CN105440173B - Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and application - Google Patents
Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and application Download PDFInfo
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- CN105440173B CN105440173B CN201410403187.XA CN201410403187A CN105440173B CN 105440173 B CN105440173 B CN 105440173B CN 201410403187 A CN201410403187 A CN 201410403187A CN 105440173 B CN105440173 B CN 105440173B
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Abstract
The catalyst for olefinic polymerization the invention discloses a kind of catalytic component for olefinic polymerization and preparation method thereof and comprising the catalytic component, and this is used for application of the catalyst of olefinic polymerization in olefinic polyreaction.The catalytic component contains the reaction product of following components：(i) magnesium-containing carrier；(ii) at least one titanium compound；And (iii) at least one internal electron donor；Wherein, the magnesium-containing carrier is that the compound shown in formula (1) reacts obtained product with the oxirane compound shown in formula (2).When the catalytic component prepared by support according to the present invention is used for into alkene (particularly propylene) polymerization, the heap density of polymerizate can be reduced, improves the hydrogen response of catalyst, and the appearance substantially without opposite sex material.MgXY·(ROH)p·(H2O)qFormula (1)；Formula (2).
Description
Technical field
The present invention relates to a kind of catalytic component for olefinic polymerization and preparation method thereof and include the catalytic component
The catalyst for olefinic polymerization, and this is used for application of the catalyst of olefinic polymerization in olefinic polyreaction.
Background technology
Gather it is well known that the Ziegler-Natta catalyst of chlorination magnesium alcoholate load is used for alkene (particularly propylene)
During conjunction, its performance is substantially better than the catalyst that other carriers are loaded.Therefore, the catalyst currently used for olefinic polymerization is mostly
By the way that halogenated titanium is carried on into what is be prepared on chlorination magnesium alcoholate., can be by being spray-dried, spraying in order to obtain ball type carrier
It is prepared by the methods of fog cooling, high pressure extrusion, high-speed stirred, mulser method and high-gravity rotating bed method, as WO99/44009 with
US4399054 etc., which is disclosed, to form spherical alcohol conjunction by being quenched after high-speed stirred emulsified magnesium chloride alcohol adduct system under high temperature
Thing.
But when the catalyst prepared by above-mentioned published chlorination magnesium alcoholate is used for into olefinic polymerization, it is polymerizeing
During be easy to occur polymer particle Fragmentation Phenomena, so as to cause fine polymer powder more.In order to overcome this shortcoming,
People attempt electron donor compound being incorporated into advance in the carrier preparation of chlorination magnesium alcoholate again, such as：CN1169840C
Internal electron donor phthalate compound commonly understood in the industry is incorporated into chlorination magnesium alcoholate with CN1286863C to carry
It is then that the carrier and titanium tetrachloride is anti-so as to obtain " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier in the synthesis of body
Should be to form catalyst.But described compound ball type carrier is easily tacky in preparation process, it is difficult to forms particle size and fits
Suitable spheric granules.
CN102040683A discloses a kind of reacted by magnesium halide alcohol adduct and oxirane compound and carried to prepare
The method of body, and specifically disclose by magnesium halide alcohol adduct melting it is scattered after, add oxirane compound；Either by halogen
Change after magnesium alcoholate melting disperses and be added directly into the reactor containing oxirane compound.However, using party's legal system
The shortcomings that it is unstable preparation process to be present in standby catalyst carrier, and carrier adhesion easily occurs, and carrier molding effect is bad.
In US4861847, magnesium chloride is dissolved using epoxide and tributyl phosphate class compound, is formed homogeneous molten
Titanium tetrachloride is reused after liquid to separate out carrier and carry out titanium load, reaction product is very complicated, and the accessory substance generated is difficult to handle,
Some precipitation additives can be also used during being separated out using titanium tetrachloride, this make it that byproduct of reaction is more complicated, carrier
Pattern is difficult to control.Also technology adds alcohol in above-mentioned dissolution system, and the addition of alcohol accelerates tributyl phosphate and epoxy pair
Its dissolution, but itself can be had an effect with titanium tetrachloride and shadow can be produced to follow-up catalyst pattern and performance
Ring.These technologies are all to separate out carrier using titanium tetrachloride to prepare catalyst, and as previously described, reaction is multiple for this process
Miscellaneous, waste liquid can not reclaim, and after introducing alcohol particularly in dissolution system, its carrier pattern is more unmanageable.
The content of the invention
It is an object of the invention to provide the drawbacks described above for overcoming existing carrier for olefin polymerization catalyst, and provide a kind of new
Catalyst component for olefin polymerization and preparation method thereof.
It is a further object to provide comprising above-mentioned catalytic component for olefinic polymerization catalyst and its
Application in olefinic polyreaction.
The present invention provides a kind of catalytic component for olefinic polymerization, and the catalytic component contains the reaction of following components
Product：
(i) magnesium-containing carrier；
(ii) at least one titanium compound；And
(iii) at least one internal electron donor；
Characterized in that, the magnesium-containing carrier is the compound shown in formula (1) and the ethylene oxide chemical combination shown in formula (2)
Thing reacts obtained product,
MgXY·(ROH)p·(H2O)qFormula (1),Formula (2),
Wherein, R C1-C12Straight or branched alkyl；X and Y are identical or different, are each independently halogen；R’1With
R’2It is identical or different, it is each independently hydrogen, C1-C5Straight or branched alkyl or haloalkyl；P is 1-5, and q is
0.001-0.6。
Present invention also offers a kind of method for preparing the above-mentioned catalytic component for olefinic polymerization, this method includes will
Above-mentioned magnesium-containing carrier and the titanium compound react, and before the magnesium-containing carrier and titanium compound reaction, period and
The internal electron donor is added in one or more periods afterwards.
Present invention also offers a kind of catalyst for olefinic polymerization, the catalyst contains：
(i) catalytic component, the catalytic component are the above-mentioned catalytic component for olefinic polymerization of the invention；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
Present invention also offers the above-mentioned application for the catalyst of olefinic polymerization in olefinic polyreaction.
