CN106543300A - A kind of catalyst support used for olefinic polymerization and its preparation method and application - Google Patents
A kind of catalyst support used for olefinic polymerization and its preparation method and application Download PDFInfo
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- CN106543300A CN106543300A CN201510611814.3A CN201510611814A CN106543300A CN 106543300 A CN106543300 A CN 106543300A CN 201510611814 A CN201510611814 A CN 201510611814A CN 106543300 A CN106543300 A CN 106543300A
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Abstract
The present invention relates to polymer arts, disclose a kind of catalyst support used for olefinic polymerization and its preparation method and application, the method for the present invention includes：1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound shown in OH is mixed at not higher than 35 DEG C with oxirane compound and optional inert liquid medium, obtains fluidized mixture matter；2) by step 1) the fluidized mixture matter that obtains solidified by way of spraying.The catalyst support used for olefinic polymerization prepared using the said method of the present invention is not susceptible to adhesion and pattern is preferable.
Description
Technical field
The present invention relates to polymer arts, in particular it relates to a kind of system of catalyst support used for olefinic polymerization
Preparation Method and the catalyst support used for olefinic polymerization prepared by the method and above-mentioned olefin polymerization
Application of the catalyst carrier in catalyst for olefines polymerizing is prepared.
Background technology
It is well known that the Ziegler-Natta catalyst of chlorination magnesium alcoholate load is used for alkene (particularly
Propylene) polymerization when, its performance is substantially better than the catalyst loaded by other carriers.Therefore, currently used for
The catalyst of olefinic polymerization is prepared by halogenated titanium is carried on chlorination magnesium alcoholate mostly.
In order to obtain ball type carrier, spray drying, spray cooling, high pressure extrusion, high-speed stirred, breast can be passed through
Prepared by the method such as change machine method and high-gravity rotating bed method, such as WO1999044009A1 and US4399054
Deng disclose can be quenched after high-speed stirred emulsified magnesium chloride alcohol adduct system under high temperature with
Form spherical alcohol adduct.
But, when the catalyst for preparing the chlorination magnesium alcoholate by disclosed in above-mentioned prior art is used for alkene
During polymerization, the Fragmentation Phenomena that polymer particle occurs is easy in the course of the polymerization process, so as to cause polymer
Fine powder is more.In order to overcome this shortcoming, people to attempt for electron donor compound being incorporated into chlorine in advance again
Change in the carrier preparation of magnesium alcoholate, for example：CN1169840C and CN1286863C is public by the industry
The internal electron donor phthalate compound known is incorporated in the synthesis of chlorination magnesium alcoholate carrier,
So as to obtain " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier, then by the carrier and titanium tetrachloride
React to form catalyst.But described complex ball type carrier is easily tacky in preparation process, it is difficult to
Form the suitable spheroidal particle of size.
Additionally, above-mentioned chlorination magnesium alcoholate is the alcohol adduct for adopting cryogenic quenching means to solidify high temperature melting
Body is obtained, and not only the consumption to the energy is larger, complicated process of preparation, the multiple reactors of need carry out joint system
The particle diameter distribution of standby and obtained alcohol adduct is wider.In order to solve the problem, CN102040683A
A kind of method for reacting to prepare carrier by magnesium halide alcohol adduct with oxirane compound is disclosed,
And after specifically disclosing magnesium halide alcohol adduct melting dispersion, add oxirane compound；Or
To be added directly in the reactor containing oxirane compound after magnesium halide alcohol adduct melting dispersion.So
And, preparing catalyst carrier using the method, to there is preparation process unstable, is susceptible to carrier adhesion,
And carrier molding effect is bad.
Therefore, develop a kind of new catalyst for olefines polymerizing of the drawbacks described above that can overcome prior art
Carrier is significant.
The content of the invention
The purpose of the present invention is the drawbacks described above for overcoming prior art, there is provided one kind is not susceptible to adhesion and shape
The preferable catalyst support used for olefinic polymerization of looks.
