from nitrogenous compound, oxygenatedchemicals, phosphorus-containing compound, contains
One of sulphur compound, silicon-containing compound and logical formula (I) compound represented are a variety of.It can be used as in the prior art interior to electricity
Nitrogenous compound, oxygenatedchemicals, phosphorus-containing compound, sulfur-containing compound and the silicon-containing compound of daughter are used equally for the present invention
In.It is preferred that the internal electron donor compound is oxygenatedchemicals.It is furthermore preferred that the internal electron donor compound is esters
Close object.Most preferably, the internal electron donor compound is diol-lipid compound, such as 2,4- glycol dibenzoate,
3,5- heptandiol dibenzoate, 4- ethyl -3,5- heptandiol dibenzoate etc..
In some embodiments of the invention, the logical formula (I) compound represented is selected from diisobutyl malonic acid diethyl
Ester, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate, diisobutyl dipropyl malonate, di-n-butyl third
Dipropyl malona-te, di-t-butyl dipropyl malonate, diisobutyl dibutyl malonate, di-n-butyl dibutyl malonate, two
Tert-butyl dibutyl malonate, diisobutyl malonic acid diamyl ester, di-n-butyl malonic acid diamyl ester, di-t-butyl malonic acid two
Pentyl ester, diisobutyl malonic acid dihexyl, di-n-butyl malonic acid dihexyl, di-t-butyl malonic acid dihexyl, diisobutyl
Two heptyl ester of malonic acid, two heptyl ester of di-n-butyl malonic acid, two heptyl ester of di-t-butyl malonic acid, dipropyl dipropyl malonate, two
Isoamyl-malonic acid dipropyl, two n-amyl malonic acid dipropyls, dihexyl dipropyl malonate, two n-amyl malonic acid dipropyls
Ester, phenylethyl dipropyl malonate, phenyl methyl dipropyl malonate, phenyl propyl dipropyl malonate, phenyl normal-butyl
Dipropyl malonate, phenyl isobutyl propylmalonic acid dipropyl, phenyl isoamyl-malonic acid dipropyl, phenyl n-amyl malonic acid two
Propyl ester, diphenylprop dipropyl malona-te, benzyl ethyl malonic acid dipropyl, benzyl methyl dipropyl malonate, benzyl propyl third
Dipropyl malona-te, benzyl n-butylmalonic acid dipropyl, benzyl isobutyl group dipropyl malonate, benzyl isoamyl-malonic acid dipropyl
Ester, benzyl n-amyl malonic acid dipropyl, dibenzyl dipropyl malonate, phenylethyl dibutyl malonate, phenyl methyl third
Adipate, phenyl propyl dibutyl malonate, phenyl n-butylmalonic acid dibutyl ester, two fourth of phenyl isobutyl propylmalonic acid
Ester, phenyl isoamyl-malonic acid dibutyl ester, phenyl n-amyl malonic acid dibutyl ester, diphenylprop adipate, benzyl ethyl
Dibutyl malonate, benzyl methyl dibutyl malonate, benzyl propylmalonic acid dibutyl ester, two fourth of benzyl n-butylmalonic acid
Ester, benzyl isobutyl group dibutyl malonate, benzyl isoamyl-malonic acid dibutyl ester, benzyl n-amyl malonic acid dibutyl ester, dibenzyl
Propylmalonic acid dibutyl ester, phenylethyl malonic acid diamyl ester, phenyl methyl malonic acid diamyl ester, phenyl propyl malonic acid diamyl
Ester, phenyl n-butylmalonic acid diamyl ester, phenyl isobutyl propylmalonic acid diamyl ester, phenyl isoamyl-malonic acid diamyl ester, phenyl
N-amyl malonic acid diamyl ester, diphenylprop diacid diamyl ester, benzyl ethyl malonic acid diamyl ester, benzyl methyl malonic acid diamyl
Ester, benzyl propylmalonic acid diamyl ester, benzyl n-butylmalonic acid diamyl ester, benzyl isobutyl propylmalonic acid diamyl ester, benzyl are different
Amyl malonic acid diamyl ester, benzyl n-amyl malonic acid diamyl ester, dibenzyl propylmalonic acid diamyl ester, two ring of phenylethyl malonic acid
Own ester, phenyl methyl malonic acid dicyclohexyl maleate, phenyl propyl malonic acid dicyclohexyl maleate, phenyl n-butylmalonic acid dicyclohexyl maleate,
Phenyl isobutyl propylmalonic acid dicyclohexyl maleate, phenyl isoamyl-malonic acid dicyclohexyl maleate, phenyl n-amyl malonic acid dicyclohexyl maleate, two
Phenylmalonic acid dicyclohexyl maleate, benzyl ethyl malonic acid dicyclohexyl maleate, benzyl methyl malonic acid dicyclohexyl maleate, benzyl propyl the third two
Sour dicyclohexyl maleate, benzyl n-butylmalonic acid dicyclohexyl maleate, benzyl isobutyl propylmalonic acid dicyclohexyl maleate, benzyl isoamyl-malonic acid