Present inventors discovered unexpectedly that magnesium halide alcohol adduct and oxirane compound are reacted, can make
The particle shape of obtained new olefine polymerization catalyst carrier is good, surface is smooth, is not in irregular particle substantially, and
When the catalytic component of carrier preparation by gained is used for into alkene (particularly propylene) polymerization, additionally it is possible to reduce polymerizate
Heap density, improve the hydrogen response of catalyst, and the appearance substantially without opposite sex material.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is magnesium-containing carrier pattern optical microscope photograph prepared by preparation example 1；
Fig. 2 is magnesium-containing carrier pattern optical microscope photograph prepared by preparation example 2.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of catalytic component for olefinic polymerization, and the catalytic component contains the reaction of following components
Product：
(i) magnesium-containing carrier；
(ii) at least one titanium compound；And
(iii) at least one internal electron donor；
Characterized in that, the magnesium-containing carrier is the compound shown in formula (1) and the ethylene oxide chemical combination shown in formula (2)
Thing reacts obtained product,
MgXY·(ROH)p·(H2O)qFormula (1),Formula (2),
Wherein, R C1-C12Straight or branched alkyl；X and Y are identical or different, are each independently halogen；R’1With
R’2It is identical or different, it is each independently hydrogen, C1-C5Straight or branched alkyl or haloalkyl；P is 1-5, and q is
0.001-0.6。
The main improvement of the present invention is to carry in the magnesium that contains of magnesium halide alcohol adduct and oxirane compound reaction gained
When catalyst prepared by body is used for alkene (particularly propylene) polymerization, the heap density of polymerizate can be reduced, improves catalyst
Hydrogen response, and substantially without the opposite sex material appearance.
According to the present invention, in the magnesium halide alcohol adduct shown in formula (1), it is preferable that R is preferably C1-C8Straight or branched
Alkyl, more preferably C2-C5Straight or branched alkyl, such as ethyl, propyl group, butyl or amyl group.Specifically, formula is ROH change
The instantiation of compound can be but be not limited to：Ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, just oneself
Alcohol, n-octyl alcohol and 2- ethyls-the 1- one or more in alcohol, preferably ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutyl
One or more in alcohol, n-amyl alcohol and isoamyl alcohol.
In accordance with the present invention it is preferred that X and Y are each independently bromine or chlorine, most preferably chlorine.
In accordance with the present invention it is preferred that p 1.5-3, q 0.001-0.005, most preferably, p 2.6, q 0.001-
0.005。
In the oxirane compound shown in formula (2), it is preferable that R '1And R '2It is identical or different, it is excellent independently of one another
Elect hydrogen or C as1-C3Straight or branched alkyl or haloalkyl.The C1-C3Straight or branched alkyl or alkyl halide
Base can be but be not limited to：Methyl, ethyl, propyl group, chloromethyl, chloroethyl, chloropropyl, bromomethyl, bromoethyl, bromopropyl, fluorine
Methyl, dichloromethyl, two bromomethyls, difluoromethyl, trichloromethyl, trifluoromethyl, trisbromomethyl, chlorine methyl fluoride.It is further excellent
Selection of land, the instantiation of the oxirane compound can be but be not limited to：Oxirane, expoxy propane, epoxy butane,
At least one of epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy NBB.
According to the present invention, the dosage of the compound shown in formula (1) and the oxirane compound shown in formula (2) can root
It is anticipated that the composition of carrier for olefin polymerization catalyst be adjusted, the compound shown in formula (1) and the epoxy second shown in formula (2)
The weight ratio of alkyl compound dosage can be 1：0.02-0.5, preferably 1：0.09-0.23.
According to the present invention, the compound shown in the formula (1) can prepare magnesium halide alcohol adduct according to this area routine
Method prepared, such as according to embodiment in CN1718595A 1 record method.
Under preferable case, the compound shown in the formula (1) can be prepared by the following method：
(1) it is that magnesium halide, formula shown in MgXY is that alcohol compound shown in ROH mixes with the first inert media by formula
Merge heating, obtain liquefied mixture；
(2) liquefied mixture for obtaining step (1) is emulsified, and gained emulsification product is passed through and is cooled to -40 DEG C to 10
DEG C the second inert media in chilling be molded and carry out separation of solid and liquid, obtain the solid product of the compound shown in formula (1),
Wherein, X and Y are identical or different, are each independently halogen；R is C1-C12Straight or branched alkyl.
In the magnesium halide shown in formula M gXY, it is preferable that X and Y is each independently bromine or chlorine.It is it is highly preferred that described
Magnesium halide is selected from magnesium dichloride and/or dibrominated magnesium, most preferably magnesium dichloride.
In the alcohol compound that formula is shown in ROH, R is preferably C1-C8Straight or branched alkyl, more preferably C2-
C5Straight or branched alkyl, such as ethyl, propyl group, butyl or amyl group.Specifically, formula is the instantiation of ROH compound
It can be but be not limited to：Ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2- second
Base-the 1- one or more in alcohol, preferably ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol and isoamyl alcohol
In one or more.
According to the present invention, the dosage that formula is magnesium halide shown in MgXY and formula is alcohol compound shown in ROH can
Selected with the forming for compound expected from shown in formula (1).Preferably, with every mole of magnesium member in the magnesium halide
Element meter, formula is that the dosage of the alcohol compound shown in ROH is 1-6mol；It is highly preferred that with every mole in the magnesium halide
Magnesium elements meter, formula are that the dosage of the alcohol compound shown in ROH is 2-3mol.
According to invention, the minor amount of water in above-mentioned each reactant can also participate in forming the anti-of carrier for olefin polymerization catalyst
Should.
According to the present invention, in step (1), for being that magnesium halide, formula shown in MgXY are alcohols shown in ROH by formula
Compound and the blend heated condition of the first inert media are not particularly limited, as long as the condition of the heating enables to
Formula is the magnesium halide melting shown in MgXY and is that alcohol compound shown in ROH reacts with formula.Usually,
The condition of the heating includes：Temperature can be 100-130 DEG C, and the time can be 0.5-5 hours；Preferably, the temperature is
120-125 DEG C, the time is 2-3 hours.
