CN104558273B - Catalytic component for olefinic polymerization and preparation method thereof and for the catalyst of olefinic polymerization and olefine polymerizing process - Google Patents
Catalytic component for olefinic polymerization and preparation method thereof and for the catalyst of olefinic polymerization and olefine polymerizing process Download PDFInfo
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Abstract
The invention provides a kind of catalytic component for olefinic polymerization and preparation method thereof, a kind of catalyst for olefinic polymerization and olefine polymerizing process.The described catalytic component for olefinic polymerization contains the product obtained by carrier for olefin polymerization catalyst, drink compound and internal electron donor compound reaction, and wherein, it is Mg (R that described carrier for olefin polymerization catalyst contains mountain formula4COO)2Shuttle acid magnesium salt, formula be R1The compound of OH, the epoxy ethyl chloride compounds with structure shown in formula (1) and optional inert liquid medium react the product obtained.Described carrier for olefin polymerization catalyst not only has preferable particle shape, and when olefin polymerization catalysis prepared by described carrier for olefin polymerization catalyst is used for the polymerization of alkene, also has higher catalysis activity and substantially without the appearance of abnormity material.
Description
Technical field
The present invention relates to a kind of catalytic component for olefinic polymerization, the catalyst group for olefinic polymerization
The preparation method divided, the said method catalytic component for olefinic polymerization prepared, one are for alkene
The catalyst of polymerized hydrocarbon and olefine polymerizing process.
Background technology
It is known that the Ziegler-Natta catalyst of magnesium chloride alcohol adduct load is for alkene (particularly
Propylene) polymerization time, its performance is substantially better than the catalyst that other carrier is loaded.Therefore, it is currently used for
The catalyst of olefinic polymerization prepares by being carried on by halogenated titanium on magnesium chloride alcohol adduct mostly.
In order to obtain ball type carrier, spray drying, spray cooling, high pressure extrusion, high-speed stirred, breast can be passed through
The methods such as change machine method and high-gravity rotating bed method are prepared, as WO99/44009 with US4399054 discloses
Spherical alcohol adduct can be formed by quenching after high-speed stirred emulsified magnesium chloride alcohol adduct system under high temperature.
But, when the catalyst prepared by above-mentioned published magnesium chloride alcohol adduct is used for olefinic polymerization
Time, it is easy to occur the Fragmentation Phenomena of polymer particle in the course of the polymerization process, thus causes fine polymer powder
More.In order to overcome this defect, people attempt again electron donor compound is incorporated into magnesium chloride in advance
In the preparation of alcohol adduct carrier, such as, CN1397568A and CN1563112A is by commonly understood in the industry
Internal electron donor phthalate compound is incorporated in the preparation of magnesium chloride alcohol adduct carrier, thus
Obtain " magnesium dichloride-alcohol-phthalic acid ester " complex spherical carrier, then by this carrier and titanium tetrachloride
It is reacted to form catalyst.But, above-mentioned complex spherical carrier is the most tacky in preparation process, it is difficult to
Form the spheroidal particle that size is suitable.
Additionally, above-mentioned magnesium chloride alcohol adduct is all the alcohol adduct melt system using cryogenic quenching solidification high temperature
, not only the consumption to the energy is relatively big, complicated process of preparation, the multiple reactors of palpus combine preparation, and
The particle diameter wider distribution of obtained alcohol adduct.In order to solve this problem, CN102040683A discloses
A kind of react, with epoxy ethyl chloride compounds, the method preparing carrier by magnesium halide alcohol adduct, and have
Body discloses and adds epoxy ethyl chloride compounds after melted for magnesium halide alcohol adduct dispersion；Or by halogen
Change after magnesium alcoholate melts dispersion and be added directly in the reactor containing epoxy ethyl chloride compounds.So
And, use the method to prepare catalyst carrier and there is preparation process instability, be susceptible to carrier adhesion,
And the shortcoming that carrier molding effect is bad.
Summary of the invention
First purpose of the present invention is to overcome the use using existing carrier for olefin polymerization catalyst to prepare
Drawbacks described above in the catalyst of olefinic polymerization, it is provided that a kind of new catalyst group for olefinic polymerization
Point.
Second object of the present invention is to provide this preparation method for the catalytic component of olefinic polymerization.
Third object of the present invention is to provide the urging for olefinic polymerization prepared by above-mentioned preparation method
Agent component.
Fourth object of the present invention is to provide a kind of catalyst for olefinic polymerization.
5th purpose of the present invention is to provide a kind of olefine polymerizing process.
The invention provides a kind of catalytic component for olefinic polymerization, this catalytic component contains by alkene
The product that polymerized hydrocarbon catalyst carrier, titanium compound and internal electron donor compound reaction obtain, wherein,
It is Mg (R that described carrier for olefin polymerization catalyst contains by formula4COO)2Carboxylic acid magnesium salt, formula be
R1The compound of OH, there is the epoxy ethyl chloride compounds of structure shown in formula I and optional
Inert liquid medium reacts the product obtained；
Wherein, R1For C1-C8The alkyl of straight or branched, R4Do not exist or for C1-C6Straight chain
Or the alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen
Or C1-C5The haloalkyl of straight or branched.
Present invention also offers the preparation method of a kind of catalytic component for olefinic polymerization, the method bag
Include following steps:
(1) it is Mg (R by formula4COO)2Carboxylic acid magnesium salt and formula be R1The compound of OH and
Optional inert liquid medium mixing, and the mixture heating that will obtain, make described carboxylic acid magnesium salt dissolve,
Obtain liquefied mixture；
(2) the liquefied mixture emulsifying that step (1) is obtained, and by emulsification product with there is formula I
The epoxy ethyl chloride compounds haptoreaction of shown structure, obtains carrier for olefin polymerization catalyst；
Wherein, R1For C1-C8The alkyl of straight or branched, R4Do not exist or for C1-C6Straight chain
Or the alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen
Or C1-C5The haloalkyl of straight or branched；
(3) described carrier for olefin polymerization catalyst is reacted with titanium compound, and in described olefinic polymerization
Add in one or more time periods in before and after, during catalyst carrier and the reaction of titanium compound
Enter internal electron donor compound.
The present invention also provides for the catalytic component for olefinic polymerization prepared by said method.
Present invention also offers a kind of catalyst for olefinic polymerization, this catalyst contains:
(1) the above-mentioned catalytic component for olefinic polymerization；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
Additionally, present invention also offers a kind of olefine polymerizing process, the method includes: at olefinic polymerization bar
Under part, one or more alkene are contacted with the above-mentioned catalyst for olefinic polymerization.