Prior art can usually cause material when using spray system for catalyst support used for olefinic polymerization
Cause blocking at the nozzle of spraying machine, prior art is typically more than 60 DEG C toward magnesium chloride, alcohol system
Add oxirane compound, can at once form liquid-solid two-phase system, due to suspended solid particle diameter compared with
Greatly, and easily produce liquid-solid two-phase to separate, therefore, nozzle is entered this system is conveyed, be very easy to draw
Play blocking.So as to hinder persistently carrying out for the preparation technology of catalyst support used for olefinic polymerization.The present invention's
Inventor has found under study for action, when using by magnesium halide, alcohol compound and oxirane compound
Mixed at not higher than 35 DEG C, when obtaining fluidized mixture, it is possible to be situated between inert fluid is not needed
The precursor solution of catalyst support used for olefinic polymerization is obtained on the premise of matter, also, by using spraying
Resulting precursor solution is introduced in the form of spraying when being solidified in spraying machine and will not be caused by machine
The obstruction of atomizer, so as to be conducive to persistently carrying out for preparation technology.
To achieve these goals, on the one hand, the present invention provides a kind of catalyst support used for olefinic polymerization
Preparation method, the method include：
1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound and formula shown in OH
(I) oxirane compound and optional inert liquid medium shown in enters at not higher than 35 DEG C
Row mixing, obtains fluidized mixture matter；
2) by step 1) the fluidized mixture matter that obtains solidified by way of spraying；
Wherein, in formula M gXY, X is halogen element, and Y is selected from halogen element, C1-C14Alkyl,
C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C8Alkyl or C3-C8Cycloalkyl；The oxirane
Shown in the structure of class compound such as formula (I)：
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or haloalkyl.
Second aspect, the present invention provide a kind of catalyst for olefines polymerizing load prepared by said method
Body.
The third aspect, the present invention provide catalyst support used for olefinic polymerization and are preparing catalyst for olefines polymerizing
In application.
The catalyst support used for olefinic polymerization prepared using the said method of the present invention is not susceptible to glue
Connect and pattern is preferable.
The catalyst prepared using the catalyst support used for olefinic polymerization that the present invention is prepared is had
The high advantage of catalysis activity.
When preparing catalyst support used for olefinic polymerization using the method for the present invention, it is not necessary to using prior art
Surfactant is had to use in method, and the temperature of the preparation method of the present invention is low, reduces life
Produce cost.
Used using the catalyst for olefines polymerizing that the catalyst support used for olefinic polymerization of the present invention is prepared
When olefinic polyreaction, the heap density for enabling to obtained polymeric reaction product is bright compared with prior art
It is aobvious to improve.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the catalyst support used for olefinic polymerization pattern optical microphotograph that the embodiment of the present invention 1 is prepared
Mirror figure.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of preparation method of catalyst support used for olefinic polymerization, the method
Including：
1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound and formula shown in OH
(I) oxirane compound and optional inert liquid medium shown in enters at not higher than 35 DEG C
Row mixing, obtains fluidized mixture matter；
2) by step 1) the fluidized mixture matter that obtains solidified by way of spraying；
Wherein, in formula M gXY, X is halogen element, and Y is selected from halogen element, C1-C14Alkyl,
C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C8Alkyl or C3-C8Cycloalkyl；
Shown in the structure of the oxirane compound such as formula (I)：In formula (I), R2And R3
It is each independently hydrogen, C1-C5Alkyl or haloalkyl.
In the present invention, described " and optional inert liquid medium " refers to the inert liquid medium
Can participate in mixing or being not involved in mixing.That is, can need in the method for the present invention or not
Need inert liquid medium.
In the present invention, the halogen element includes fluorine, chlorine, bromine and I.
In the present invention, the C1-C14Alkyl refer to carbon number be 1-14 alkyl, including
Alkyl group and branched alkyl, including unsubstituted alkyl and hydrogen atom optionally taken by halogen element etc. is substituted
Substituted alkyl.
In the present invention, the C1-C14Alkoxyl refer to carbon number be 1-14 alkoxyl, bag
Branched alkoxy and branched alkoxy, including unsubstituting alkoxy and hydrogen atom are included optionally by halogen element
Deng substituted substituted alkoxy.