Dicyclohexyl maleate, benzyl n-amyl malonic acid dicyclohexyl maleate, dibenzyl propylmalonic acid dicyclohexyl maleate, phenyl methyl diphenyl malonate,
Phenyl propyl diphenyl malonate, phenyl n-butylmalonic acid diphenyl ester, phenyl isobutyl propylmalonic acid diphenyl ester, phenyl isopentyl
Diphenyl malonate, phenyl n-amyl malonic acid diphenyl ester, diphenyl diphenyl malonate, benzyl ethyl malonic acid diphenyl ester,
Benzyl methyl diphenyl malonate, benzyl propylmalonic acid diphenyl ester, benzyl n-butylmalonic acid diphenyl ester, benzyl isobutyl group third
Two diphenyl phthalates, benzyl isoamyl-malonic acid diphenyl ester, benzyl n-amyl malonic acid diphenyl ester, dibenzyl diphenyl malonate,
Fluorenyl methyl malonic acid dicyclohexyl maleate, fluorenyl propylmalonic acid dicyclohexyl maleate, fluorenyl n-butylmalonic acid dicyclohexyl maleate, fluorenyl are different
Butylmalonic acid dicyclohexyl maleate, fluorenyl isoamyl-malonic acid dicyclohexyl maleate, fluorenyl n-amyl malonic acid dicyclohexyl maleate, two fluorenyls third
Dicyclohexyl sulfosuccinnate ester, allyl methyl diphenyl malonate, allyl propylmalonic acid diphenyl ester, allyl n-butylmalonic acid
Diphenyl ester, allyl isobutyl group diphenyl malonate, allyl isoamyl-malonic acid diphenyl ester, allyl n-amyl malonic acid two
Phenyl ester, diallyl diphenyl malonate, allyl methyl dimethyl malenate, allyl propylmalonic acid dimethyl ester, allyl
Base n-butylmalonic acid dimethyl ester, allyl isobutyl group dimethyl malenate, allyl isoamyl-malonic acid dimethyl ester, allyl
N-amyl malonic acid dimethyl ester, diallyl dimethyl malenate, allyl methyl diethyl malonate, allyl propyl the third two
Diethyl phthalate, allyl diethyl butylmalonate, allyl iso-butyl diethyl malonate, allyl isoamyl-malonic acid
Diethylester, allyl n-amyl malonic acid diethylester, diallyl diethyl malonate, allyl methyl dipropyl malonate,
Allyl propylmalonic acid dipropyl, allyl n-butylmalonic acid dipropyl, allyl isobutyl group dipropyl malonate, allyl
Base isoamyl-malonic acid dipropyl, allyl n-amyl malonic acid dipropyl, diallyl dipropyl malonate, allyl methyl
Dibutyl malonate, allyl propylmalonic acid dibutyl ester, allyl n-butylmalonic acid dibutyl ester, allyl isobutyl group the third two
Dibutyl phthalate, allyl isoamyl-malonic acid dibutyl ester, allyl n-amyl malonic acid dibutyl ester, two fourth of diallyl malonic acid
Ester, allyl methyl malonic acid diamyl ester, allyl propylmalonic acid diamyl ester, allyl n-butylmalonic acid diamyl ester, alkene
Propyl isobutyl propylmalonic acid diamyl ester, allyl isoamyl-malonic acid diamyl ester, allyl n-amyl malonic acid diamyl ester, diene
Propylmalonic acid diamyl ester, allyl methyl malonic acid dicyclohexyl maleate, allyl propylmalonic acid dicyclohexyl maleate, the positive fourth of allyl
Propylmalonic acid dicyclohexyl maleate, allyl isobutyl propylmalonic acid dicyclohexyl maleate, allyl isoamyl-malonic acid dicyclohexyl maleate, allyl
One or more of n-amyl malonic acid dicyclohexyl maleate and diallyl malonic acid dicyclohexyl maleate.It is preferred that the logical formula (I) institute
The compound shown be selected from diisobutyl diethyl malonate, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate,
Diisobutyl dipropyl malonate, di-n-butyl dipropyl malonate, di-t-butyl dipropyl malonate, benzyl malonic acid diethyl
Ester, benzyl malonic acid dipropyl, ethyl benzoic acid, phenylethyl dipropyl malonate, dipropyl propylmalonic acid two
One of ethyl ester, dipropyl dipropyl malonate, diallyl diethyl malonate and diallyl dipropyl malonate or
It is several.
In some embodiments of the invention, the magnesium compound is selected from magnesium dihalide, alkoxyl magnesium, alkyl magnesium, dihalo-
One of halogen atom is by oxyl or halogenated oxyl institute in the hydrate or alcohol adduct and magnesium dihalide molecular formula of change magnesium
Displaced derivative.It is preferred that the magnesium compound is the alcohol adduct of magnesium dihalide or magnesium dihalide, such as magnesium dichloride, dibrominated
Magnesium, magnesium diiodide and their alcohol adduct.