According to the present invention, in step (1), the dosage of first inert media can be the halogen shown in MgXY according to formula
The dosage for changing magnesium selects.Usually, in terms of every mole of magnesium elements in the magnesium halide, the dosage of first inert media
Can be 0.5-10L, preferably 0.5-3L.Second inert media can be it is commonly used in the art it is various not with reactant and
Chemically interactive liquid medium occurs for reaction product.Such as：First inert media can be silicone oil and/or inert liquid
Body varsol.Specifically, first inert media can be kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, second
One or more in base silicone oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.First inertia of the present invention is situated between
Matter is particularly preferably white oil.
According to the present invention it is possible to the liquid that step (1) obtains is mixed using well known to a person skilled in the art various methods
Compound emulsifies.For example, the liquefied mixture can be subjected to low velocity shear or high speed shear, so as to be emulsified.It is described low
The stir speed (S.S.) of speed shearing is usually 400-800 revs/min.The method of the high speed shear by those skilled in the art public affairs
Know, as disclosed in CN1151183C high-speed mixing method (that is, by the solution containing liquid halogenated magnesium adduct with 2000-5000 turn/
The speed of minute is stirred).Further, it is also possible to method emulsifies the liquefied mixture with reference to disclosed in following patent：
CN1267508C is disclosed to carry out the scattered (speed of rotation of rotation by the solution containing liquid halogenated magnesium adduct in hypergravity bed
Degree can be 100-3000 revs/min)；By the solution containing liquid halogenated magnesium adduct in mulser disclosed in CN1463990A
In exported with 1500-8000 revs/min of speed；US6020279 is disclosed will to contain liquid halogenated magnesium adduction by spray-on process
The emulsifying soln of thing.
According to the present invention, by gained emulsification product be passed through in the second inert media for be cooled to -40 DEG C to 10 DEG C chilling into
Type simultaneously carries out separation of solid and liquid, it is preferable that gained emulsification product is passed through in the second inert media for being cooled to -35 DEG C to -20 DEG C
Chilling is molded and carries out separation of solid and liquid.
According to the present invention, second inert media is the relatively low inertia hydrocarbon compound of boiling point.With in the magnesium halide
Every mole of magnesium elements meter, the dosage of second inert media can be 0.5-15L, preferably 1-12L；Second inertia
Medium can be the one or more in hexane, heptane and toluene, it is preferable that second inert media is hexane and/or heptan
Alkane.
According to the present invention, the separation of solid and liquid can be the existing various methods that can realize solid phase and liquid phase separation,
Such as filter, press filtration or centrifugation, under preferable case, the method for the separation of solid and liquid is filter press technique.
In accordance with the present invention it is preferred that the preparation method of the compound shown in formula (1) also includes consolidating what step (2) obtained
Phase product is washed and dried.The washing can be using well known to a person skilled in the art the solid product that method will obtain
Washed, for example, can use inert hydrocarbon solvent (such as：Pentane, hexane, heptane, petroleum ether and gasoline) consolidate to what is obtained
State particle is washed, and is preferably washed 3-5 times.There is no particular limitation for condition of the present invention to the drying, such as described dry
Dry temperature can be 30-50 DEG C, and the time of the drying can be 0.5-10 hours.According to the present invention, the drying can be with
Carried out under normal pressure or reduced pressure.
A preferred embodiment of the invention, the average particulate diameter of the magnesium-containing carrier is 10-100 microns,
Particle diameter distribution is less than 1.2；Preferably, the average particulate diameter of the magnesium-containing carrier is 40-60 microns, particle diameter distribution 0..6-
1.1.In the preferred embodiment, the catalyst prepared by the magnesium-containing carrier can have higher hydrogen response and obtain
Olefin polymer with more low bulk density.In the present invention, the average particulate diameter of the magnesium-containing carrier and particle diameter distribution can
To be measured using Master Sizer2000 laser particle analyzers (being manufactured by Malvern Instruments Ltd).
According to the present invention, the magnesium-containing carrier is prepared by the following method, and this method includes：In depositing for the 3rd inert media
Under, by the oxirane compound haptoreaction shown in the compound shown in formula (1) and formula (2).
MgXY·(ROH)p·(H2O)qFormula (1),Formula (2),
Wherein, R C1-C12Straight or branched alkyl；X and Y are identical or different, are each independently halogen；R’1With
R’2It is identical or different, it is each independently hydrogen, C1-C5Straight or branched alkyl or haloalkyl；P is 1-5, and q is
0.001-0.6。
According to the present invention, on R, X, Y, p, q and R '1And R '2Selection with it is described above consistent, will not be repeated here.
According to the present invention, the dosage of the compound shown in formula (1) and the oxirane compound shown in formula (2) can root
It is anticipated that the composition of carrier for olefin polymerization catalyst be adjusted, the compound shown in formula (1) and the epoxy second shown in formula (2)
The weight ratio of alkyl compound dosage can be 1：0.02-0.5, preferably 1：0.09-0.23.
According to the present invention, the compound shown in the formula (1) can be according to the system of the conventional magnesium halide alcohol adduct in this area
Prepared by Preparation Method, under preferable case, the compound shown in the formula (1) can be prepared by the following method：
(1) it is that magnesium halide, formula shown in MgXY is that alcohol compound shown in ROH mixes with the first inert media by formula
Merge heating, obtain liquefied mixture；
(2) liquefied mixture for obtaining step (1) is emulsified, and gained emulsification product is passed through and is cooled to -40 DEG C to 10
DEG C the second inert media in chilling be molded and carry out separation of solid and liquid, obtain the solid product of the compound shown in formula (1),
Wherein, X and Y are identical or different, are each independently halogen；R is C1-C12Straight or branched alkyl.
It is same as described above on the compounds process for production thereof shown in the formula (1) according to the present invention, that is, the original used
The selection of material and condition is consistent with being described above, and will not be repeated here.