The present inventor in experimentation it was unexpectedly observed that method provided by the present invention is prepared into
To carrier for olefin polymerization catalyst not only there is preferable particle shape, and described olefinic polymerization is urged
Olefin polymerization catalysis prepared by agent carrier, when the polymerization of alkene (particularly propylene), also has
Higher catalysis activity and the appearance substantially expected without abnormity, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
According to the first aspect of the invention, the catalytic component for olefinic polymerization that the present invention provides contains
Have and reacted, by carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound, the product obtained,
Wherein, described carrier for olefin polymerization catalyst contains by formula is Mg (R4COO)2Carboxylic acid magnesium salt, logical
Formula is R1The compound of OH, there is the epoxy ethyl chloride compounds of structure shown in formula I and appoint
The inert liquid medium of choosing reacts the product obtained；
Wherein, R1For C1-C8The alkyl of straight or branched, R4Do not exist or for C1-C6Straight chain
Or the alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen
Or C1-C5The haloalkyl of straight or branched.Preferably, R1For C1-C5The alkane of straight or branched
Base, R4Do not exist or for C1-C5The alkyl of straight or branched, R5For hydrogen, R6For bromine, chlorine,
C1-C5The chloro alkyl of straight or branched or bromo alkyl.
Described C1-C5The example of alkyl of straight or branched include but not limited to: methyl, ethyl, just
Propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle penta
Base or neopentyl.Described C1-C5The chloro alkyl of straight or branched or the example of bromo alkyl include but
Be not limited to: chloromethane, bromomethane, chloric ethane, bromic ether, chloro-propane, bromo propane,
Chloro-butane, butyl bromide, chloro-pentane or bromo pentane.
The consumption of the above-mentioned each material in described carrier for olefin polymerization catalyst is not had the most especially by the present invention
Limit, such as, on the basis of the described carboxylic acid magnesium salt of 1mol, formula is R1The use of the compound of OH
Amount can be 4-30mol, and the consumption of the epoxy ethyl chloride compounds with structure shown in formula I can
Think 1-10mol；Preferably, on the basis of the described carboxylic acid magnesium salt of 1mol, formula is R1The change of OH
The consumption of compound is 6-20mol, has the use of the epoxy ethyl chloride compounds of structure shown in formula I
Amount is 1.5-6mol.
According to the present invention, the kind of described carboxylic acid magnesium salt can be the conventional selection of this area, such as, and its
Instantiation includes but not limited to: magnesium formate, magnesium acetate, propanoic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium
In one or more.The angle being easy to get from raw material, described carboxylic acid magnesium salt is particularly preferably magnesium acetate.
Furthermore, it is necessary to explanation, described carboxylic acid magnesium salt generally with water of crystallization, is preparing described olefinic polymerization
During catalyst carrier, can directly use the carboxylic acid magnesium salt with water of crystallization as raw material, it is also possible to first will
Water of crystallization removing in described carboxylic acid magnesium salt, then using the carboxylic acid magnesium salt after removing water of crystallization as raw material.
According to the present invention, at general formula R1In OH, R1For C1-C8The alkyl of straight or branched, preferably
For C1-C5The alkyl of straight or branched.Correspondingly, formula is R1The instantiation of the compound of OH
Can include but not limited to: ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, different
One or more in amylalcohol, hexanol, n-octyl alcohol and 2-Ethylhexyl Alcohol, preferably ethanol, normal propyl alcohol,
One or more in isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol and isoamyl alcohol.
The concrete kind of described epoxy chloroethane compound is not particularly limited by the present invention, as long as having
Structure shown in formula I, from the angle that raw material is ready availability, described epoxy ethyl chloride chemical combination
Thing is particularly preferably epoxy ethyl chloride, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromine
One or more in butane.
According to the present invention, the consumption of described inert liquid medium can select according to the consumption of carboxylic acid magnesium salt
Select.Usually, on the basis of the described carboxylic acid magnesium salt of 1mol, the consumption of described inert liquid medium can
Think 0.8-10L, preferably 2-8L.Described inert liquid medium can be commonly used in the art various not
Chemically interactive liquid medium is there is with reactant and product.Such as, described inert fluid is situated between
Matter can be silicone oil and/or inert fluid varsol.Specifically, described inert liquid medium can be coal
Oil, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl
One or more in silicone oil and methyl phenyl silicone oil, particularly preferably white oil.
A preferred embodiment of the invention, the average grain of described carrier for olefin polymerization catalyst
A diameter of 10-100 micron, more preferably 35-60 micron；Particle diameter distribution preferably smaller than 1.2, more preferably
For 0.6-1.In this preferred implementation, this carrier for olefin polymerization catalyst the catalyst tool prepared
There is higher catalysis activity.In the present invention, the average particulate diameter of described carrier for olefin polymerization catalyst
Master Sizer2000 laser particle analyzer can be used (by Malvern Instruments with particle diameter distribution
Ltd manufactures) record.
The preparation method of described carrier for olefin polymerization catalyst is not particularly limited by the present invention, preferably feelings
Under condition, described carrier for olefin polymerization catalyst prepares in accordance with the following methods:
(1) it is Mg (R by formula4COO)2Carboxylic acid magnesium salt and formula be R1The compound of OH and
Optional inert liquid medium mixing, and the mixture heating that will obtain, make described carboxylic acid magnesium salt dissolve,
Obtain liquefied mixture；
(2) the liquefied mixture emulsifying that step (1) is obtained, and by emulsification product with there is formula I
The epoxy ethyl chloride compounds haptoreaction of shown structure；
Wherein, R1For C1-C8The alkyl of straight or branched, R4Do not exist or for C1-C6Straight chain
Or the alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen
Or C1-C5The haloalkyl of straight or branched；Preferably, R1For C1-C5The alkane of straight or branched
Base, R4Do not exist or for C1-C5The alkyl of straight or branched, R5For hydrogen, R6For bromine, chlorine,
C1-C5The chloro alkyl of straight or branched or bromo alkyl.
Wherein, described carboxylic acid magnesium salt, formula are R1The compound of OH, there is structure shown in formula I
Epoxy ethyl chloride compounds, the kind of inert liquid medium and consumption have been described above, at this
Will not be described in great detail.
The condition of heating described in step (1) is not particularly limited, as long as enabling to by the present invention
Described carboxylic acid magnesium salt dissolves, and such as, the condition of described heating includes: the temperature of heating can be
60-120 DEG C, preferably 80-100 DEG C；Heat time heating time can be 0.5-5 hour, preferably 0.5-2 hour.
Well known to a person skilled in the art that step (1) is obtained by various method according to the present invention it is possible to use
The liquefied mixture emulsifying arrived.For example, it is possible to described liquefied mixture is carried out low velocity shear or cuts at a high speed
Cut, thus be emulsified.The stir speed (S.S.) of described low velocity shear is usually 400-800 rev/min.Described
The method of high speed shear is known to those skilled in the art, high-speed stirred as disclosed in CN1151183C
Method (that is, will be stirred with the speed of 2000-5000 rev/min containing the solution of liquid halogenated magnesium adduct
Mix).Further, it is also possible to reference to method disclosed in following patent by described liquefied mixture emulsifying:
CN1267508C is disclosed will be rotated in hypergravity bed containing the solution of liquid halogenated magnesium adduct
Dispersion (speed of rotation can be 100-3000 rev/min)；Will be containing liquid disclosed in CN1463990A
The solution of state adduct of magnesium halides exports with the speed of 1500-8000 rev/min in mulser；
The disclosed nebulization of passing through of US6020279 is by the emulsifying soln containing liquid halogenated magnesium adduct.