In other embodiments of the invention, the organic acid compound anhydride be selected from acetic anhydride, phthalic anhydride,
One of succinic anhydride, maleic anhydride and pyromellitic acid anhydride are a variety of.
According to the method for the present invention, the general formula of the titanium compound is TiXm(OR1)4-m, wherein R1Selected from C1-C20Alkyl；X
For halogen；1≤m≤4.The specific example of the titanium compound, such as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four butoxy
Titanium, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine.It is preferred that the titanium compound is
Titanium tetrachloride.
In some embodiments of the invention, the precipitation agent is metal halide；It is preferred that the precipitation agent is halogenated titanium；
It is furthermore preferred that the precipitation agent is titanium tetrachloride.
Organic epoxy compound object, organic phosphorus compound in the present invention can be found in Chinese patent CN85100997, phase
Hold inside the Pass and is incorporated herein by reference.
It is emphasized that wherein organic epoxy compound object include carbon atom number be the aliphatic olefin of 2-8, alkadienes or
At least one of the oxide of halogenated aliphatic alkene or alkadienes, glycidol ether and inner ether.Particular compound is such as: epoxy
Ethane, propylene oxide, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether,
Diglycidyl ether, tetrahydrofuran.Wherein organic phosphorus compound includes the hydrocarbyl carbonate or halogenated of ortho-phosphoric hydrocarbyl carbonate, phosphorous acid
Hydrocarbyl carbonate, specifically such as: orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, phosphorous acid front three
Ester, triethyl phosphite, tributyl phosphite, phosphorous triphenyl phosphate methyl esters.
In the preparation method of catalytic component of the present invention, based on the magnesium elements in every mole of magnesium compound,
The dosage of compound shown in logical formula (I) is 0.005-2 moles；It is preferred that 0.01-0.5 moles；The dosage of organic acid compound anhydride
0.005-2 moles；It is preferred that 0.01-0.2 moles；The dosage of titanium compound is 3-40 moles；It is preferred that 5-30 moles；Internal electron donor
The dosage of compound be 0.005-15, preferably 0.05-5 moles；The dosage of organic epoxy compound object is 0.2-10 moles；It is organic phosphorus
The dosage of compound is 0.1-3 moles.
In certain embodiments of the present invention, in stepb, with obtained solid object in titanium compound processing step A, warp
After being filtered, washed, drying, dry catalytic component is made.
Second aspect of the present invention provides a kind of catalyst for olefinic polymerization, the reaction product comprising following components:
Component L, the catalytic component that as described in the first aspect of the invention prepared by method；
Component M, alkyl aluminum compound；And optional
Component N, external electron donor component.
According to the present invention, the general formula of the alkyl aluminum compound is AlRnX3-n, wherein R is selected from hydrogen, C1-C20Alkyl.X
For halogen.0 n≤3 <.Specifically can be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, tri-n-octylaluminium,
One hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and dichloro
One of aluminium ethide is a variety of.It is preferred that the alkyl aluminum compound is triethyl aluminum and/or triisobutyl aluminium.
Term of the present invention " optional, external electron donor component " means as needed, selection plus or be not added it is outer to
Electron compound.
In the present invention, the external electron donor component includes but is not limited to general formula (II) compound represented (i.e. organosilicon
Compound):
(R2)kSi(OR3)4-k (Ⅱ)
In the general formula (II), 0≤k≤3；R2Selected from halogen, hydrogen atom, C1-C20Alkyl, C3-C20Naphthenic base, C6-
C20Aryl, C1-C20Halogenated alkyl and amino；R3Selected from C1-C20Alkyl, C3-C20Naphthenic base, C6-C20Aryl,
C1-C20Halogenated alkyl and amino.The specific example of the organo-silicon compound includes, for example: trimethylmethoxysilane, three
Methylethoxy base silane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, dimethoxydiphenylsilane, hexichol
Base diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxysilane, cyclohexyl first
Base dimethoxysilane, methyl-t-butyldimethoxysilane.
In the present invention, the molar ratio of component L, component M and component N are with titanium: aluminium: external electron donor is calculated as 1:(5-1000):
(0-500).The molar ratio of preferred ingredient L, component M and component N are with titanium: aluminium: external electron donor is calculated as 1:(25-100): (25-
100).When the external donor compound of component N is the organo-silicon compound of logical formula (II), component L, component M and component N's
Molar ratio is with titanium: aluminium: silicon is calculated as 1:(5-1000): (0-500).The molar ratio of preferred ingredient L, component M and component N are with titanium: aluminium:
Silicon is calculated as 1:(25-100): (25-100).