According to the present invention, the species of the oxirane compound shown in the formula (2) is same as described above, herein not
Repeat again.
According to the present invention, the 3rd inert media can be the relatively low inertia hydrocarbon compound of boiling point, with 1g formulas (2) institute
On the basis of the oxirane compound stated, the dosage of the 3rd inert media is 3-20mL, preferably 3-15mL；Described
Three inert medias can be the one or more in hexane, heptane, decane and white oil, it is preferable that the 3rd inert media is
One or more in hexane, heptane and decane.
According to the present invention, the compound shown in formula (1) and the catalytic bar of oxirane compound shown in formula (2)
Part can be adjusted according to the composition of expected carrier for olefin polymerization catalyst, and the catalytic condition includes：Temperature
For 0-100 DEG C, time 0.5-10h；Preferably, the catalytic condition includes：Temperature is 10-80 DEG C, time 1-
6h。
In the case of, according to the invention it is preferred to, the preparation method of the carrier for olefin polymerization catalyst also includes formula (1) Suo Shi
Compound and formula (2) shown in the obtained product of oxirane compound haptoreaction carry out press filtration, washing and drying.
The method that the press filtration can use those skilled in the art to be understood is carried out, and is repeated no more herein.
The washing can use and be washed obtained solid product well known to a person skilled in the art method, and
Press filtration is carried out after washing to remove cleaning solvent every time.Such as can use inert hydrocarbon solvent (such as：Pentane, hexane, heptan
Alkane, petroleum ether and gasoline) obtained solid product is washed, preferably wash 3-5 times.
There is no particular limitation for condition of the present invention to the drying, such as the temperature of the drying can be 25-50 DEG C,
The time of the drying can be 0.5-10 hours.According to the present invention, the drying can be carried out under normal pressure or reduced pressure.
According to the present invention, the water that contains in the magnesium-containing carrier comes from the micro of synthesis material and reaction medium institute band
Water.
According to the present invention, the dosage of the titanium compound and internal electron donor can be carried out according to the conventional amount used of this area
Selection.During the catalytic component for olefinic polymerization is prepared, with often rubbing in formula (1), shown magnesium-containing carrier
That magnesium elements meter, the content of the titanium compound can be 3-60 moles, preferably 3-25 moles；The internal electron donor contains
Amount can be 0.02-1 moles, preferably 0.02-0.2 moles.
According to the present invention, the titanium compound can be various titanium compounds commonly used in the art.For example, the titanium
Compound can be Ti (OR selected from formulaI)4-aX’aTitanium compound, wherein, RIFor C1-C14Aliphatic group, preferably C1-C8
Alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc.；X ' can be halogen, preferably F, Cl
Or Br；A is 0-4 integer.Under preferable case, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four fourths
Epoxide titanium, purity titanium tetraethoxide, the titanium butoxide of a chlorine three, dichloro dibutoxy titanium, the titanium butoxide of trichlorine one, a chlorine triethoxy
One or more in titanium, dichlorodiethyl epoxide titanium and the ethanolato-titanium of trichlorine one.
According to the present invention, the internal electron donor can be conventional use of internal electron donor in the art, such as described
Internal electron donor can be the one or more in ester, ether, ketone, nitrile, amine, acid amides and alkoxy silane.Under preferable case, in order to
Allow to use the olefin polymerization catalysis of the catalytic component olefin polymerization process have higher hydrogen response with
And making olefin polymer that there is lower heap density, the internal electron donor is preferably phthalate compound, glycol
One or more in ester type compound, 1,3- diether compounds and succinate compound compound.
According to the present invention, the phthalate compound is the compound shown in formula (3),
In formula (3), R "1And R "2It is identical or different, it is each independently C1-C10Straight or branched alkyl, C3-C20Ring
Alkyl, C6-Cl0Aryl, C7-Cl0Alkaryl or C7-C20Aryl；R”3、R”4、R”5And R "6It is identical or different, each
It independently is hydrogen or Cl-Cl0Alkyl, the C of straight or branched3-Cl0Cycloalkyl, C6-Cl0Aryl, C7-Cl0Alkaryl or virtue
Alkyl, and R "3、R”4、R”5And R "6In two or more be mutually bonded, to form ring.
According to the present invention, the diol-lipid compound is the compound shown in formula (4),
In formula (4), R " '1And R " '2It is identical or different, it is each independently C1-C20Straight or branched alkyl, C3-C20's
Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl, C7-C20Alkaryl, C2-C20Straight or branched alkylene or C10-
C20Fused ring aryl；
R”’3、R”’4、R”’5、R”’6And R1-R2nIt is identical or different, it is each independently hydrogen, halogen, C1-C20Straight chain or
Branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20Aralkyl, C2-C20Straight chain or
Branched-chain alkene base or C10-C20Fused ring aryl, or, R " '3、R”’4、R”’5、R”’6And R1-R2nIn two or more
It is mutually bonded, to form ring；
N is 0-10 integer.
According to the present invention, 1, the 3- diether compounds are the compound shown in formula (5),
In formula (5), R 'ⅠAnd R 'ⅡIt is identical or different, it is each independently C1-C20Straight or branched alkyl or C3-C20's
Cycloalkyl；
R’ⅢAnd R 'ⅣIt is identical or different, it is each independently hydrogen, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl
C6-C20Aryl, C7-C20Aralkyl and C7-C20Alkaryl in one kind, or, R 'ⅢAnd R 'ⅣIt is mutually bonded, to be formed
Ring；
According to the present invention, the succinate compound compound is the compound shown in formula (6),
In formula (6), R "ⅠAnd R "ⅡIt is identical or different, it is each independently C1-C20Straight or branched alkyl or C3-C20's
Cycloalkyl；
R”Ⅲ、R”Ⅳ、R”ⅤAnd R "ⅥIt is identical or different, it is each independently hydrogen, C1-C20Straight or branched alkyl, C3-C20
Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl and C7-C20Alkaryl in one kind, or, R "Ⅲ、R”Ⅳ、R”ⅤWith
R”ⅥIn two or more be mutually bonded, to form ring.
