CN104558272B - A kind of carrier for olefin polymerization catalyst and preparation method thereof - Google Patents
A kind of carrier for olefin polymerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of carrier for olefin polymerization catalyst and preparation method thereof.The preparation method of described carrier for olefin polymerization catalyst comprises the following steps: formula is Mg (R by (1)4COO)2Carboxylic acid magnesium salt and formula be R1The compound of OH and the mixing of optional inert liquid medium, 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 and the epoxy ethyl chloride compounds haptoreaction with structure shown in formula II；In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is at least to there is a unimodal diffraction spectral line in the range of 9 ° 10 °, and the angle of diffraction 2 θ angle is the diffraction spectral line that there is a broad peak in the range of 10 ° 20 °.Described carrier for olefin polymerization catalyst not only has a preferable particle shape, and when the catalyst prepared is used for the polymerization of alkene, also has higher catalysis activity and substantially without the special-shaped appearance expected.
Description
Technical field
The present invention relates to a kind of carrier for olefin polymerization catalyst, the preparation of a kind of carrier for olefin polymerization catalyst
Method and the carrier for olefin polymerization catalyst prepared by said method.
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 being incorporated into internal electron donor compound in advance chlorination
In the preparation of magnesium alcoholate carrier, such as, CN1397568A and CN1563112A is by known in the industry
Internal electron donor phthalate compound be incorporated in the preparation of magnesium chloride alcohol adduct carrier, from
And obtain " magnesium dichloride-alcohol-phthalic acid ester " complex spherical carrier, then by this carrier and four chlorinations
Titanium is reacted to form catalyst.But, above-mentioned complex spherical carrier is the most tacky in preparation process, difficult
In forming 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 above-mentioned of existing carrier for olefin polymerization catalyst to lack
Fall into, and a kind of new carrier for olefin polymerization catalyst is provided.
Second object of the present invention is to provide another kind of carrier for olefin polymerization catalyst.
Third object of the present invention is to provide the preparation method of a kind of carrier for olefin polymerization catalyst.
Fourth object of the present invention is to provide the carrier for olefin polymerization catalyst that said method prepares.
The invention provides a kind of carrier for olefin polymerization catalyst, wherein, described olefin polymerization catalysis carries
Body has a structure shown in formula (I):
Wherein, R1For C1-C8The alkyl of straight or branched, R2For hydrogen, C1-C6Straight or branched
Alkyl or haloalkyl, R3For halogen or C1-C6The haloalkyl of straight or branched, R4Do not exist
Or it is C1-C6The alkyl of straight or branched, m be 0.1-1.9, n be 0.1-1.9, and m+n=2；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
The invention provides a kind of carrier for olefin polymerization catalyst, wherein, described olefin polymerization catalysis carries
It is Mg (R that body contains by formula4COO)2Carboxylic acid magnesium salt, formula be R1The compound of OH, there is formula
(II) the epoxy ethyl chloride compounds of structure shown in and the reaction of optional inert liquid medium obtain
Product；
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；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
Present invention also offers the preparation method of a kind of carrier for olefin polymerization catalyst, the method includes following
Step:
(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 II
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；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
Present invention also offers the carrier for olefin polymerization catalyst prepared by said method.
The present inventor people in experimentation it was unexpectedly observed that prepared by method provided by the present invention
The carrier for olefin polymerization catalyst obtained not only has preferable particle shape, and by described olefinic polymerization
Olefin polymerization catalysis prepared by catalyst carrier, when the polymerization of alkene (particularly propylene), also has
There is higher catalysis activity and substantially without the appearance of abnormity material, great prospects for commercial application.