Third aspect present invention provides a kind of pre-polymerized catalyst for olefinic polymerization, including such as first party of the present invention
The catalytic component or catalyst as described in respect of the second aspect of the invention and prepolymerization alkene of face the method preparation carry out pre-polymerization
Close resulting prepolymer.
Term " pre-polymerized catalyst " of the present invention refers to the catalyst for passing through polymerization procedure with lower transforming degree.This
In invention, the pre-polymerization multiple of the prepolymer is 0.1-1000g olefin polymer/g ingredient of solid catalyst.Preferably, pre-polymerization
Multiple is about 0.2-500 grams polymer/g ingredient of solid catalyst.
Term " prepolymerization alkene " of the present invention refer to for catalytic component of the present invention or catalyst into
Row prepolymerization is to obtain the alkene of pre-polymerized catalyst.It is preferred that the prepolymerization alkene is ethylene and/or propylene.
Prepolymerization process can carry out in a liquid or in gas phase at a temperature of -20 DEG C to 80 DEG C, preferably 0-50 DEG C.
Prepolymerization step can be used as the online progress of a part in continuous polymerization technique, or independently carry out in intermittently operated.
Fourth aspect present invention provides a kind of method for olefinic polymerization, and the alkene is in first aspect present invention institute
State prepolymerization described in the catalytic component of method preparation, catalyst or third aspect present invention described in second aspect of the present invention
It is polymerize in the presence of catalyst.
Catalyst of the invention can be directly added into reactor in polymerization process.Alternatively, catalyst can add
Prepolymerization is carried out before entering first polymer reactor, participates in reacting in a manner of pre-polymerized catalyst.
In the present invention, the general formula of the alkene is CH2=CHR, wherein R is selected from hydrogen, C1-C12Alkyl and C6-C12Virtue
Base.It is preferred that the alkene is ethylene and/or propylene.
Olefin polymerization of the invention is carried out according to well known polymerization, can be carried out in liquid phase or gas phase, or
Person can also carry out under the operation that liquid and gas polymerization stage combines.Using conventional technique such as slurry process, gas phase fluidization
Bed etc., wherein alkene is selected from ethylene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexene, the homopolymerization of special propylene or third
The combined polymerization of alkene and other alkene.Preferably be to use following reaction condition: polymerization temperature is 0-150 DEG C.It is preferred that the polymerization
Temperature is 60-90 DEG C.Polymerization pressure is 0.01-10MPa.
It is had the advantage that provided by the present invention for the preparation method of the catalytic component of olefinic polymerization
(1) logical formula (I) compound represented and organic acid compound anhydride are added in the preparation process of catalytic component
Collectively as precipitation additive, the catalyst activity of preparation is higher than urging when one of compound is used alone as precipitation additive
Agent activity, maintains high capacity of orientation, shows certain synergistic effect, can satisfy industrialized requirement, has
There is wide prospects for commercial application.
(2) present invention gained catalyst good fluidity, particle shape be good, even particle size distribution, catalyst it is comprehensive
It can be excellent.
(3) when present invention gained catalyst is used for olefinic polymerization, especially propylene polymerization, have good hydrogen tune sensitive
Property, obtained fine polymer powder is few, and stereoregularity is good, and molecular weight distribution is wide.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
Test method of the invention is as follows:
(1) polymer isotactic index II: use the measurement of heptane extraction process (heptane boiling extracting 6 hours): 2g is dry to be gathered
Object sample is closed, is placed in extractor after being extracted 6 hours with boiling heptane, residue is dry to the resulting polymer weight of constant weight
(g) ratio with 2 is isotactic index.
(2) it melt index MI: using fusion index instrument under 230 DEG C, 2.16kg pressure, " is used according to ASTM D1238-99
Squeeze the standard test method of plastometer measurement thermoplasticity fusing flow rate " measurement.
(3) polymer molecular weight distribution MWD (MWD=Mw/Mn): using the Waters Alliance of Waters company
The measurement of GPC2000 gel permeation chromatograph, with 1,2,4- trichloro-benzenes for solvent, styrene is standard specimen.
Embodiment
Embodiment 1: the preparation of catalytic component
In the reactor that pure nitrogen gas is sufficiently displaced from, magnesium chloride 4.8g, toluene 95mL, epoxychloropropane 4mL, phosphorus are sequentially added
Sour tributyl 12.5mL, is warming up to 50 DEG C, and maintain 2.5h under stirring, solid is completely dissolved, and dibutyl malonic acid diethyl is added
Ester 2mmol, phthalic anhydride 8mmol continue to 1h.Solution is cooled to -29 DEG C hereinafter, TiCl is added dropwise in 1h456mL,
It drips and is at the uniform velocity warming up to 80 DEG C of addition 6mmol 3,5- heptandiol dibenzoates, maintain temperature 1h, after filtering, use first respectively
Benzene 70mL is washed twice, and obtains solid sediment.Then toluene 60mL and TiCl are added into sediment440mL is warming up to
110 DEG C, maintain 1h, filtering；Same operation is in triplicate.And then with toluene 70mL, the time is respectively 10min, then uses hexane
60mL, twice, room temperature washes twice washing precipitate at 60 DEG C, after dry, obtains dry catalytic component.