In the present invention, the C6-C14Aryl refer to carbon number be 6-14 aryl, the virtue
Base includes phenyl, the C6-C14Aryl can include hydrogen atom by the substituted aryl such as halogen element.
In the present invention, the C6-C14Aryloxy group refer to carbon number be 6-14 aryloxy group, institute
Stating aryloxy group includes phenoxy group, the C6-C14Aryloxy group can be replaced by halogen element etc. including hydrogen atom
Aryloxy group.
In the present invention, the C1-C5Alkyl include methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, isobutyl group, n-pentyl, isopentyl.
In the present invention, it is preferred in the case of, in formula M gXY, X be fluorine, chlorine or bromine element, Y
Selected from fluorine element, chlorine element, bromo element, C1-C5Alkyl, C1-C5Alkoxyl, C6-C10's
Aryl or C6-C10Aryloxy group composition group.The C1-C5Alkyl for example can for methyl, ethyl,
N-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle
Amyl group or neopentyl, the C1-C5Alkoxy such as can for methoxyl group, ethyoxyl, propoxyl group,
Isopropoxy, butoxy or isobutoxy, the C6-C10Aryl can for example be phenyl, adjacent toluene
Base, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, it is described
C6-C10Aryloxy group can for example be phenoxy group or naphthoxy.Formula is that the magnesium halide of MgXY can be
A kind of magnesium halide, or the mixture of various magnesium halides.Formula is concrete for the magnesium halide of MgXY
Example can be but be not limited to：Magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and
One or more in chlorination n-butoxy magnesium.From the ready availability angle of raw material, preferably magnesium chloride.
In the present invention, it is preferred in the case of, in general formula R1In OH, R1For C1-C6Alkyl or C3-C8
Cycloalkyl.In the case of more preferably, in general formula R1In OH, R1For C1-C5Alkyl or C3-C6
Cycloalkyl.In the case of particularly preferably, in general formula R1In OH, R1For methyl, ethyl, n-pro-pyl,
Isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, cyclopropyl, cyclopenta, methylcyclopropyl groups,
Dimethvlcvclopropvl, cyclohexyl, methylcyclopentyl.
Another kind of preferred embodiment of the invention, in the present invention, the general formula R1OH
Shown alcohol compound is selected from ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, amylalcohol, different
The group of amylalcohol, hexanol, n-octyl alcohol and 2-Ethylhexyl Alcohol composition.
In the present invention, in formula (I), R2And R3It is each independently hydrogen, methyl, ethyl, just
Propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethene
Base, chloropropyl, bromopropyl.
Another kind of preferred embodiment of the invention, in the present invention, the formula (I)
Shown oxirane compound is selected from oxirane, expoxy propane, epoxy butane, epoxy chloropropionate
The group of alkane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide composition.
In the present invention, it is preferred to the process of the solidification is implemented in the spraying machine with atomizer, institute
State atomizer and contain material conduit and nozzle head, the fluidized mixture matter is drawn by the material conduit
Into the nozzle head, and sprayed by the nozzle head to the tower body containing inert media of spraying machine
Inside solidified, temperature of the fluidized mixture matter in the material conduit is subzero 50 DEG C extremely above freezing
Between 50 DEG C, and temperature of the fluidized mixture matter in the nozzle head is 80-170 DEG C；More
It is preferred that temperature of the fluidized mixture matter in the nozzle head is 120-170 DEG C.
In the present invention, it is preferred to the inert liquid medium is silicone oil and/or inert fluid varsol.
In the case of particularly preferably, in the present invention, the inert liquid medium is kerosene, paraffin oil, all
Intellectual circle's oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and aminomethyl phenyl
At least one in silicone oil.