Catalytic condition described in step (2) is not particularly limited by the present invention, such as,
Generally include: Contact Temperature can be 60-120 DEG C, preferably 80-100 DEG C；Time of contact can be
20-60 minute, preferably 20-50 minute.
The preparation method of the carrier for olefin polymerization catalyst that the present invention provides can also include haptoreaction
The product obtained carries out solid-liquid separation, is washed by solid product and is dried.Described solid-liquid separation is permissible
It is the existing various method being capable of solid phase and liquid phase separation, such as sucking filtration, filter pressing or centrifugation,
Under preferable case, the method for described solid-liquid separation is filter press technique.The present invention is the most special to the condition of filter pressing
Ground limits, and separates with liquid phase and is as the criterion realizing solid phase the most fully.Described washing can use this
Known to skilled person, various methods are carried out, such as, can use inert hydrocarbon solvent (such as: penta
Alkane, hexane, heptane, petroleum ether and gasoline) solid product obtained is washed.The present invention for
Described dry condition is not particularly limited, and such as, described dry condition includes: baking temperature is permissible
For 20-70 DEG C, drying time can be 0.5-10 hour.According to the present invention, described being dried can be often
Carry out under pressure or reduced pressure.
In the present invention, described in the catalytic component of olefinic polymerization, titanium elements, magnesium elements and
The weight ratio of internal electron donor compound can be 1:5-15:2-15, preferably 1:6-13:3-12.
In the present invention, described carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound
The condition of reaction there is no particular limitation, under preferable case, the condition of this reaction may include that reaction
Temperature is 80-130 DEG C, and the response time is 0.5-10 hour.
In the present invention, described titanium compound can be that preparation is during the catalyst of olefinic polymerization
Conventional use of various titanium compound.Generally, described titanium compound can be such as that formula is
Ti(OR′)3-aZaAnd/or Ti (OR ')4-bZbCompound, wherein, R ' is C1-C20Alkyl, Z be F,
Cl, Br or I, a is the integer of 1-3, and b is the integer of 1-4.Under preferable case, described titanizing is closed
Thing is titanium tetrachloride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, two fourth oxygen
Base titanium chloride, butoxy titanous chloride., triethoxy titanium chloride, diethoxy titanium chloride, ethoxy
One or more in base titanous chloride. and titanous chloride..
In the present invention, described internal electron donor compound can be the preparation catalyst for olefinic polymerization
During conventional use of various internal electron donor compound, can be such as carboxylate, alcohol ester, ether,
One or more in ketone, amine and silane, preferably unitary or polyhydric aliphatic race carboxylate, unitary or many
One or more in unit's aromatic carboxylic acid esters, binary alcohol esters and binary ether.
Described unitary or polyhydric aliphatic carboxylate can be such as diethyl malonate, malonic acid di-tert-butyl ester,
2,3-diisopropyl diethyl succinate, 2,3-diisopropyl di-iso-octyl succinate, 2,3-diisopropyl amber
Amber acid di-n-butyl, 2,3-diisopropyl succinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl ester,
2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl diethyl succinate, diethylene adipate,
Dibutyl adipate, ethyl sebacate, dibutyl sebacate, diethyl maleate, maleic
One or more in diacid di-n-butyl, naphthalene dicarboxylic acids diethylester and naphthalene dicarboxylic acids dibutyl ester.
Described unitary or polynary aromatic carboxylic acid esters can be such as ethyl benzoate, phthalic acid ester two
Ethyl ester, phthalic acid ester diisobutyl ester, phthalic acid ester di-n-butyl, phthalic acid ester two are different
Monooctyl ester, phthalic acid ester di-n-octyl, triethyl trimellitate, tributyl trimellitate, even benzene three
One in triethylenetetraminehexaacetic acid ester, benzene-1,2,3-tricarboxylic acid tributyl, PMA tetra-ethyl ester and PMA four butyl ester or
Multiple.
Described binary alcohol esters can be the compound represented by following formula (1),
Wherein, R14And R15Can be identical or different, and can be each halogen, substituted or unsubstituted
The C of straight or branched1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Virtue
Alkyl or C2-C20Alkylene；In formula (1), the content representation of bracket [] has d carbon atom successively
Be bonded, and each carbon atom be also bonded with 2 substituent groups, i.e. in bracket total d carbon atom with
R1、R2、R3…R2dDeng 2d substituent group, R10-R13And R1-R2dIdentical or different, and respectively hydrogen,
Halogen, the C of substituted or unsubstituted straight or branched1-C20Alkyl, C3-C20Cycloalkyl, C6-C20
Aryl, C7-C20Aralkyl, C2-C20Alkylene, containing heteroatomic C1-C20Alkyl,
Containing heteroatomic C3-C20Cycloalkyl, containing heteroatomic C6-C20Aryl, containing heteroatomic
C7-C20Aralkyl, containing heteroatomic C2-C20Alkylene or R10-R13And R1-R2dIn
Two or more bondings form saturated or undersaturated ring structure, described hetero atom can be halogen, nitrogen,
One or more in oxygen, sulfur, silicon and phosphorus, d is the integer of 0-10, as d=0, then formula (1)
In shown binary alcohol esters, substituent group is R10、R11Carbon atom directly and substituent group is R12、R13Carbon
Atom is bonded.
Under preferable case, described binary alcohol esters is the compound represented by following formula (2):
Wherein, R14And R15Identical with the definition in above-mentioned formula (1)；R10′-R13′、R16And R17Permissible
Identical or different, and can be each the C of hydrogen, halogen, straight or branched1-C20Alkyl, C3-C20
Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl, C2-C20Alkylene, containing hetero atom
C1-C20Alkyl, containing heteroatomic C3-C20Cycloalkyl, containing heteroatomic C6-C20Virtue
Base, containing heteroatomic C7-C20Aralkyl, containing heteroatomic C2-C20Alkylene or
R10′-R13′、R16And R17In two or more bondings form saturated or undersaturated ring structure, described
Hetero atom can be one or more in halogen, nitrogen, oxygen, sulfur, silicon and phosphorus.