Embodiment 2: the preparation of catalytic component
Method is with embodiment 1, the difference is that 4- glycol dibenzoate substitutes 3,5- heptandiol hexichol first with 2
Acid esters.
Embodiment 3: the preparation of catalytic component
Method is with embodiment 1, the difference is that substituting dibutyl malonic acid two using diisobutyl diethyl malonate
Ethyl ester.
Embodiment 4: the preparation of catalytic component
Method is with embodiment 1, the difference is that the additional amount of dibutyltin diethyl malonate is 1mmol, O-phthalic
The additional amount of acid anhydrides is 9mmol.
Embodiment 5: the preparation of catalytic component
Method is with embodiment 1, the difference is that the additional amount of dibutyltin diethyl malonate is 4mmol, O-phthalic
The additional amount of acid anhydrides is 6mmol.
Embodiment 6: the preparation of catalytic component
Method is with embodiment 1, the difference is that the additional amount of dibutyltin diethyl malonate is 8mmol, O-phthalic
The additional amount of acid anhydrides is 2mmol.
Embodiment 7: the preparation of catalytic component
Method is with embodiment 1, the difference is that the additional amount of dibutyltin diethyl malonate is 9mmol, O-phthalic
The additional amount of acid anhydrides is 1mmol.
Comparative example 1: the preparation of catalytic component
Method is with embodiment 1, the difference is that substituting dibutyl malonic acid diethyl using phthalic anhydride 10mmol
Ester 2mmol, phthalic anhydride 8mmol.
Comparative example 2: the preparation of catalytic component
Method is with comparative example 1, the difference is that using dibutyltin diethyl malonate 10mmol substitution dibutyl the third two
Diethyl phthalate 2mmol, phthalic anhydride 8mmol.
Comparative example 3: the preparation of catalytic component
Method is with embodiment 1, the difference is that substituting dibutyltin diethyl malonate using phthalic anhydride 8mmol
2mmol, phthalic anhydride 8mmo；80 DEG C of addition 6mmol 3,5- heptandiol dibenzoates, meanwhile, bis- fourth of 2mmol is added
Propylmalonic acid diethylester.
Propylene polymerization experiment
Catalytic component is subjected to propylene polymerization respectively.The method of propylene polymerization are as follows: volume is the stainless steel cauldron of 5L,
After gaseous propylene is sufficiently displaced from, AlEt is added32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.lmmol, then
It is separately added into catalytic component 8-10mg and 1.2L hydrogen (standard state) obtained by embodiment 1-7 and comparative example 1-2, is passed through liquid
Body propylene 2.3L, is warming up to 70 DEG C, maintains this temperature 1 hour.Cooling, pressure release obtain PP powder.The activity of catalyst is calculated,
The isotactic index and melt index of resulting polymers are measured, specific data are shown in Table shown in 1.
1 propylene polymerization experimental results of table
| Catalytic component | Active (kgPP/gcat/hr) | Isotactic index (%) | Melt index (g/10min) |
| Embodiment 1 | 71.0 | 98.2 | 2.9 |
| Embodiment 2 | 83.5 | 98.3 | 1.2 |
| Embodiment 3 | 66.8 | 98.1 | 3.5 |
| Embodiment 4 | 66.1 | 98.4 | 3.0 |
| Embodiment 5 | 71.8 | 98.1 | 2.8 |
| Embodiment 6 | 69.9 | 98.0 | 2.9 |
| Embodiment 7 | 68.1 | 97.9 | 4.6 |
| Comparative example 1 | 52.1 | 98.3 | 2.6 |
| Comparative example 2 | 63.9 | 97.3 | 3.7 |
| Comparative example 3 | 48.0 | 96.6 | 4.1 |
The data from table 1 are it is known that using logical formula (I) compound represented and organic acid anhydride collectively as precipitation additive
Catalyst obtained by preparation has preferable comprehensive performance, and catalyst activity is used as higher than one of compound of exclusive use and helps analysis
Catalyst activity when agent out, obtained polymer isotacticity with higher, is conducive to industrial applications.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (22)
1. a kind of preparation method of the catalytic component for olefinic polymerization comprising:
Magnesium compound is dissolved in containing organic epoxide, organic phosphorus compound, logical formula (I) compound represented and is had by step A
In the dicyandiamide solution of machine anhydride compound, under precipitation agent effect, solids is made；
Step B is filtered, washed with obtained solid object in titanium compound processing step A, and catalytic component is made；
In logical formula (I), R1And R2It is identical or different, it is each independently selected from C1-C20Substituted or unsubstituted linear chain or branched chain
Alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substitution or not
Alkaryl, the C of substituted linear chain or branched chain7-C20Substituted or unsubstituted linear chain or branched chain aralkyl, C2-C20Substitution
Or unsubstituted alkylene and C10-C20Substituted or unsubstituted fused ring aryl；
R3And R4It is identical or different, it is each independently selected from hydrogen, C1-C20Substituted or unsubstituted linear chain or branched chain alkyl,
C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20It is substituted or unsubstituted straight
The alkaryl of chain or branch, C7-C20Substituted or unsubstituted linear chain or branched chain aralkyl, C2-C20It is substituted or unsubstituted
Alkylene and C10-C20Substituted or unsubstituted fused ring aryl；R3And R4It is optionally bonded cyclic or not cyclic.