According to the present invention, for formula is R for the magnesium halide and formula of MgXY1The compound of OH and knot
The mixture and optional inert liquid medium of oxirane compound of the structure as shown in formula (I) exists
The condition mixed at less than 35 DEG C is not particularly limited, as long as the condition of the mixing causes formula
It is R for the magnesium halide of MgXY, formula1Epoxy second of the compound and structure of OH as shown in formula (I)
The mixture of alkyl compound forms fluidized mixture matter, and the fluidized mixture matter enters lazy in spraying machine
Can solidify during property medium.It is preferred that the condition of the mixing includes：Mixing temperature be subzero 30 DEG C extremely
35 DEG C above freezing, the time is 0.5-5h.
Noble gases medium or inert liquid medium in the method for the present invention preferably spraying machine
Temperature is 60-200 DEG C, it is further preferred that the temperature is 90-150 DEG C.
In the present invention, the inert media can include noble gases medium and inert liquid medium, right
There is no particular limitation for the species of the noble gases medium, for example, can be nitrogen or helium, or
Other suitable gas such as carbon dioxide etc..
In the present invention, the consumption of the inert liquid medium in the spraying machine according to formula can be
The consumption of the magnesium halide of MgXY is selecting.Usually, the magnesium halide with 1mol formulas as MgXY is
Benchmark, the consumption of the inert liquid medium can be 0.8-10L；Preferably 2-8L.The inert liquid
Body medium can be commonly used in the art various chemical interaction does not occur with reactant and product
Liquid medium.For example：The inert liquid medium can be silicone oil and/or inert fluid varsol.
Specifically, the inert liquid medium can be kerosene, paraffin oil, vaseline oil, white oil, methyl silicon
One or more in oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
Inert liquid medium of the present invention is particularly preferably white oil.
In the present invention, by the fluidized mixture matter, by way of spraying, the condition that solidified can be with
For the existing various conditions that can form catalyst support used for olefinic polymerization, for example, the fluidised form is mixed
Compound matter is sprayed in spraying machine so that the inert media in the fluidized mixture matter and spraying machine can be with
Inert media therein is contacted.
A kind of preferred embodiment of the invention, it is in the present invention, described by formula
Magnesium halide and general formula R shown in MgXY1Alcohol compound shown in OH and the ring shown in logical formula (I)
The step of oxidative ethane class compound and optional inert liquid medium are mixed at not higher than 35 DEG C
Can include：First by the magnesium halide shown in formula M gXY, general formula R1Alcohol compound shown in OH with
And the optional inert liquid medium carries out the first contact, the mixture obtained after then contact first
The second contact is carried out with the oxirane compound shown in logical formula (I).The present invention first contact and
Second contact is conventionally referred contact in the art, and described first and described second merely to area
Point.
In the case of particularly preferably, in the present invention, the condition of first contact includes：Temperature is 60 DEG C
To between 150 DEG C, the time is 0.5-5h.
In the case of particularly preferably, in the present invention, the condition of second contact includes：Temperature is subzero
Between 30 DEG C to 35 DEG C above freezing, the time is 0.1-4h.
It was found by the inventors of the present invention that it is special using first by the magnesium halide shown in formula M gXY, logical
Formula R1Alcohol compound and the optional inert liquid medium shown in OH is carried out under these conditions
First contact, the mixture obtained after then contact first and the ethylene oxide shown in logical formula (I)
When compound carries out the second contact under these conditions, the performance of the fluidized mixture matter of acquisition is enabled to
More preferably, and obtain carrier pattern it is more preferable.