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 described carrier for olefin polymerization catalyst that the present invention provides has
Structure shown in formula (I):
Wherein, R1For C1-C8The alkyl of straight or branched, R2For hydrogen, C1-C6Straight or branched
Alkyl or haloalkyl, R3For halogen or C1-C6The haloalkyl of straight or branched, R4Do not exist
Or it is C1-C6The alkyl of straight or branched, m be 0.1-1.9, n be 0.1-1.9, and m+n=2；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
In the present invention, the test condition of X-ray diffraction includes that pipe pressure is 40KV, and pipe flow is 40mA,
Target is Cu,Divergent slit is 1 ° with the angle of divergence of the anti-slit that shines, and receives slit
For 0.3mm, sweep limits is 5 °-75 °, and scanning speed is 3 ° of min-1。
According to the present invention, needed for preparation has the carrier for olefin polymerization catalyst of structure shown in formula (I)
The ready availability angle of raw material set out, it is preferable that R1For C1-C5The alkyl of straight or branched, R2For
Hydrogen or methyl, R3For bromine, chlorine, C1-C6The chloro alkyl of straight or branched or bromo alkyl, R4No
Exist or be C1-C5The alkyl of straight or branched.
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-C6The 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, bromo pentane, chloro-hexane or bromo hexane.
In accordance with the present invention it is preferred that, the angle of diffraction 2 θ angle is spreading out of a unimodal diffraction spectral line of 9 °-10 °
Firing angle is 9.2 ± 0.2 °；It is highly preferred that the intensity of the diffraction spectral line that the angle of diffraction 2 θ angle is 10 °-20 ° is more than
The angle of diffraction is the intensity of the diffraction spectral line of 9.2 ± 0.2 °.
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.
According to the second aspect of the invention, the another kind of carrier for olefin polymerization catalyst that the present invention provides contains
Having by formula is Mg (R4COO)2Carboxylic acid magnesium salt, formula be R1The compound of OH, there is formula II
Epoxy ethyl chloride compounds and the optional inert liquid medium of shown structure react 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；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
According to the present invention, the angle that raw material needed for preparing described carrier for olefin polymerization catalyst is ready availability
Set out, it is preferable that R1For C1-C5The alkyl of straight or branched, R4Do not exist or for C1-C5's
The 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.
In accordance with the present invention it is preferred that, the angle of diffraction 2 θ angle is spreading out of a unimodal diffraction spectral line of 9 °-10 °
Firing angle is 9.2 ± 0.2 °；It is highly preferred that the intensity of the diffraction spectral line that the angle of diffraction 2 θ angle is 10 °-20 ° is more than
The angle of diffraction is the intensity of the diffraction spectral line of 9.2 ± 0.2 °.
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 II 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 II
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.
According to the third aspect of the present invention, the preparation side of the carrier for olefin polymerization catalyst that the present invention provides
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 II
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；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
According to the present invention, from the angle that raw material is ready availability, it is preferable that R1For C1-C5Straight chain or
The alkyl of side chain, 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 C1-C5Straight chain or
The alkyl of side chain and described C1-C5The chloro alkyl of straight or branched or the object lesson of bromo alkyl
Being described, therefore not to repeat here.
According to the present invention, in the carrier for olefin polymerization catalyst prepared according to the method described above, preferably
Ground, the angle of diffraction 2 θ angle be the angle of diffraction of a unimodal diffraction spectral line of 9 °-10 ° be 9.2 ± 0.2 °；More excellent
Selection of land, the angle of diffraction 2 θ angle be the intensity of the diffraction spectral line of 10 °-20 ° be 9.2 ± 0.2 ° spread out more than the angle of diffraction
Penetrate the intensity of spectral line.
Wherein, described carboxylic acid magnesium salt, formula are R1The compound of OH, there is structure shown in formula II
The kind of epoxy ethyl chloride compounds have been described above, will not be described in great detail at this.
According to the present invention, described carboxylic acid magnesium salt, formula are R1The compound of OH, there is formula II institute
Show that the consumption of the epoxy ethyl chloride compounds of structure can be according to intended carrier for olefin polymerization catalyst
Composition properly select, such as, on the basis of the described carboxylic acid magnesium salt of 1mol, formula is R1OH
The consumption of compound can be 4-30mol, there is the epoxy chloroethene alkanes of structure shown in formula II
The consumption of compound can be 1-10mol；Preferably, on the basis of the described carboxylic acid magnesium salt of 1mol, formula
For R1The consumption of the compound of OH is 6-20mol, has the epoxy ethyl chloride of structure shown in formula II
The consumption of compounds is 1.5-6mol.