2. preparation method according to claim 1, which is characterized in that R1And R2It is each independently selected from C1-C10Substitution or
Unsubstituted linear or branched alkyl group, C3-C10Substituted or unsubstituted naphthenic base, C6-C10Substituted or unsubstituted aryl,
C7-C10Substituted or unsubstituted linear chain or branched chain alkaryl, C7-C10Substituted or unsubstituted linear chain or branched chain aralkyl
Base and C2-C10Substituted or unsubstituted alkylene.
3. preparation method according to claim 1 or 2, which is characterized in that in the process with titanium compound processing solids
In and/or processing before be added internal electron donor compound.
4. preparation method according to claim 3, which is characterized in that the internal electron donor compound is selected from nitrogenous chemical combination
One of object, oxygenatedchemicals, phosphorus-containing compound, sulfur-containing compound, silicon-containing compound and logical formula (I) compound represented or
It is a variety of.
5. the preparation method according to claim 4, which is characterized in that the internal electron donor compound is oxygen-containing chemical combination
Object.
6. preparation method according to claim 4 or 5, which is characterized in that the internal electron donor compound is esters
Close object.
7. preparation method according to claim 6, which is characterized in that the internal electron donor compound is diol-lipid
Close object.
8. preparation method according to claim 1 or 2, which is characterized in that the logical formula (I) compound represented is selected from two
Iso-butyl diethyl malonate, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate, diisobutyl malonic acid two
Propyl ester, di-n-butyl dipropyl malonate, di-t-butyl dipropyl malonate, diisobutyl dibutyl malonate, di-n-butyl
Dibutyl malonate, di-t-butyl dibutyl malonate, diisobutyl malonic acid diamyl ester, di-n-butyl malonic acid diamyl ester,
Di-t-butyl malonic acid diamyl ester, diisobutyl malonic acid dihexyl, di-n-butyl malonic acid dihexyl, di-t-butyl malonic acid
Dihexyl, two heptyl ester of diisobutyl malonic acid, two heptyl ester of di-n-butyl malonic acid, two heptyl ester of di-t-butyl malonic acid, dipropyl
Dipropyl malonate, diisoamyl dipropyl malonate, two n-amyl malonic acid dipropyls, dihexyl dipropyl malonate, two
N-amyl malonic acid dipropyl, phenylethyl dipropyl malonate, phenyl methyl dipropyl malonate, phenyl propyl malonic acid two
Propyl ester, phenyl n-butylmalonic acid dipropyl, phenyl isobutyl propylmalonic acid dipropyl, phenyl isoamyl-malonic acid dipropyl, benzene
Base n-amyl malonic acid dipropyl, diphenylprop dipropyl malona-te, benzyl ethyl malonic acid dipropyl, benzyl methyl malonic acid two
Propyl ester, benzyl propylmalonic acid dipropyl, benzyl n-butylmalonic acid dipropyl, benzyl isobutyl group dipropyl malonate, benzyl
Isoamyl-malonic acid dipropyl, benzyl n-amyl malonic acid dipropyl, dibenzyl dipropyl malonate, phenylethyl malonic acid two
Butyl ester, phenyl methyl dibutyl malonate, phenyl propyl dibutyl malonate, phenyl n-butylmalonic acid dibutyl ester, phenyl are different
Butylmalonic acid dibutyl ester, phenyl isoamyl-malonic acid dibutyl ester, phenyl n-amyl malonic acid dibutyl ester, diphenylprop diacid two
Butyl ester, benzyl ethyl malonic acid dibutyl ester, benzyl methyl dibutyl malonate, benzyl propylmalonic acid dibutyl ester, the positive fourth of benzyl
Propylmalonic acid dibutyl ester, benzyl isobutyl group dibutyl malonate, benzyl isoamyl-malonic acid dibutyl ester, benzyl n-amyl malonic acid
Dibutyl ester, dibenzyl dibutyl malonate, phenylethyl malonic acid diamyl ester, phenyl methyl malonic acid diamyl ester, phenyl propyl
Malonic acid diamyl ester, phenyl n-butylmalonic acid diamyl ester, phenyl isobutyl propylmalonic acid diamyl ester, phenyl isoamyl-malonic acid two
Pentyl ester, phenyl n-amyl malonic acid diamyl ester, diphenylprop diacid diamyl ester, benzyl ethyl malonic acid diamyl ester, benzyl methyl