Another kind of preferred embodiment of the invention, it is in the present invention, described by formula
Magnesium halide and general formula R shown in MgXY1Alcohol compound shown in OH and the ring shown in logical formula (I)
The step of oxidative ethane class compound and optional inert liquid medium are mixed at not higher than 35 DEG C
Can include：By the magnesium halide shown in formula M gXY, general formula R1It is alcohol compound shown in OH, logical
Oxirane compound and the optional inert liquid medium shown in formula (I) carries out the 3rd and connects
Touch, the condition of the 3rd contact includes：Temperature is that between subzero 30 DEG C to 35 DEG C above freezing the time is
0.1-4h。
According to the present invention it is possible to adopt well known to a person skilled in the art the fluidised form is mixed by various methods
Material carries out emulsifying.For example, the fluidized mixture matter can be carried out high speed shear, so as to which is newborn
Change.The method of the high speed shear is known to those skilled in the art, for example, will be containing liquid halogenated
The solution of magnesium adduct is stirred with 2000-5000 rev/min of speed.Further, it is also possible to reference to
Method disclosed in lower prior art is by the liquefied mixture emulsifying：To contain disclosed in CN1267508C
The solution of liquid halogenated magnesium adduct carries out rotation dispersion in hypergravity bed, and (speed of rotation can be
100-3000 rev/min)；CN1463990A is disclosed to exist the solution containing liquid halogenated magnesium adduct
Exported with 1500-8000 rev/min of speed in mulser；US6020279 is disclosed will by nebulization
Emulsifying soln containing liquid halogenated magnesium adduct.
According to the present invention, the consumption of the above-mentioned each component prepared in catalyst support used for olefinic polymerization can
To be selected in the larger context and be changed.
In the present invention, it is relative to the magnesium halide described in 1mol shown in formula M gXY, preferably described logical
Formula R1The consumption of the alcohol compound shown in OH be 4-30mol, the epoxy second shown in the logical formula (I)
The consumption of alkyl compound is 1-10mol.
In the case of more preferably, in the present invention, relative to the halogen described in 1mol shown in formula M gXY
Change magnesium, the preferably general formula R1The consumption of the alcohol compound shown in OH be 6-20mol, the formula
(I) consumption of the oxirane compound shown in is 2-6mol.
According to the present invention, the method can also include for products therefrom after solidification carrying out solid-liquid separation, will be solid
Phase product is washed and is dried.The solid-liquid separation can existing various can realize solid phase and liquid
The method of phase separation, such as sucking filtration, filter pressing or centrifugation, under preferable case, the solid-liquid separation
Method is filter press technique.The present invention is not particularly limited to the condition of filter pressing, fully to realize as far as possible
Solid phase is separated with liquid phase and is defined.The washing can be adopted well known to a person skilled in the art method is incited somebody to action
To solid product washed, for example can using inert hydrocarbon solvent (for example：Pentane, hexane,
Heptane, petroleum ether and gasoline) solid product to obtaining washs.The present invention is for the drying
Condition is not particularly limited, for example：The temperature of the drying can be 20-70 DEG C, the drying when
Between can be 0.5-10 hours.According to the present invention, the drying can be carried out under normal pressure or reduced pressure.
Second aspect, the invention provides a kind of catalyst for olefines polymerizing prepared by said method
Carrier.
According to catalyst support used for olefinic polymerization of the present invention, the average grain of the preferably carrier is straight
Footpath is 10-100 microns, and particle diameter distribution is less than 1.2.
In the case of more preferably, the average particulate diameter of carrier of the present invention is 30-70 microns, particle diameter
It is distributed as 0.7-0.9.In the preferred implementation, the alkene prepared by the catalyst support used for olefinic polymerization
Polymerized hydrocarbon catalyst can obtain the olefin polymer with more high-bulk-density.In the present invention, institute
The average particulate diameter and particle diameter distribution for stating carrier for olefin polymerization catalyst can adopt Master Sizer
2000 laser particle analyzers (being manufactured by Malvern Instruments Ltd) are measured.
The method according to the invention, the minor amount of water in above-mentioned each reactant can also participate in forming olefinic polymerization
With the reaction of catalyst carrier.
According to the present invention, the possible water contained in the catalyst support used for olefinic polymerization comes from synthesis
The minor amount of water of raw material and reaction medium institute band.
The third aspect, the invention provides catalyst support used for olefinic polymerization is preparing olefin polymerization catalysis
Application in agent.
The present invention answering in catalyst for olefines polymerizing is prepared to the catalyst support used for olefinic polymerization
There is no particular limitation for condition, and those skilled in the art can prepare this using conventional technique means
The described catalyst for olefines polymerizing of invention.Exemplarily adopt present invention system in embodiments of the invention
The standby carrier for obtaining carries out haptoreaction and prepares catalyst with titanium source and internal electron donor compound, to institute
There is no particular limitation to state catalytic temperature and time, and those skilled in the art are should not be construed as to this
The restriction of the technical scheme of invention.