Under preferable case, the internal electron donor is diethyl phthalate, diisobutyl phthalate, adjacent benzene two
Formic acid di-n-butyl, phthalic acid 2- ethylhexyl esters, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 9,9- are double
(methoxy) fluorenes, 2,3- diisopropyls succinate, 4- ethyl -3,5- heptandiols dibenzoate, 3,5- heptandiols two
One or more in benzoic ether, 2,4-PD dibenzoate.
Present invention also offers the preparation method of the above-mentioned catalytic component for olefinic polymerization, this method includes：Will be upper
Magnesium-containing carrier is stated to react with titanium compound, and one before and after, during the magnesium-containing carrier and titanium compound reaction
Or the internal electron donor is added in multiple periods.
The selection of the magnesium-containing carrier, titanium compound and internal electron donor is identical with foregoing description, will not be repeated here.
In the present invention, the condition of the reaction of the magnesium-containing carrier, titanium compound and internal electron donor compound is not special
Restriction, under preferable case, the condition of the reaction can include：Reaction temperature is 80-130 DEG C, and the reaction time is that 0.5-10 is small
When.
In the case of, according to the invention it is preferred to, the preparation method of the catalytic component for olefinic polymerization also includes will
Liquid filters and reclaims solid, and the titanium compound (such as titanium tetrachloride) of reusable liquid washed once or repeatedly to recovery solid, excellent
Elect as 2-4 times；Then obtained ingredient of solid catalyst is repeatedly washed with atent solvent again.The atent solvent can be selected from fat
Fat hydrocarbon and aromatic hydrocarbons, for example, hexane, heptane, octane, decane, toluene etc..
According to the present invention, the internal electron donor can the magnesium-containing carrier and titanium compound reaction before, period and
Added in one or more periods afterwards.In the case that the internal electron donor includes at least two internal electron donors,
The internal electron donor can be added separately to, and can also together be added, be added preferably together.Under preferable case, contain by described in
The mixture of magnesium carrier and titanium compound adds internal electron donor during being heated up.
According to the present invention, the reaction of the magnesium-containing carrier and titanium compound can according to disclosed in prior art method come real
Apply, for example, titanium compound can be cooled to less than 0 DEG C (being preferably -5 to -20 DEG C), then add magnesium-containing carrier, and at this
At a temperature of be stirred 10-60 minutes, be warming up to reaction temperature (be preferably 80-130 DEG C) afterwards, and tieed up under the reaction temperature
Hold 0.5-10 hours.Internal electron donor is added in temperature-rise period.Then liquid is filtered and reclaims solid, and with the titanium of liquid
The solid of compound processing recovery is one or many, finally, is repeatedly washed with atent solvent, so as to obtain catalyst group
Point.
Present invention also offers a kind of catalyst for olefinic polymerization, the catalyst contains：
(i) catalytic component, the catalytic component are the above-mentioned catalytic component for olefinic polymerization provided by the invention；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
Described in the catalyst of olefinic polymerization, the alkyl aluminum compound can be commonly used in the art each
Kind alkyl aluminum compound, for example, the formula of the alkyl aluminum can be AlR5R6R7, wherein, R5、R6And R7It is each independently
C1-C8Alkyl or haloalkyl, and R5、R6And R7One or both of group can be halogen；The C1-C8Alkyl tool
Body example can include but is not limited to：Methyl, ethyl, propyl group, normal-butyl, isobutyl group, amyl group, hexyl, n-heptyl, n-octyl,
The halogen can be fluorine, chlorine, bromine, iodine.Specifically, the alkyl aluminum compound can for example be selected from triethyl aluminum, three isobutyls
Base aluminium, three n-butylaluminums, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, two positive fourth of a chlorine
Base aluminium, a chlorine di-n-hexyl aluminium, the aluminium ethide of dichloro one, the aluminium isobutyl of dichloro one, the n-butylaluminum of dichloro one and the n-hexyl of dichloro one
One or more in aluminium.
Described in the catalyst of olefinic polymerization, the external electron donor can be commonly used in the art various outer gives
Electron, for example, the external electron donor can be selected from carboxylic acid, carboxylic acid anhydrides, carboxylate, ketone, ether, alcohol, lactone, organophosphor chemical combination
Thing and organo-silicon compound.Preferably, the external electron donor contains at least one Si-OR keys and formula is (R8)x(R9)ySi
(OR10)zSilicon compound, wherein, R8、R9And R10It is identical or different, it is each independently C1-C18Alkyl, x and y are each only
Found the integer for 0-2, z is 1-3 integer, and x, y and z and be 4.Preferably, R8And R9It is each independently C1-C4Alkane
Base, C5-C6Cycloalkyl；R10For C1-C10Alkyl, x and y each stand alone as 1, z 2.Specifically, the external electron donor example
Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, two can be such as selected from
Isobutyl group dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane and bicyclopentyl dimethoxy
One or more in base silane.
According to the present invention, the dosage of the alkyl aluminum compound and external electron donor can be the conventional amount used of this area,
Usually, described in the catalyst of olefinic polymerization, aluminium in the alkyl aluminum compound with the catalytic component
The mol ratio of titanium be 50-1000：1, preferably 200-500：1；The external electron donor and the alkyl in terms of aluminium element
The mol ratio of aluminium compound dosage can be 0.005-0.5：1, preferably 0.01-0.25：1.
According to the present invention, in the preparation process for the catalyst of olefinic polymerization, alkyl aluminum and optionally outer electron
Body compound can react with after being mixed for the catalytic component of olefinic polymerization respectively, or can also by alkyl aluminum and optionally
Mix and react with for the catalytic component of olefinic polymerization again after the mixing in advance of ground external electron donor.
It is described for olefinic polymerization when by olefinic polymerization is used for for the catalyst of olefinic polymerization according to the present invention
Catalytic component, alkyl aluminum and optionally external electron donor can be separately added into polymer reactor, added after can also mixing poly-
Close in reactor, can also use prepolymerization method commonly understood in the industry to be added to after alkene pre-polymerization in polymer reactor.