Malonic acid diamyl ester, benzyl propylmalonic acid diamyl ester, benzyl n-butylmalonic acid diamyl ester, benzyl isobutyl propylmalonic acid diamyl
Ester, benzyl isoamyl-malonic acid diamyl ester, benzyl n-amyl malonic acid diamyl ester, dibenzyl propylmalonic acid diamyl ester, phenylethyl
Malonic acid dicyclohexyl maleate, phenyl methyl malonic acid dicyclohexyl maleate, phenyl propyl malonic acid dicyclohexyl maleate, phenyl n-butylmalonic acid
Dicyclohexyl maleate, phenyl isobutyl propylmalonic acid dicyclohexyl maleate, phenyl isoamyl-malonic acid dicyclohexyl maleate, phenyl n-amyl malonic acid two
Cyclohexyl, diphenylprop dicyclohexyl sulfosuccinnate ester, benzyl ethyl malonic acid dicyclohexyl maleate, benzyl methyl malonic acid dicyclohexyl maleate, benzyl
Base propylmalonic acid dicyclohexyl maleate, benzyl n-butylmalonic acid dicyclohexyl maleate, benzyl isobutyl propylmalonic acid dicyclohexyl maleate, benzyl are different
Amyl malonic acid dicyclohexyl maleate, benzyl n-amyl malonic acid dicyclohexyl maleate, dibenzyl propylmalonic acid dicyclohexyl maleate, phenyl methyl the third two
Diphenyl phthalate, phenyl propyl diphenyl malonate, phenyl n-butylmalonic acid diphenyl ester, phenyl isobutyl propylmalonic acid diphenyl ester,
Phenyl isoamyl-malonic acid diphenyl ester, phenyl n-amyl malonic acid diphenyl ester, diphenyl diphenyl malonate, benzyl ethyl the third two
Diphenyl phthalate, benzyl methyl diphenyl malonate, benzyl propylmalonic acid diphenyl ester, benzyl n-butylmalonic acid diphenyl ester, benzyl
Base isobutyl group diphenyl malonate, benzyl isoamyl-malonic acid diphenyl ester, benzyl n-amyl malonic acid diphenyl ester, dibenzyl the third two
Diphenyl phthalate, fluorenyl methyl malonic acid dicyclohexyl maleate, fluorenyl propylmalonic acid dicyclohexyl maleate, two hexamethylene of fluorenyl n-butylmalonic acid
Ester, fluorenyl isobutyl propylmalonic acid dicyclohexyl maleate, fluorenyl isoamyl-malonic acid dicyclohexyl maleate, two hexamethylene of fluorenyl n-amyl malonic acid
Ester, two fluorenyl malonic acid dicyclohexyl maleates, allyl methyl diphenyl malonate, allyl propylmalonic acid diphenyl ester, allyl
N-butylmalonic acid diphenyl ester, allyl isobutyl group diphenyl malonate, allyl isoamyl-malonic acid diphenyl ester, allyl are just
Amyl malonic acid diphenyl ester, diallyl diphenyl malonate, allyl methyl dimethyl malenate, allyl propylmalonic acid
Dimethyl ester, allyl n-butylmalonic acid dimethyl ester, allyl isobutyl group dimethyl malenate, allyl isoamyl-malonic acid two
Methyl esters, allyl n-amyl malonic acid dimethyl ester, diallyl dimethyl malenate, allyl methyl diethyl malonate, alkene
Propyl propylmalonic acid diethylester, allyl diethyl butylmalonate, allyl iso-butyl diethyl malonate, allyl
Isoamyl-malonic acid diethylester, allyl n-amyl malonic acid diethylester, diallyl diethyl malonate, allyl methyl third
Dipropyl malona-te, allyl propylmalonic acid dipropyl, allyl n-butylmalonic acid dipropyl, allyl isobutyl propylmalonic acid
Dipropyl, allyl isoamyl-malonic acid dipropyl, allyl n-amyl malonic acid dipropyl, diallyl malonic acid dipropyl
Ester, allyl methyl dibutyl malonate, allyl propylmalonic acid dibutyl ester, allyl n-butylmalonic acid dibutyl ester, alkene
Propyl isobutyl group dibutyl malonate, allyl isoamyl-malonic acid dibutyl ester, allyl n-amyl malonic acid dibutyl ester, diene
Propylmalonic acid dibutyl ester, allyl methyl malonic acid diamyl ester, allyl propylmalonic acid diamyl ester, allyl normal-butyl third
Diacid diamyl ester, allyl isobutyl propylmalonic acid diamyl ester, allyl isoamyl-malonic acid diamyl ester, allyl n-pentyl the third two
Sour diamyl ester, diallyl malonic acid diamyl ester, allyl methyl malonic acid dicyclohexyl maleate, two hexamethylene of allyl propylmalonic acid
Ester, allyl n-butylmalonic acid dicyclohexyl maleate, allyl isobutyl propylmalonic acid dicyclohexyl maleate, allyl isoamyl-malonic acid two
One or more of cyclohexyl, allyl n-amyl malonic acid dicyclohexyl maleate and diallyl malonic acid dicyclohexyl maleate.