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.
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.
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, and is washed by solid product and be dried.Described solid-liquid separation can
To be the existing various method being capable of solid phase and liquid phase separation, such as sucking filtration, filter pressing or centrifugal point
From, under preferable case, the method for described solid-liquid separation is filter press technique.The condition of filter pressing is not had by the present invention
Limit especially, separate with liquid phase and be as the criterion realizing solid phase the most fully.Described washing can be adopted
With well known to a person skilled in the art that various method is carried out, it is for instance possible to use inert hydrocarbon solvent (example
As: pentane, hexane, heptane, petroleum ether and gasoline) solid product obtained is washed.This
Bright being not particularly limited for described dry condition, such as, described dry condition includes: be dried temperature
Degree can be 20-70 DEG C, and drying time can be 0.5-10 hour.According to the present invention, described being dried can
To carry out under normal pressure or reduced pressure.
According to the fourth aspect of the present invention, present invention also offers the alkene prepared by said method
Polymerizing catalyst carrier.
Hereinafter will be described the present invention by embodiment.
In preparation example and contrast preparation example:
1, average particulate diameter and the particle diameter distribution of carrier for olefin polymerization catalyst uses Masters Sizer
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.
3, X-ray powder diffraction: using the model purchased from Philips company of Holland is X'Pert MPD
Multi-functional X ray diffractometer be measured, wherein, test condition include pipe pressure for 40KV, pipe flow
For 40mA, target is Cu,Divergent slit is 1 ° with the angle of divergence of the anti-slit that shines,
Reception slit is 0.3mm, and sweep limits is 5 °-75 °, and scanning speed is 3 ° of min-1。
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.
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst Z1, the angle of diffraction 2 θ angle is
There is a unimodal diffraction spectral line in the range of 9 °-10 °, the angle of diffraction 2 θ is 9.18 ° (91), and the angle of diffraction
2 θ are the diffraction spectral line that there is a broad peak in the range of 10 °-20 °, and the angle of diffraction 2 θ is 13.6 ° (100).
Wherein, the digitized representation in bracket is relative to the intensity I/I of strongest line0。
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.
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst Z2, the angle of diffraction 2 θ angle is
There is a unimodal diffraction spectral line in the range of 9 °-10 °, the angle of diffraction 2 θ is 9.21 ° (92), and the angle of diffraction
2 θ angles are the diffraction spectral line that there is a broad peak in the range of 10 °-20 °, and the angle of diffraction 2 θ is 13.9 ° (100).
Wherein, the digitized representation in bracket is relative to the intensity I/I of strongest line0。
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.
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst Z3, the angle of diffraction 2 θ angle is
There is a unimodal diffraction spectral line in the range of 9 °-10 °, the angle of diffraction 2 θ is 9.4 ° (92), and the angle of diffraction
2 θ angles are the diffraction spectral line that there is a broad peak in the range of 10 °-20 °, and the angle of diffraction 2 θ is 14.2 ° (100).
Wherein, the digitized representation in bracket is relative to the intensity I/I of strongest line0。
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-20
30min is stirred at DEG C.Afterwards, it is to slowly warm up to 110 DEG C, temperature-rise period adds the neighbour of 1.5mL
Phthalic acid diisobutyl ester, filters off liquid after maintaining 30min at 110 DEG C.Then, four chlorinations are added
Titanium washs 2 times, finally washes 3 times with hexane, obtains catalyst component for olefin polymerization C1 after drying.Adopt
With 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；Root
The content of diisobutyl phthalate in this catalytic component, result is detected according to liquid phase chromatographic analysis method
Record the quality of titanium elements, magnesium elements and diisobutyl phthalate in this catalyst component for olefin polymerization
Ratio is 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, described olefin polymerization catalysis
Polymerization activity be 3.0kgPP/g Cat.Additionally, described polypropylene powder granule J1 form is good, base
There is not abnormity material in this.