In the present invention, described binary alcohol esters can be such as 1,3-PD dibenzoate, 2-methyl
-1,3-propylene glycol dibenzoate, 2-ethyl-1,3-propylene glycol dibenzoate, 2,2-dimethyl-1,3-the third two
Alcohol dibenzoate, (R)-1-phenyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1,3-propylene glycol two
Benzoate, 1,3-diphenyl-1,3-propylene glycol two n Propanoic acid ester, 1,3-diphenyl-2-methyl-1,3-propanediol
Dipropionate, 1,3-diphenyl-2-methyl-1,3-propanediol diacetate esters, 1,3-diphenyl-2,2-dimethyl
-1,3-propylene glycol dibenzoate, 1,3-diphenyl-2,2-dimethyl-1,3-propylene glycol dipropionate, 1,3-bis-
The tert-butyl group-2-ethyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1,3-propylene-glycol diacetate, 1,3-
Diisopropyl-1,3-propanol two (4-butylbenzoic acid) ester, 1-phenyl-2-amino-1,3-dipropylene
Ester, 1-phenyl-2-methyl isophthalic acid, 3-butanediol dibenzoate, 2,4-PD dibenzoate, 3-butyl-2,4-
Glycol dibenzoate, 3,3-dimethyl-2,4-PD dibenzoate, 2,4-PD two are (to chlorine
Benzoic acid) ester, 2,4-PD two (m-chlorobenzoic acid) ester, 2,4-PD two (parabromobenzoic acid) ester, 2,4-
Pentanediol two (o-bromobenzoic acid) ester, 2,4-PD two (p-methylbenzoic acid) ester, 2,4-PD two are (right
P t butylbenzoic acid) ester, 2,4-PD two (to butylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two is (right
Chlorobenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester, 2-butyl-1,3-pentanediol two
(p-methylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester, 2-methyl isophthalic acid, 3-penta
Glycol pivalate, 2-methyl isophthalic acid, 3-pentanediol benzoic acid cinnamate, 2,2-dimethyl-1,3-pentanediol two
Benzoate, 2,2-dimethyl-1,3-pentanediol benzoic acid cinnamate, 2-ethyl-1,3-pentanediol hexichol first
Acid esters, 2-butyl-1,3-glycol dibenzoate, 2-pi-allyl-1,3-glycol dibenzoate, 2-
Methyl isophthalic acid, 3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate, 2-propyl group-1,3-penta
Bisbenzoate, 2-butyl-1,3-glycol dibenzoate, 1,3-pentanediol two (parachlorobenzoic-acid)
Ester, 1,3-pentanediol two (m-chlorobenzoic acid) ester, 1,3-pentanediol two (parabromobenzoic acid) ester, 1,3-pentanediol
Two (o-bromobenzoic acid) ester, 1,3-pentanediol two (p-methylbenzoic acid) ester, 1,3-pentanediol two are (to the tert-butyl group
Benzoic acid) ester, 1,3-pentanediol two (to butylbenzoic acid) ester, 1,3-pentanediol benzoic acid cinnamate, 1,3-
Pentanediol two cinnamate, 1,3-pentanediol dipropionate, 2,2,4-trimethyl-1,3-pentanediol diisopropyl
Formic acid esters, 1-trifluoromethyl-3-methyl-2,4-PD dibenzoate, 2,4-PD two are to fluoro first
Yl benzoic acid ester, 2,4-pentanediol two (2-furancarboxylic acid) ester, 2-methyl-6-heptene-2,4-heptandiol hexichol
Formic acid esters, 3-methyl-6-heptene-2,4-heptandiol dibenzoate, 4-methyl-6-heptene-2,4-heptandiol two
Benzoate, 5-methyl-6-heptene-2,4-heptandiol dibenzoate, 6-methyl-6-heptene-2,4-heptandiol
Dibenzoate, 3-ethyl-6-heptene-2,4-heptandiol dibenzoate, 4-ethyl-6-heptene-2,4-heptan two
Alcohol dibenzoate, 5-ethyl-6-heptene-2,4-heptandiol dibenzoate, 6-ethyl-6-heptene-2,4-heptan
Bisbenzoate, 3-propyl group-6-heptene-2,4-heptandiol dibenzoate, 4-propyl group-6-heptene-2,4-
Heptandiol dibenzoate, 5-propyl group-6-heptene-2,4-heptandiol dibenzoate, 6-propyl group-6-heptene
-2,4-heptandiol dibenzoate, 3-butyl-6-heptene-2,4-heptandiol dibenzoate, 4-butyl-6-heptan
Alkene-2,4-heptandiol dibenzoate, 5-butyl-6-heptene-2,4-heptandiol dibenzoate, 6-butyl-6-
Heptene-2,4-heptandiol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptandiol dibenzoate, 3,5-
Diethyl-6-heptene-2,4-heptandiol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptandiol hexichol first
Acid esters, 3,5-dibutyl-6-heptene-2,4-heptandiol dibenzoate, 3,3-dimethyl-6-heptene-2,4-heptan
Bisbenzoate, 3,3-diethyl-6-heptene-2,4-heptandiol dibenzoate, 3,3-dipropyl-6-
Heptene-2,4-heptandiol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptandiol dibenzoate, 3-
Ethyl-3,5-heptandiol dibenzoate, 4-ethyl-3,5-heptandiol dibenzoate, 3-propyl group-3,5-heptan
Bisbenzoate, 4-propyl group-3,5-heptandiol dibenzoate, 3-butyl-3,5-heptandiol hexichol first
Acid esters, 2,3-dimethyl-3,5-heptandiol dibenzoate, 2,4-dimethyl-3,5-heptandiol dibenzoate,
2,5-dimethyl-3,5-heptandiol dibenzoate, 4,4-dimethyl-3,5-heptandiol dibenzoate, 4,5-
Dimethyl-3,5-heptandiol dibenzoate, 4,6-dimethyl-3,5-heptandiol dibenzoate, 6,6-diformazan
Base-3,5-heptandiol dibenzoate, 2-methyl-3-ethyl-3,5-heptandiol dibenzoate, 2-methyl-4-
Ethyl-3,5-heptandiol dibenzoate, 2-methyl-5-ethyl-3,5-heptandiol dibenzoate, 3-methyl
-4-ethyl-3,5-heptandiol dibenzoate, 3-methyl-5-ethyl-3,5-heptandiol dibenzoate, 4-first
Base-3-ethyl-3,5-heptandiol dibenzoate, 4-methyl-4-ethyl-3,5-heptandiol dibenzoate, 9,9-
Double ((meta-methoxy benzoyloxy) methyl) fluorenes of double (benzoyloxy methyl) fluorenes, 9,9-, double ((the chlorobenzene first of 9,9-
Carboxyl) methyl) fluorenes, double ((to the chlorobenzene carboxyphenyl) methyl) fluorenes of 9,9-, 9,9-double (Cortex Cinnamomi carboxymethyl group) fluorenes, 9-(benzene
Carboxyphenyl methyl)-9-(the third carboxymethyl group) fluorenes, double (the third carboxymethyl group) fluorenes of 9,9-, double (the propylene carboxyl first of 9,9-
Base) fluorenes and 9, one or more in double (neopentyl carboxymethyl group) fluorenes of 9-, cited part binary alcohol esters
Being commercially available, other are referred to the method synthesis described in CN1436796A.
Described binary ether can be the compound represented by following formula (3),
Wherein, R18And R19Can be identical or different, and can be each the C of straight chain or straight chain1-C20
Alkyl, C3-C20Cycloalkyl, C6-C20Aryl or C7-C20Aralkyl；R20-R25Can be
Identical or different, and can be each the C of hydrogen, halogen, straight chain or straight chain1-C20Alkyl, C3-C20
Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl or R20-R25In two or more keys
Close the ring structure formed.In the preferred case, R18And R19Identical or different, and respectively straight chain or straight
The C of chain1-C10Alkyl；R20、R21、R24And R25It is hydrogen；R22And R23Identical or different, and
It is respectively straight chain or the C of straight chain1-C18Alkyl, C3-C18Cycloalkyl, C6-C18Aryl, C7-C18
Aralkyl or R22And R23It is mutually bonded the ring structure of formation.