9. preparation method according to claim 8, which is characterized in that it is different that the logical formula (I) compound represented is selected from two
Diethyl butylmalonate, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate, diisobutyl malonic acid dipropyl
Ester, di-n-butyl dipropyl malonate, di-t-butyl dipropyl malonate, diethyl benzyl malonate, benzyl malonic acid dipropyl
Ester, ethyl benzoic acid, phenylethyl dipropyl malonate, dipropyl diethyl malonate, dipropyl propylmalonic acid
One or more of dipropyl, diallyl diethyl malonate and diallyl dipropyl malonate.
10. preparation method according to claim 1 or 2, which is characterized in that
The magnesium compound is selected from magnesium dihalide, alkoxyl magnesium, alkyl magnesium, the hydrate of magnesium dihalide or alcohol adduct and dihalo-
Change the derivative that one of halogen atom is replaced by oxyl or halogenated oxyl in magnesium molecular formula；
The organic acid compound anhydride is selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride and equal benzene four
One or more of formic acid dianhydride；
The general formula of the titanium compound is TiXm(OR1)4-m, wherein R1Selected from C1-C20Alkyl；X is halogen；1≤m≤4.
11. preparation method according to claim 1 or 2, which is characterized in that the precipitation agent is metal halide；It is preferred that
The precipitation agent is halogenated titanium.
12. preparation method according to claim 11, which is characterized in that the precipitation agent is titanium tetrachloride.
13. preparation method according to claim 1 or 2, which is characterized in that based on the magnesium elements in every mole of magnesium compound
Meter, the dosage for leading to compound shown in formula (I) is 0.005-2 moles；0.005-2 moles of the dosage of organic acid compound anhydride；Titanium
The dosage of compound is 3-40 moles；The dosage of internal electron donor compound is 0.005-15；The dosage of organic epoxy compound object
It is 0.2-10 moles；The dosage of organic phosphorus compound is 0.1-3 moles.
14. preparation method according to claim 13, which is characterized in that based on the magnesium elements in every mole of magnesium compound
Meter, the dosage for leading to compound shown in formula (I) is 0.01-0.5 moles；The dosage of organic acid compound anhydride is rubbed for 0.01-0.2
You；The dosage of titanium compound is 5-30 moles；The dosage of internal electron donor compound is 0.05-5 moles.
15. a kind of catalyst for olefinic polymerization, the reaction product comprising following components:
Component L, the catalytic component prepared such as any one of claim 1-14 the method；
Component M, alkyl aluminum compound；And optional
Component N, external electron donor component.
16. catalyst according to claim 15, which is characterized in that the external electron donor component includes general formula (II) institute
The compound shown:
(R2)kSi(OR3)4-k (Ⅱ)
In the general formula (II), 0≤k≤3；R2Selected from halogen, hydrogen atom, C1-C20Alkyl, C3-C20Naphthenic base, C6-C20Virtue
Base, C1-C20Halogenated alkyl and amino；R3Selected from C1-C20Alkyl, C3-C20Naphthenic base, C6-C20Aryl, C1-C20's
Halogenated alkyl and amino.
17. catalyst according to claim 15 or 16, which is characterized in that the molar ratio of component L, component M and component N with
Titanium: aluminium: external electron donor is calculated as 1:(5-1000): (0-500).
18. catalyst according to claim 17, which is characterized in that the molar ratio of component L, component M and component N are with titanium:
Aluminium: external electron donor is calculated as 1:(25-100): (25-100).
19. a kind of pre-polymerized catalyst for olefinic polymerization, including such as any one of claim 1-14 the method system
Standby catalytic component or the catalyst as described in any one of claim 15-18 and prepolymerization alkene carry out prepolymerization institute
The prepolymer obtained, wherein the pre-polymerization multiple of the prepolymer is 0.1-1000g olefin polymer/g ingredient of solid catalyst.
20. a kind of method for olefinic polymerization, the alkene is prepared in any one of claim 1-14 the method
Pre-polymerized catalyst described in catalyst described in any one of catalytic component, claim 15-18 or claim 19
In the presence of polymerize.
21. according to the method for claim 20, which is characterized in that the general formula of the alkene is CH2=CHR, wherein R is selected from
Hydrogen, C1-C12Alkyl and C6-C12Aryl.
22. according to the method for claim 21, which is characterized in that the alkene is ethylene and/or propylene.
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