Present invention also offers the above-mentioned application for the catalyst of olefinic polymerization in olefinic polyreaction.
Theing improvement is that for the present invention employs a kind of new catalyst for olefinic polymerization, and the specific kind of alkene
Class, the polymerisation process of alkene and condition can be with same as the prior art.
According to the present invention, above-mentioned catalyst is CH especially suitable for formula2(wherein, R is hydrogen or C to=CHR1-C12Alkane
Base) alkene homopolymerization and copolyreaction.
According to the present invention, the polymerisation of the alkene can be carried out according to existing method, specifically, in inert gas
Protection under, in liquid monomer or atent solvent containing polymerized monomer, or in the gas phase, or pass through the combination in liquid phase
Polymerization technique carries out polymerisation.The temperature of the polymerisation can be typically 0-150 DEG C, be preferably 60-100 DEG C.It is described
The pressure of polymerisation can be normal pressure or higher；Such as can be 0.01-10MPa, preferably 0.01-2MPa, it is more preferably
0.1-2MPa.The pressure of the present invention refers both to gauge pressure.In addition, in the polymerization process of alkene, the inert gas, solvent
Species and dosage are known to the skilled person, and will not be described in great detail herein.
The present invention will be described in detail by way of examples below.
1st, the average particulate diameter of carrier for olefin polymerization catalyst and particle diameter distribution use Masters Sizer2000 granularities
Instrument (being manufactured by Malvern Instruments Ltd) is measured；
2nd, the apparent form of carrier for olefin polymerization catalyst passes through the model Eclipse E200 commercially available from Nikon companies
Light microscope observed；
3rd, the heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
4th, melt index is determined according to ASTM D1238-99 methods for measuring.
Preparation example 1
The preparation example is used to illustrate magnesium-containing carrier provided by the invention and preparation method thereof.
(1) chlorination magnesium alcoholate solid is prepared according to method disclosed in embodiment in CN1718595A 1, specifically such as
Under：
In the reactor of the 150L with agitating device, by 10kg (105mol) magnesium chlorides and 12.6kg ethanol (273mol)
60L viscosity is added in the white oil of 30 centipoises (20 DEG C), to be reacted 2 hours at 125 DEG C.Then by obtained molten adduct with
The mixed liquor of white oil is transferred in the methyl-silicone oil medium for being pre-heated to 125 DEG C, and the viscosity of methyl-silicone oil is 300 centipoises (20
DEG C), the dosage of methyl-silicone oil is 120L；10-30 minutes are stirred with 200 revs/min of rotating speed, obtain mixed liquor.By the mixing
Liquid introduce it is high-gravity rotating bed is disperseed, and under agitation, will it is scattered after mixed liquor introduce and be cooled to -35 DEG C in advance
Hexane medium in, the dosage of hexane is 1200L, is separated into the cooled solidification of magnesium chloride/alcohol adducts melt of droplet, into
For spherical solid particles.Particulate solid is filtered out in the suspension of gained after chilling, this is washed at room temperature with hexane
Grain thing, hexane dosage are 100L/ times, wash 5 times altogether, are vacuumized at 30 DEG C and obtain magnesium chloride alcohol adduct solid A1, through red
External spectrum method and1H-NMR methods determine, and chlorination magnesium alcoholate solid A1 molecular formula is MgCl2(C2H5OH)2.6(H2O)0.001。
(2) in 1.5L reactor, add 600mL hexanes, 60g (0.279mol) chlorination magnesium alcoholate solid A1,
1.8mL (0.023mol) epoxychloropropane, press filtration after being reacted 5 hours at 40 DEG C.Gained press filtration product is washed 5 with hexane
It is secondary.Finally product is dried in vacuo 1 hour at 25 DEG C, obtains magnesium-containing carrier Z1.
The average particulate diameter (D50) of the magnesium-containing carrier Z1 is 53 microns, and particle diameter distribution ((D90-D10)/D50) is
1.1.It is as shown in Figure 1 using the particle morphology of observation by light microscope.It can be seen that magnesium-containing carrier Z1 particle shape
More regular, surface is smooth, is essentially all spherical, particle size distribution compares concentration.
Preparation example 2
The preparation example is used to illustrate magnesium-containing carrier provided by the invention and preparation method thereof.
Chlorination magnesium alcoholate solid A2 is prepared according to the step (1) in preparation example 1.
In 0.6L reactor, 200mL hexanes, 60g (0.279mol) chlorination magnesium alcoholate solid A2, epoxy chlorine are added
Propane 3.9mL (0.05mol), press filtration after being reacted 6 hours at 10 DEG C.Gained press filtration product is washed 5 times with hexane.Finally will
Product is dried in vacuo 2 hours at 50 DEG C, obtains magnesium-containing carrier Z2.
The average particulate diameter (D50) of the magnesium-containing carrier Z2 is 52 microns, and particle diameter distribution ((D90-D10)/D50) is
0.8.It is as shown in Figure 2 using the particle morphology of observation by light microscope.It can be seen that carrier for olefin polymerization catalyst Z2
Particle shape it is more regular, surface is smooth, is essentially all spherical, particle size distribution compares concentration.
Preparation example 3
The preparation example is used to illustrate magnesium-containing carrier provided by the invention and preparation method thereof.
Chlorination magnesium alcoholate solid A3 is prepared according to the step (1) in preparation example 1.
In 0.6L reactor, 200mL hexanes, 60g (0.279mol) chlorination magnesium alcoholate carrier A3, epoxy third are added
Alkane 3.4mL (0.043mol), press filtration after being reacted 1 hour at 80 DEG C.Gained press filtration product is washed 5 times with hexane.Finally will
Product is dried in vacuo 2 hours at 30 DEG C, obtains magnesium-containing carrier Z3.
The average particulate diameter (D50) of the magnesium-containing carrier Z3 is 52 microns, and particle diameter distribution ((D90-D10)/D50) is
1.0.Using observation by light microscope particle morphology, Z3 particle shape is more regular, and surface is smooth, is essentially all spherical
, particle size distribution compares concentration.