In the present invention, described binary ether can be such as 2-(2-ethylhexyl)-1,3-dimethoxy propane,
2-isopropyl-1,3-dimethoxy propane, 2-butyl-1,3-dimethoxy propane, 2-sec-butyl-1,3-dimethoxy
Base propane, 2-cyclohexyl-1,3-dimethoxy propane, 2-phenyl-1,3-dimethoxy propane, 2-(2-phenyl
Ethyl)-1,3-dimethoxy propane, 2-(2-cyclohexyl-ethyl)-1,3-dimethoxy propane, 2-(p-chlorobenzene
Base)-1,3-dimethoxy propane, 2-(diphenyl methyl)-1,3-dimethoxy propane, 2,2-dicyclohexyl-1,3-
Dimethoxy propane, 2,2-bicyclopentyl-1,3-dimethoxy propane, 2,2-diethyl-1,3-dimethoxy third
Alkane, 2,2-dipropyl-1,3-dimethoxy propane, 2,2-diisopropyl-1,3-dimethoxy propane, 2,2-bis-
Butyl-1,3-dimethoxy propane, 2-methyl-2-propyl-1,3-dimethoxy propane, 2-methyl-2-benzyl-1,3-
Dimethoxy propane, 2-methyl-2-ethyl-1,3-dimethoxy propane, 2-methyl-2-isopropyl-1,3-diformazan
Epoxide propane, 2-methyl-2-phenyl-1,3-dimethoxy propane, 2-methyl-2-cyclohexyl-1,3-dimethoxy
Propane, 2,2-double (2-cyclohexyl-ethyl)-1,3-dimethoxy propane, 2-methyl-2-isobutyl group-1,3-dimethoxy
Base propane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-dimethoxy
Base propane, 2,2-diphenyl-1,3-dimethoxy propane, 2,2-dibenzyl-1,3-dimethoxy propane, 2,2-
Double (cyclohexyl methyl)-1,3-dimethoxy propane, 2-isobutyl group-2-isopropyl-1,3-dimethoxy propane,
2-(1-methyl butyl)-2-isopropyl-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy
Base propane, 2-phenyl-2-isopropyl-1,3-dimethoxy propane, 2-phenyl-2-sec-butyl-1,3-dimethoxy
Propane, 2-benzyl-2-isopropyl-1,3-dimethoxy propane, 2-cyclopenta-2-isopropyl-1,3-dimethoxy
Propane, 2-cyclopenta-2-sec-butyl-1,3-dimethoxy propane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxy
Base propane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxy propane, 2-isopropyl-2-sec-butyl-1,3-two
Methoxy propane, 2-cyclohexyl-2-cyclohexyl methyl-1,3-dimethoxy propane and 9,9-dimethoxy-methyl
One or more in fluorenes.
According to the third aspect of the present invention, present invention also offers a kind of catalyst for olefinic polymerization
The preparation method of component, the method comprises the following steps:
(1) it is Mg (R by formula4COO)2Carboxylic acid magnesium salt and formula be R1The compound of OH and
Optional inert liquid medium mixing, and the mixture heating that will obtain, make described carboxylic acid magnesium salt dissolve,
Obtain liquefied mixture；
(2) the liquefied mixture emulsifying that step (1) is obtained, and by emulsification product with there is formula I
The epoxy ethyl chloride compounds haptoreaction of shown structure, obtains carrier for olefin polymerization catalyst；
Wherein, R1For C1-C8The alkyl of straight or branched, R4Do not exist or for C1-C6Straight chain
Or the alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen
Or C1-C5The haloalkyl of straight or branched；Preferably, R1For C1-C5The alkane of straight or branched
Base, R4Do not exist or for C1-C5The alkyl of straight or branched, R5For hydrogen, R6For bromine, chlorine,
C1-C5The chloro alkyl of straight or branched or bromo alkyl；
(3) described carrier for olefin polymerization catalyst is reacted with titanium compound, and in described olefinic polymerization
Add in one or more time periods in before and after, during catalyst carrier and the reaction of titanium compound
Enter internal electron donor compound.
Above-mentioned in the preparation method of the catalytic component of olefinic polymerization, step (1) and (2) with
Step (1) in the preparation method of carrier for olefin polymerization catalyst described above is identical with (2),
This does not repeats.
Described in the preparation method of the catalytic component of olefinic polymerization, step (3) described alkene
Polymerizing catalyst carrier and titanium compound react and can carry out, specifically in the way of employing is same as the prior art
, such as, in step (3), described carrier for olefin polymerization catalyst and titanium compound are reacted
Concrete operation method preferably includes: titanium compound is cooled to less than 0 DEG C (preferably-5 to-25 DEG C),
It is subsequently adding in step (2) carrier for olefin polymerization catalyst obtained, and stirs mixing at such a temperature
10-60 minute, it is warming up to reaction temperature (the most about 80-130 DEG C) afterwards, and maintains under this reaction temperature
0.5-10 hour.Described in the preparation method of the catalytic component of olefinic polymerization, described interior to electricity
Donor compound is before and after, during described carrier for olefin polymerization catalyst with the reaction of titanium compound
In one or more time periods in add, preferably at described carrier for olefin polymerization catalyst and titanium compound
Reaction before add.Time period before the reaction of described carrier for olefin polymerization catalyst and titanium compound
Refer to after described carrier for olefin polymerization catalyst adds in reactor and be warming up to reaction temperature it
The front time period.
Described in the preparation method of the catalytic component of olefinic polymerization, in step (3), with
Adding of the carrier for olefin polymerization catalyst of magnesium elements meter, the titanium compound in terms of titanium elements and internal electron donor
The mol ratio entering amount can be 1:20-150:0.005-1, preferably 1:30-120:0.01-0.6.
Described in the preparation method of the catalytic component of olefinic polymerization, described titanium compound and interior give
Electron is identical with the titanium compound hereinbefore described and internal electron donor respectively, and therefore not to repeat here.
According to the third aspect of the present invention, present invention also offers by said method prepare for alkene
The catalytic component of polymerization.
According to the fourth aspect of the present invention, present invention also offers a kind of catalysis for olefinic polymerization
Agent, this catalyst contains:
(1) the described catalytic component for olefinic polymerization；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
Described composition of catalytic component for olefinic polymerization and preparation method thereof has entered
Go detailed description, do not repeated them here.
The improvements of the present invention essentially consist in the described catalytic component for olefinic polymerization, and described alkane
Base aluminium compound and the kind of external donor compound and consumption all can be same as the prior art.This
Outward, when the described catalyst being used for olefinic polymerization is used as the catalyst of olefinic polyreaction, can not only
Demonstrate higher polymerization activity, and the polymer that particle shape is good can be prepared, substantially without abnormity
Material occurs.