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 (33)
1. a carrier for olefin polymerization catalyst, it is characterised in that described carrier for olefin polymerization catalyst
There is the structure shown in formula (I):
Wherein, R1For C1-C8The alkyl of straight or branched, R2For hydrogen, C1-C6Straight or branched
Alkyl or haloalkyl, R3For halogen or C1-C6The haloalkyl of straight or branched, R4For H or
Person is C1-C6The alkyl of straight or branched, m be 0.1-1.9, n be 0.1-1.9, and m+n=2；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
Carrier for olefin polymerization catalyst the most according to claim 1, wherein, R1For C1-C5's
The alkyl of straight or branched, R2For hydrogen or methyl, R3For bromine, chlorine, C1-C6The chlorine of straight or branched
Substituted alkyl or bromo alkyl, R4For H or be C1-C5The alkyl of straight or branched.
Carrier for olefin polymerization catalyst the most according to claim 1 and 2, wherein, the angle of diffraction 2 θ
Angle be the angle of diffraction of a unimodal diffraction spectral line of 9 °-10 ° be 9.2 ± 0.2 °.
Carrier for olefin polymerization catalyst the most according to claim 3, wherein, the angle of diffraction 2 θ angle is
The intensity of the diffraction spectral line of 10 °-20 ° is more than the intensity of the diffraction spectral line that the angle of diffraction is 9.2 ± 0.2 °.
Carrier for olefin polymerization catalyst the most according to claim 1 and 2, wherein, described alkene
The average particulate diameter of polymerizing catalyst carrier is 10-100 micron, and particle diameter distribution is less than 1.2.
Carrier for olefin polymerization catalyst the most according to claim 5, wherein, described olefinic polymerization
The average particulate diameter of catalyst carrier is 35-60 micron, and particle diameter is distributed as 0.6-1.
7. a carrier for olefin polymerization catalyst, it is characterised in that described carrier for olefin polymerization catalyst
Containing by formula is Mg (R4COO)2Carboxylic acid magnesium salt, formula be R1The compound of OH, there is formula II
Compound and the optional inert liquid medium of shown structure react the product obtained；
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；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
Carrier for olefin polymerization catalyst the most according to claim 7, wherein, R1For C1-C5's
The alkyl of straight or branched, 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.
9. according to the carrier for olefin polymerization catalyst described in claim 7 or 8, wherein, the angle of diffraction 2 θ
Angle be the angle of diffraction of a unimodal diffraction spectral line of 9 °-10 ° be 9.2 ± 0.2 °.
Carrier for olefin polymerization catalyst the most according to claim 9, wherein, the angle of diffraction 2 θ angle
It is that the intensity of diffraction spectral line of 10 °-20 ° is more than the intensity of diffraction spectral line that the angle of diffraction is 9.2 ± 0.2 °.
11. according to the carrier for olefin polymerization catalyst described in claim 7 or 8, wherein, with 1mol
Described carboxylic acid magnesium salt on the basis of, formula is R1The consumption of the compound of OH is 4-30mol, has formula
(II) consumption of the compound of structure shown in is 1-10mol.
12. carrier for olefin polymerization catalyst according to claim 11, wherein, with the institute of 1mol
On the basis of stating carboxylic acid magnesium salt, formula is R1The consumption of the compound of OH is 6-20mol, has formula II
The consumption of the compound of shown structure is 1.5-6mol.
13. carrier for olefin polymerization catalyst according to claim 11, wherein, described magnesium carboxylates
Salt is one or more in magnesium formate, magnesium acetate, propanoic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium.
14. carrier for olefin polymerization catalyst according to claim 11, wherein, formula is R1OH
Compound be in ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol and isoamyl alcohol
One or more.