Preparation example 4
The preparation example is used to illustrate magnesium-containing carrier provided by the invention and preparation method thereof.
Chlorination magnesium alcoholate solid A4 is prepared according to the step (1) in preparation example 1.
In 0.6L reactor, add 200mL hexanes, 60g (0.279mol) chlorination magnesium alcoholate carrier A4, add ring
Oxidative ethane 5mL (0.064mol), press filtration after 5 hours is reacted at 20 DEG C.Gained press filtration product is washed 5 times with hexane.Most
Product is dried in vacuo 1 hour at 25 DEG C afterwards, obtains magnesium-containing carrier Z4.
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z4 is 53 microns, particle diameter distribution ((D90-
D10)/D50) it is 1.0.Using observation by light microscope particle morphology, Z4 particle shape is more regular, and surface is smooth, substantially
On be all spherical, particle size distribution compares concentration.
Contrast preparation example 1
Chlorination magnesium alcoholate solid is prepared according to the step (1) in embodiment 1, as reference carrier DZ1.
Embodiment 1
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
(1) preparation of catalyst component for olefin polymerization
In 300mL glass reaction bottle, 100mL (0.912mol) titanium tetrachloride is added, -20 DEG C are cooled to, by 40
Gram the magnesium-containing carrier Z1 obtained by preparation example 1 be added thereto, and stir 30min at -20 DEG C.Afterwards, start slow
110 DEG C are warming up to, 1.5mL (0.006mol) diisobutyl phthalate is added in temperature-rise period, is maintained at 110 DEG C
Liquid is filtered off after 30min.Then, add titanium tetrachloride to wash 2 times, finally washed 3 times with hexane, obtaining olefinic polymerization after drying urges
Agent component C1.
(2) propylene polymerization
In 5L stainless steel autoclave, purged using stream of nitrogen gas, then drawn in stream of nitrogen gas
Enter hexane solution (concentration of triethyl aluminum is 0.5mmol/mL), the 0.05mmol methylcyclohexyl of 1mmol triethyl aluminum
Catalyst component for olefin polymerization C1,1.5L for being obtained by step (1) of dimethoxysilane, 10mL anhydrous hexane and 10mg
The hydrogen of (normal volume) and 2.5L liquid propene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling, is bled off pressure,
Discharging is dried to obtain polypropylene powder.Gained polypropylene powder is weighed and analyzed, as a result as shown in table 1.In addition, this is poly-
Propylene powder particles form is good, is substantially not present special-shaped material.
Embodiment 2
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 1 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In propylene polymerization processes, added hydrogen is 6.5L (normal volume).Gained polypropylene powder is weighed and analyzed, as a result
As shown in table 1.In addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Embodiment 3
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 1 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In the preparation process of catalyst component for olefin polymerization, the magnesium-containing carrier Z2 obtained with the preparation example 2 of identical weight substitutes institute
State magnesium-containing carrier Z1 and obtain polypropylene powder.Gained polypropylene powder is weighed and analyzed, as a result as shown in table 1.In addition,
The polypropylene powder particle shape is good, is substantially not present special-shaped material.
Embodiment 4
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 3 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In propylene polymerization processes, added hydrogen is 6.5L (normal volume).Gained polypropylene powder is weighed and analyzed, as a result
As shown in table 1.In addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Embodiment 5
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 1 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In the preparation process of catalyst component for olefin polymerization, the magnesium-containing carrier Z4 replacements obtained with the preparation example 4 of identical weight contain
Magnesium carrier Z1 obtains polypropylene powder.Gained polypropylene powder is weighed and analyzed, as a result as shown in table 1.In addition, this is poly-
Propylene powder particles form is good, is substantially not present special-shaped material.
Embodiment 6
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 5 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In propylene polymerization processes, added hydrogen is 6.5L (normal volume).Gained polypropylene powder is weighed and analyzed, as a result
As shown in table 1.In addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Embodiment 7
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 1 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In the preparation process of catalyst component for olefin polymerization, the magnesium-containing carrier Z4 obtained with the preparation example 4 of identical weight is substituted containing magnesium load
Body Z1 obtains polypropylene powder.Gained polypropylene powder is weighed and analyzed, as a result as shown in table 1.In addition, the polypropylene
Powder particles form is good, is substantially not present special-shaped material.
Embodiment 8
The embodiment is used to illustrate catalyst component for olefin polymerization and olefin polymerization catalysis provided by the invention and its system
The application of Preparation Method and olefin polymerization catalysis in olefinic polyreaction.
Method according to embodiment 7 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that,
In propylene polymerization processes, added hydrogen is 6.5L (normal volume).Gained polypropylene powder is weighed and analyzed, as a result
As shown in table 1.In addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Comparative example 1
Method according to embodiment 1 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that, use
The reference carrier DZ1 that the contrast preparation example 1 of identical weight obtains substitutes the magnesium-containing carrier Z1, obtains polypropylene powder.To institute
Obtain polypropylene powder to weigh and analyzed, as a result as shown in table 1.