Usually, described in the catalyst of olefinic polymerization, alkyl aluminum compound in terms of aluminum and with
The mol ratio of the catalytic component for olefinic polymerization of titanium meter can be 1-2000:1, is preferably
20-500:1；Described external donor compound can be 0.005-0.5 with the mol ratio of alkyl aluminum compound:
1, preferably 0.01-0.4:1.
Described alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art.Such as, described
Alkyl aluminum compound can be triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, one
Chlorodiethyl aluminium, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminum, a chlorine di-n-hexyl aluminum, dichloro one
One or many in aluminium ethide, dichloro one aluminium isobutyl, dichloro one n-butylaluminum and dichloro one n-hexyl aluminum
Kind.
Described external donor compound can be various external donor compounds commonly used in the art, example
As, described external electron donor can be carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and
One or more in organo-silicon compound；Preferably, described external electron donor is organo-silicon compound.
The example of described organo-silicon compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, two different
Propyldimethoxy-silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, hexichol
Base dimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-second
Phenylpiperidines base-2-t-butyldimethoxysilane and (1,1,1-tri-fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy
Base silane and (1,1,1-tri-fluoro-2-propyl group)-methyl dimethoxysilane.
According to the fifth aspect of the present invention, present invention also offers a kind of olefine polymerizing process, the method
Including: under olefin polymerization conditions, one or more alkene are contacted with catalyst, wherein, described in urge
Agent is the above-mentioned catalyst for olefinic polymerization.
Described alkene can be such as ethylene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-
One in methyl isophthalic acid-butylene, 2-methyl-2-butene, 1-amylene, 2-amylene, 1-hexene and styrene or
Multiple, preferably one or more in ethylene, propylene, 1-butylene, 2-butylene and styrene.
According to the olefine polymerizing process of the present invention, described olefinic polymerization can be according to the conventional method of this area
Carry out.Such as, described olefinic polymerization can be polymerisation in bulk, gas-phase polymerization or slurry polymerization.According to this
The olefine polymerizing process of invention, described olefin polymerization conditions can be the normal condition of this area, such as,
Polymerization temperature can be 0-150 DEG C, preferably 60-90 DEG C；Polymerization pressure can be normal pressure or pressurization.
The invention will be further described by the following examples.It is to be understood, however, that these are real
Execute example be merely to illustrate and explain the present invention, be not limited to the present invention.
In preparation example and contrast preparation example:
1, average particulate diameter and the particle diameter distribution of carrier for olefin polymerization catalyst uses Masters S I zer
2000 particle size analyzers (being manufactured by Malvern Instruments Ltd) are measured；
2, the apparent form of carrier for olefin polymerization catalyst by the model commercially available from Nikon company is
The optical microscope of Eclipse E200 is observed.
Preparation example 1
Carrier for olefin polymerization catalyst that this preparation example provides for the present invention is described and preparation method thereof.
In the reactor of 1.6L, adding 200mL white oil, 20g(0.09mol) magnesium acetate is (containing four
Individual water of crystallization), 95mL(1.6mol) ethanol, be under agitation warming up to 90 DEG C and isothermal reaction 1 hours
After, the mixture high-speed stirred (stir speed (S.S.) is 1600rpm, lower same) obtained is disperseed 30 minutes,
To carry out emulsifying, obtain emulsification product.And in above-mentioned emulsification product, add 35mL(0.45mol) ring
Oxygen chloropropane, controls filter pressing after 90 DEG C of reaction half an hours by temperature.The solid product that filter pressing is obtained
Wash 5 times with hexane, finally product vacuum is dried, obtains carrier for olefin polymerization catalyst Z1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z1 is 40 microns, particle diameter
Distribution ((D90-D10)/D50) is 1.0.Arrived by observation by light microscope, olefin polymerization catalysis
The particle shape of carrier Z1 is more regular, smooth surface, is substantially spherical, and there is no
Irregular particle exists.
Preparation example 2
Carrier for olefin polymerization catalyst that this preparation example provides for the present invention is described and preparation method thereof.
In the reactor of 1.6L, add 300mL white oil, 12.8g(0.09mol) anhydrous acetic acid magnesium
(being prepared by the magnesium acetate dehydration containing four water of crystallization), 99mL(1.7mol) ethanol, under agitation
After being warming up to 100 DEG C and isothermal reaction 0.5 hour, the mixture stirring at low speed (stir speed (S.S.) that will obtain
It is 800 revs/min, lower same) disperse 30 minutes, to carry out emulsifying, obtain emulsification product.And upper
State addition 12.5mL(0.16mol in emulsification product) epoxychloropropane, temperature is controlled at 100 DEG C anti-
Answer filter pressing after 20 minutes.Solid product hexane filter pressing obtained washs 5 times, after having washed every time
Filter pressing, is finally dried product vacuum, obtains carrier for olefin polymerization catalyst Z2.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z2 is 35 microns, particle diameter
Distribution ((D90-D10)/D50) is 0.9.Arrived by observation by light microscope, olefin polymerization catalysis
The particle shape of carrier Z2 is more regular, smooth surface, is substantially spherical, and there is no
Irregular particle exists.
Preparation example 3
Carrier for olefin polymerization catalyst that this preparation example provides for the present invention is described and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 15.3g(0.09mol) propanoic acid magnesium, 68mL
(0.54mol) ethanol, after being under agitation warming up to 80 DEG C and isothermal reaction 2 hours, mixed by obtain
Compound high-speed stirred is disperseed 30 minutes, to carry out emulsifying, obtains emulsification product.And produce in above-mentioned emulsifying
Thing adds 23mL(0.27mol) epoxy bromopropane, temperature is controlled after 80 DEG C of reactions 50 minutes
Filter pressing.Solid product hexane filter pressing obtained washs 5 times, is finally dried by product vacuum, obtains
Carrier for olefin polymerization catalyst Z3.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z3 is 40 microns, particle diameter
Distribution ((D90-D10)/D50) is 0.8.Arrived by observation by light microscope, olefin polymerization catalysis
The particle shape of carrier Z3 is more regular, smooth surface, is substantially spherical, and there is no
Irregular particle exists.
Embodiment 1
The carrier for olefin polymerization catalyst that this embodiment provides for the present invention is described is in preparing alkene
Application.
(1) for the preparation of catalyst component for olefin polymerization:
In the glass reaction bottle of 300mL, add the titanium tetrachloride of 100mL and be cooled to-20 DEG C, will
The described carrier for olefin polymerization catalyst Z1 obtained by preparation example 1 of 40 grams is added thereto, and at-20 DEG C
Lower stirring 30min.Afterwards, it is to slowly warm up to 110 DEG C, temperature-rise period adds the adjacent benzene of 1.5mL
Dioctyl phthalate diisobutyl ester, filters off liquid after maintaining 30min at 110 DEG C.Then, titanium tetrachloride is added
Wash 2 times, finally wash 3 times with hexane, obtain catalyst component for olefin polymerization C1 after drying.Use
Grating spectrophotometer, according to the titanium elements in this catalyst component for olefin polymerization of spectrophotometry
Content；The content of magnesium elements in this catalyst component for olefin polymerization is detected according to compleximetry；According to
Liquid phase chromatographic analysis method detects the content of the diisobutyl phthalate in this catalytic component, and result is surveyed
Obtain titanium elements, magnesium elements and the weight ratio of diisobutyl phthalate in this catalyst component for olefin polymerization
For 3:16:8.