15. carrier for olefin polymerization catalyst according to claim 11, wherein, have formula II
Shown in the compound of structure be epoxy ethyl chloride, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and
One or more in epoxy n-butyl bromide.
16. according to the carrier for olefin polymerization catalyst described in claim 7 or 8, wherein, with 1mol
Described carboxylic acid magnesium salt on the basis of, the consumption of described inert liquid medium is 0.8-10L, and described inertia
Liquid medium is silicone oil and/or inert fluid varsol.
17. according to the carrier for olefin polymerization catalyst described in claim 7 or 8, wherein, and described inertia
Liquid medium be kerosene, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil,
One or more in phenyl silicone oil and methyl phenyl silicone oil.
18. according to the carrier for olefin polymerization catalyst described in claim 7 or 8, wherein, and described alkene
The average particulate diameter of polymerizing catalyst carrier is 10-100 micron, and particle diameter distribution is less than 1.2.
19. carrier for olefin polymerization catalyst according to claim 18, wherein, described alkene gathers
The average particulate diameter closing catalyst carrier is 35-60 micron, and particle diameter is distributed as 0.6-1.
The preparation method of 20. 1 kinds of carrier for olefin polymerization catalyst, 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 II
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；
In the X-ray diffraction spectrogram of described carrier for olefin polymerization catalyst, the angle of diffraction 2 θ angle is 9 °-10 °
In the range of at least there is a unimodal diffraction spectral line, and the angle of diffraction 2 θ angle is to deposit in the range of 10 °-20 °
Diffraction spectral line at a broad peak.
21. preparation methoies according to claim 20, 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.
22. preparation methoies according to claim 20, wherein, the angle of diffraction 2 θ angle is 9 °-10 °
Article one, the angle of diffraction of unimodal diffraction spectral line is 9.2 ± 0.2 °.
23. preparation methoies according to claim 22, wherein, the angle of diffraction 2 θ angle is 10 °-20 °
The intensity of diffraction spectral line more than the intensity of diffraction spectral line that the angle of diffraction is 9.2 ± 0.2 °.
24. according to the preparation method described in any one in claim 20-23, wherein, with 1mol
Described carboxylic acid magnesium salt on the basis of, formula is R1The consumption of the compound of OH is 4-30mol, has formula
(II) consumption of the compound of structure shown in is 1-10mol.
25. preparation methoies according to claim 24, 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 II
The consumption of compound be 1.5-6mol.
26. preparation methoies according to claim 24, wherein, described carboxylic acid magnesium salt be magnesium formate,
One or more in magnesium acetate, propanoic acid magnesium, magnesium butyrate and 2 Ethylbutanoic acid magnesium.
27. preparation methoies according to claim 24, wherein, formula is R1The compound of OH
For the one in ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol and isoamyl alcohol or many
Kind.
28. preparation methoies according to claim 24, wherein, have structure shown in formula II
Compound be epoxy ethyl chloride, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromine fourth
One or more in alkane.
29. according to the preparation method described in any one in claim 20-23, wherein, and step (1)
In, the condition of described heating includes: heating-up temperature is 60-120 DEG C, and heat time heating time is 0.5-5 hour.
30. according to the preparation method described in any one in claim 20-23, wherein, and step (2)
In, described catalytic condition includes: Contact Temperature is 60-120 DEG C, and time of contact is that 20-60 divides
Clock.
31. according to the preparation method described in any one in claim 20-23, wherein, with 1mol
Described carboxylic acid magnesium salt on the basis of, the consumption of described inert liquid medium is 0.8-10L, and described inertia
Liquid medium is silicone oil and/or inert fluid varsol.
32. according to the preparation method described in any one in claim 20-23, wherein, and described inertia
Liquid medium be kerosene, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil,
One or more in phenyl silicone oil and methyl phenyl silicone oil.
33. olefinic polymerization catalysis prepared by the method described in any one in claim 20-32
Agent carrier.
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| CN109400778B (en) * | 2017-08-18 | 2021-02-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method |
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