Comparative example 2
Method according to comparative example 1 carries out preparation and the propylene polymerization of catalyst component for olefin polymerization, except that, hydrogen
Gas addition is 6.5L (normal volume).Gained polypropylene powder is weighed and analyzed, as a result as shown in table 1
Table 1
From the results shown in Table 1, for the carrier for olefin polymerization catalyst being prepared using the method for the present invention
Grain form is good, surface is smooth, is not in irregular particle substantially, and the catalytic component prepared with the carrier of gained is used for
During alkene (particularly propylene) polymerization, additionally it is possible to reduce the heap density of polymerizate, improve the hydrogen response of catalyst, substantially
Appearance without opposite sex material.In addition, it can be seen that new alkene from the contrast of embodiment 1 and embodiment 2 and comparative example 1 and comparative example 2
The hydrogen regulation performance of catalyst prepared by polymerized hydrocarbon catalyst carrier is relatively good, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (23)
1. a kind of catalytic component for olefinic polymerization, the catalytic component contains the reaction product of following components：
(i) magnesium-containing carrier；
(ii) at least one titanium compound；And
(iii) at least one internal electron donor；
Characterized in that, the magnesium-containing carrier is that the compound shown in formula (1) and the oxirane compound shown in formula (2) are anti-
The product that should be obtained,
MgXY·(ROH)p·(H2O)qFormula (1),
Wherein, R C1-C12Straight or branched alkyl；X and Y are identical or different, are each independently halogen；R’1And R '2Phase
It is same or different, it is each independently hydrogen, C1-C5Straight or branched alkyl or haloalkyl；P is 1-5, q 0.001-0.6,
The mol ratio of compound shown in the formula (1) and the oxirane compound dosage shown in formula (2) is 1：0.02-
0.5,
Compound shown in the formula (1) is prepared by the following method：
(1) it is that magnesium halide, formula shown in MgXY is that alcohol compound shown in ROH mixes simultaneously with the first inert media by formula
Heating, obtains liquefied mixture；
(2) liquefied mixture for obtaining step (1) is emulsified, and gained emulsification product is passed through and is cooled to -40 DEG C to 10 DEG C
Chilling is molded and carries out separation of solid and liquid in second inert media, obtains the solid product of the compound shown in formula (1),
Wherein, X and Y are identical or different, are each independently halogen；R is C1-C12Straight or branched alkyl,
In terms of every mole of magnesium elements in the magnesium halide, formula is that the dosage of the alcohol compound shown in ROH is 2-3mol, institute
The average particulate diameter for stating magnesium-containing carrier is 40-60 microns, particle diameter distribution 0.6-1.1.
2. catalytic component according to claim 1, wherein, R C1-C8Straight or branched alkyl；R’1And R '2Respectively
From independently being hydrogen, C1-C3Straight or branched alkyl or haloalkyl；X and Y is each independently bromine or chlorine；P is 1.5-
3, q 0.001-0.005.
3. catalytic component according to claim 1, wherein, the compound shown in the formula (1) and the ring shown in formula (2)
The mol ratio of oxidative ethane class compound amount is 1：0.09-0.23.
4. the catalytic component according to claim 1 or 3, wherein, the oxirane compound choosing shown in the formula (2)
From in oxirane, expoxy propane, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy NBB
It is one or more.
5. catalytic component according to claim 1, wherein, in step (1), the temperature of the heating is 100-130 DEG C,
Time is 0.5-5 hours.
6. catalytic component according to claim 5, wherein, the temperature of the heating is 120-125 DEG C, time 2-3
Hour.
7. catalytic component according to claim 1, wherein, in step (1), with every mole of magnesium member in the magnesium halide
Element meter, the dosage of first inert media is 0.5-10L；First inert media is silicone oil and/or inert fluid hydro carbons
Solvent.
8. catalytic component according to claim 1, wherein, first inert media is kerosene, paraffin oil, vaseline
One or more in oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
9. catalytic component according to claim 1, wherein, in step (2), with every mole of magnesium member in the magnesium halide
Element meter, the dosage of second inert media is 0.5-15L；Second inert media is one in hexane, heptane and toluene
Kind is a variety of.
10. catalytic component according to claim 1, wherein, second inert media is hexane and/or heptane.
11. catalytic component according to claim 1, wherein, the magnesium-containing carrier is prepared by the following method, this method
Including：In the presence of the 3rd inert media, by the oxirane compound shown in the compound shown in formula (1) and formula (2)
Haptoreaction.
12. catalytic component according to claim 11, wherein, it is described on the basis of the compound shown in formula (1) by 1g
The dosage of 3rd inert media is 3-20mL；3rd inert media is one kind or more in hexane, heptane, decane and white oil
Kind.
13. catalytic component according to claim 12, wherein, the 3rd inert media is hexane, heptane and decane
In one or more.
14. catalytic component according to claim 11, wherein, the catalytic condition includes：Temperature is 0-100
DEG C, time 0.5-10h.
15. catalytic component according to claim 14, wherein, the catalytic condition includes：Temperature is 10-80
DEG C, time 1-6h.
16. catalytic component according to claim 1, wherein, in terms of every mole of magnesium elements in the magnesium-containing carrier, institute
The content for stating titanium compound is 3-60 moles；The content of the internal electron donor is 0.02-1 moles.
17. the catalytic component according to claim 1 or 16, wherein, the titanium compound is Ti (OR selected from formulaI)4- aX’aTitanium compound, wherein, RIFor C1-C14Aliphatic group, X ' is halogen, and a is 0-4 integer.
18. catalytic component according to claim 17, wherein, the titanium compound be selected from titanium tetrachloride, titanium tetrabromide,
Titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, the titanium butoxide of a chlorine three, dichloro dibutoxy titanium, the titanium butoxide of trichlorine one,
One or more in one chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and the ethanolato-titanium of trichlorine one.
19. the catalytic component according to claim 1 or 16, wherein, the internal electron donor be ester, ether, ketone, nitrile, amine,
One or more in acid amides and alkoxy silane.
20. catalytic component according to claim 19, wherein, the internal electron donor is phthalate chemical combination
One or more in thing, diol-lipid compound, 1,3- diether compounds and succinate compound compound.
21. prepare the method for the catalytic component for olefinic polymerization in claim 1-20 described in any one, this method
Including：The magnesium-containing carrier and the titanium compound are reacted, and before the magnesium-containing carrier and titanium compound reaction,
During and after one or more periods in add the internal electron donor.
22. a kind of catalyst for olefinic polymerization, the catalyst contains：
(i) catalytic component, the catalytic component are the catalytic component or right described in any one in claim 1-20
It is required that the described catalytic component that 21 methods describeds are prepared；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
23. the application for the catalyst of olefinic polymerization in olefinic polyreaction described in claim 22.
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| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
| CN102040681A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Carrier for preparing olefin polymerization catalyst and preparation method thereof |
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| CN102040681A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Carrier for preparing olefin polymerization catalyst and preparation method thereof |
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