(2) propylene polymerization:
In the rustless steel autoclave of a 5L, stream of nitrogen gas is used to purge, then at nitrogen
(concentration of triethyl aluminum is to introduce the hexane solution of the triethyl aluminum of 1mmol in entraining air stream
0.5mmol/mL), the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and
Catalyst component for olefin polymerization C1,1.5L(normal volume obtained by step (1) of 10mg)
Hydrogen and the liquid propene of 2.5L.It is warming up to 70 DEG C, and reaction 1 hour at such a temperature, drop afterwards
Temperature also bleeds off pressure, and discharging is dried to obtain polypropylene powder granule J1.It is computed, this olefin polymerization catalysis
Polymerization activity is 3.0kgPP/g Cat.Additionally, described polypropylene powder granule J1 form is good, substantially
There is not abnormity material.
Embodiment 2
The carrier for olefin polymerization catalyst that this embodiment provides for the present invention is described is in preparing alkene
Application.
Carrying out propylene polymerization according to the method for embodiment 1, except for the difference that, described olefin polymerization catalysis carries
The described carrier for olefin polymerization catalyst Z2 that body Z1 preparation example 2 obtains substitutes, and obtains olefinic polymerization and urges
Agent and polypropylene powder granule J2.Being computed, the polymerization activity of described olefin polymerization catalysis is
3.6kgPP/g·Cat.Additionally, described polypropylene powder granule J2 form is good, it is substantially not present abnormity material.
Embodiment 3
The carrier for olefin polymerization catalyst that this embodiment provides for the present invention is described is in preparing alkene
Application.
Carrying out propylene polymerization according to the method for embodiment 1, except for the difference that, described olefin polymerization catalysis carries
The described carrier for olefin polymerization catalyst Z3 that body Z1 preparation example 3 obtains substitutes, and obtains olefinic polymerization and urges
Agent and polypropylene powder granule J3.Being computed, the polymerization activity of described olefin polymerization catalysis is
3.0kgPP/g·Cat.Additionally, described polypropylene powder granule J3 form is good, it is substantially not present abnormity material.
As can be seen from the above results, the olefin polymerization catalysis using the method for the present invention to prepare carries
The distribution of particles of body is preferable, and the catalyst prepared by the carrier for olefin polymerization catalyst of gained is used
When alkene (particularly propylene) is polymerized, also there is higher activity and substantially without the appearance of abnormity material,
Great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (29)
1., for a catalytic component for olefinic polymerization, this catalytic component contains is urged by olefinic polymerization
Agent carrier, titanium compound and internal electron donor compound react the product obtained, it is characterised in that institute
Stating carrier for olefin polymerization catalyst and containing by formula is Mg (R4COO)2Carboxylic acid magnesium salt, formula be R1OH
Compound, the compound with structure shown in formula I and optional inert liquid medium react
The product arrived；
Wherein, R1For C1-C8The alkyl of straight or branched, R4For H or be C1-C6Straight chain or
The alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen or
C1-C5The haloalkyl of straight or branched.
Catalytic component the most according to claim 1, wherein, R1For C1-C5Straight chain or
The alkyl of chain, R4For H or be C1-C5The alkyl of straight or branched, R5For hydrogen, R6For bromine,
Chlorine, C1-C5The chloro alkyl of straight or branched or bromo alkyl.
Catalytic component the most according to claim 1 and 2, wherein, with the described carboxylic acid of 1mol
On the basis of magnesium salt, formula is R1The consumption of the compound of OH is 4-30mol, has shown in formula I
The consumption of the compound of structure is 1-10mol.
Catalytic component the most according to claim 3, wherein, with the described carboxylic acid magnesium salt of 1mol
On the basis of, formula is R1The consumption of the compound of OH is 6-20mol, has structure shown in formula I
The consumption of compound be 1.5-6mol.
Catalytic component the most according to claim 1 and 2, wherein, described carboxylic acid magnesium salt is first
One or more in acid magnesium, magnesium acetate, propanoic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium.
Catalytic component the most according to claim 1 and 2, wherein, formula is R1The change of OH
Compound is the one in ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol and isoamyl alcohol
Or it is multiple.
Catalytic component the most according to claim 1 and 2, wherein, has shown in formula I
The compound of structure is epoxy ethyl chloride, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy
One or more in n-butyl bromide.
Catalytic component the most according to claim 1 and 2, wherein, with the described carboxylic acid of 1mol
On the basis of magnesium salt, the consumption of described inert liquid medium is 0.8-10L, and described inert liquid medium is
Silicone oil and/or inert fluid varsol.
Catalytic component the most according to claim 1 and 2, wherein, described inert liquid medium
For kerosene, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil
With one or more in methyl phenyl silicone oil.
Catalytic component the most according to claim 1 and 2, wherein, described olefinic polymerization catalysis
The average particulate diameter of agent carrier is 10-100 micron, and particle diameter distribution is less than 1.2.
11. catalytic components according to claim 1 and 2, wherein, described olefinic polymerization catalysis
The average particulate diameter of agent carrier is 35-60 micron, and particle diameter is distributed as 0.6-1.
12. catalytic components according to claim 1 and 2, wherein, described olefinic polymerization catalysis
Agent carrier prepares in accordance with the following methods:
(1) it is Mg (R by formula4COO)2Carboxylic acid magnesium salt and formula be R1The compound of OH and
Optional inert liquid medium mixing, and the mixture heating that will obtain, make described carboxylic acid magnesium salt dissolve,
Obtain liquefied mixture；
(2) the liquefied mixture emulsifying that step (1) is obtained, and by emulsification product with there is formula I
The compound haptoreaction of shown structure；
Wherein, R1For C1-C8The alkyl of straight or branched, R4For H or be C1-C6Straight chain or
The alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen or
C1-C5The haloalkyl of straight or branched.
13. catalytic components according to claim 12, wherein, R1For C1-C5Straight chain or
The alkyl of side chain, R4For H or be C1-C5The alkyl of straight or branched, R5For hydrogen, R6For bromine,
Chlorine, C1-C5The chloro alkyl of straight or branched or bromo alkyl.
14. catalytic components according to claim 12, wherein, in step (1), described in add
The condition of heat includes: heating-up temperature is 60-120 DEG C, and heat time heating time is 0.5-5 hour.
15. catalytic components according to claim 12, wherein, in step (2), described in connect
The condition touching reaction includes: Contact Temperature is 60-120 DEG C, and time of contact is 20-60 minute.
16. 1 kinds of preparation methoies for the catalytic component of olefinic polymerization, the method comprises the following steps:
(1) it is Mg (R by formula4COO)2Carboxylic acid magnesium salt and formula be R1The compound of OH and
Optional inert liquid medium mixing, and the mixture heating that will obtain, make described carboxylic acid magnesium salt dissolve,
Obtain liquefied mixture；
(2) the liquefied mixture emulsifying that step (1) is obtained, and by emulsification product with there is formula I
The compound haptoreaction of shown structure, obtains carrier for olefin polymerization catalyst；
Wherein, R1For C1-C8The alkyl of straight or branched, R4For H or be C1-C6Straight chain or
The alkyl of side chain, R5For hydrogen, C1-C5The alkyl of straight or branched or haloalkyl, R6For halogen or
C1-C5The haloalkyl of straight or branched；
(3) described carrier for olefin polymerization catalyst is reacted with titanium compound, and in described olefinic polymerization
Add in one or more time periods in before and after, during catalyst carrier and the reaction of titanium compound
Enter internal electron donor compound.
17. preparation methoies according to claim 16, wherein, R1For C1-C5Straight chain or
The alkyl of chain, R4For H or be C1-C5The alkyl of straight or branched, R5For hydrogen, R6For bromine,
Chlorine, C1-C5The chloro alkyl of straight or branched or bromo alkyl.
18. according to the preparation method described in claim 16 or 17, wherein, with the described carboxylic of 1mol
On the basis of acid magnesium salt, formula is R1The consumption of the compound of OH is 4-30mol, has formula I institute
The consumption showing the compound of structure is 1-10mol.
19. preparation methoies according to claim 18, wherein, with the described carboxylic acid magnesium salt of 1mol
On the basis of, formula is R1The consumption of the compound of OH is 6-20mol, has structure shown in formula I
The consumption of compound be 1.5-6mol.
20. according to the preparation method described in claim 16 or 17, and wherein, described carboxylic acid magnesium salt is first
One or more in acid magnesium, magnesium acetate, propanoic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium.
21. according to the preparation method described in claim 16 or 17, wherein, general formula R1The chemical combination of OH
Thing be the one in ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol and isoamyl alcohol or
Multiple.
22. according to the preparation method described in claim 16 or 17, wherein, has shown in formula I
The compound of structure is epoxy ethyl chloride, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy
One or more in n-butyl bromide.
23. according to the preparation method described in claim 16 or 17, wherein, in step (1), and institute
The condition stating heating includes: heating-up temperature is 60-120 DEG C, and heat time heating time is 0.5-5 hour.
24. according to the preparation method described in claim 16 or 17, wherein, in step (2), and institute
Stating catalytic condition to include: Contact Temperature is 60-120 DEG C, time of contact is 20-60 minute.
25. according to the preparation method described in claim 16 or 17, wherein, with the described carboxylic of 1mol
On the basis of acid magnesium salt, the consumption of described inert liquid medium is 0.8-10L, and described inert liquid medium
For silicone oil and/or inert fluid varsol.
26. according to the preparation method described in claim 16 or 17, wherein, and described inert liquid medium
For kerosene, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil
With one or more in methyl phenyl silicone oil.
27. by the method described in any one in claim 16-26 prepare for olefinic polymerization
Catalytic component.
28. 1 kinds of catalyst for olefinic polymerization, this catalyst contains:
(1) the catalyst group for olefinic polymerization described in any one in claim 1-15 and 27
Point；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
29. 1 kinds of olefine polymerizing process, the method includes: under olefin polymerization conditions, by one or many
Plant alkene to contact with catalyst, it is characterised in that described catalyst is the use described in claim 28
Catalyst in olefinic polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310468309.9A CN104558273B (en) | 2013-10-09 | 2013-10-09 | Catalytic component for olefinic polymerization and preparation method thereof and for the catalyst of olefinic polymerization and olefine polymerizing process |
Applications Claiming Priority (1)
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| CN106543307B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | The preparation method and catalyst for olefines polymerizing of catalyst for olefines polymerizing and its application |
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| CN106543299B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application and the method for olefinic polymerization |
| CN106543300B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
| CN111072803B (en) * | 2018-10-19 | 2022-07-12 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170568A (en) * | 1976-03-01 | 1979-10-09 | Bp Chemicals Limited | Polymerization catalyst |
| US4361685A (en) * | 1981-06-01 | 1982-11-30 | The Dow Chemical Company | Polymerization of olefins in the presence of catalyst prepared from organo zirconium-chromium mixtures |
| CN87103194A (en) * | 1986-04-01 | 1987-12-09 | 液体公司 | Catalyst component in the alpha-olefin polymerization catalyst and manufacture method thereof |
| CN87105136A (en) * | 1986-06-17 | 1988-06-22 | 阿莫科公司 | Olefin polymerization catalysis |
| JPH0345608A (en) * | 1989-07-13 | 1991-02-27 | Showa Denko Kk | Production of olefin polymerization catalyst and polymerization of olefin |
| CN1048500C (en) * | 1991-07-12 | 2000-01-19 | Ecp埃尼化学有限公司 | Solid component of catalyst for polymerization of ethylene and 2-olefins |
| CN1315968A (en) * | 1999-06-04 | 2001-10-03 | Lg化学株式会社 | Process for preparing polyolefin polymerization catalysts |
| WO2002048207A1 (en) * | 2000-12-15 | 2002-06-20 | China Petro-Chemical Corporation | Spherical catalyst for (co)polymerization of ethylene, preparation and use of the same |
| CN1958623A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application |
| CN101544710B (en) * | 2008-03-28 | 2012-04-18 | 中国石油化工股份有限公司 | Magnesium halide alcohol adduct and preparation method and application thereof |
-
2013
- 2013-10-09 CN CN201310468309.9A patent/CN104558273B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170568A (en) * | 1976-03-01 | 1979-10-09 | Bp Chemicals Limited | Polymerization catalyst |
| US4361685A (en) * | 1981-06-01 | 1982-11-30 | The Dow Chemical Company | Polymerization of olefins in the presence of catalyst prepared from organo zirconium-chromium mixtures |
| CN87103194A (en) * | 1986-04-01 | 1987-12-09 | 液体公司 | Catalyst component in the alpha-olefin polymerization catalyst and manufacture method thereof |
| CN87105136A (en) * | 1986-06-17 | 1988-06-22 | 阿莫科公司 | Olefin polymerization catalysis |
| JPH0345608A (en) * | 1989-07-13 | 1991-02-27 | Showa Denko Kk | Production of olefin polymerization catalyst and polymerization of olefin |
| CN1048500C (en) * | 1991-07-12 | 2000-01-19 | Ecp埃尼化学有限公司 | Solid component of catalyst for polymerization of ethylene and 2-olefins |
| CN1315968A (en) * | 1999-06-04 | 2001-10-03 | Lg化学株式会社 | Process for preparing polyolefin polymerization catalysts |
| WO2002048207A1 (en) * | 2000-12-15 | 2002-06-20 | China Petro-Chemical Corporation | Spherical catalyst for (co)polymerization of ethylene, preparation and use of the same |
| CN1958623A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application |
| CN101544710B (en) * | 2008-03-28 | 2012-04-18 | 中国石油化工股份有限公司 | Magnesium halide alcohol adduct and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543307B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | The preparation method and catalyst for olefines polymerizing of catalyst for olefines polymerizing and its application |
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