Hereinafter will be described the present invention by embodiment.
In following examples, comparative example and test case, in case of no particular description, used
Various raw materials be all from it is commercially available.
1st, the average particulate diameter and particle diameter distribution of catalyst support used for olefinic polymerization adopts Masters Sizer
2000 particle size analyzers (being manufactured by Malvern Instruments Ltd) are measured；
2nd, the apparent form of catalyst support used for olefinic polymerization is by the model commercially available from Nikon companies
The optical microscope of Eclipse E200 is observed；
3rd, the heap density of polyolefine powder is measured using the method that GB/T 1636-2008 specify.
In order to verify that the catalyst that the carrier that the method for the present invention is obtained is prepared has preferably catalysis
The heap density of performance and the polymerizate for obtaining is higher, exemplarily using normal in following examples
One kind in rule technical scheme is illustrating.Specific experimental technique is as shown in following test case.
Embodiment 1
The present embodiment be used to illustrating the preparation method of catalyst support used for olefinic polymerization of the present invention with
And the catalyst support used for olefinic polymerization prepared by methods described.
In the reactor of 1.6L, 0.08mol magnesium chlorides, 1.6mol ethanol are added, is heated up under agitation
To 90 DEG C, after isothermal reaction 1h, 20 DEG C are cooled to, are subsequently adding 0.3mol epoxychloropropane, obtain
To fluidized mixture matter.Using the spraying machine containing nozzle head and material conduit by the fluidized mixture matter
Spray in 120 DEG C of white oils.Wherein, temperature of the fluidized mixture matter in the material conduit is
20 DEG C, the temperature in the nozzle head is 150 DEG C.The carrier predecessor obtained in the white oil is used
Hexane is washed 4 times, obtains catalyst support used for olefinic polymerization Z1 after vacuum drying 1h.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 32 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.Using particle morphology such as Fig. 1 of observation by light microscope
It is shown.It can be seen that the particle shape of catalyst support used for olefinic polymerization Z1 is more regular,
It is essentially all spherical, particle size distribution compares concentration, and there is no that irregular particle is present.
During catalyst support used for olefinic polymerization Z1 is prepared, do not have at the nozzle head of the spraying machine
There is blockage phenomenon, 12g carrier Z1 are obtained.
Comparative example 1
In the reactor of 1.6L, 0.08mol magnesium chlorides, 1.6mol ethanol are added, is heated up under agitation
To 90 DEG C, after isothermal reaction 1h, 0.3mol epoxychloropropane is added, using containing nozzle head and material
The spraying machine of conduit sprays into the fluidized mixture matter after the emulsifying in 120 DEG C of white oils, and the fluidised form is mixed
Temperature of the compound matter in the material conduit is 90 DEG C, and the temperature in the nozzle head is 150 DEG C.
The carrier predecessor obtained in the white oil is washed with hexane 4 times, after vacuum drying 1h, alkene is obtained
Catalyst for polymerization carrier D-Z1.
During catalyst support used for olefinic polymerization D-Z1 is prepared, at the nozzle head of the spraying machine
Generation is blocked twice, and 8g carriers are obtained after cleaning shower nozzle.
Embodiment 2
The present embodiment be used to illustrating the preparation method of catalyst support used for olefinic polymerization of the present invention with
And the catalyst support used for olefinic polymerization prepared by methods described.
In the reactor of 1.6L, 0.08mol magnesium chlorides, 1.4mol ethanol are added, is heated up under agitation
To 120 DEG C, after isothermal reaction 1.2h, 30 DEG C are cooled to, are subsequently adding 0.35mol epoxychloropropane,
Fluidized mixture matter is obtained, breast is carried out to the fluidized mixture matter using high-speed stirred (1800rpm)
Change, and the spraying machine containing nozzle head and material conduit is used by the fluidized mixture matter after the emulsifying
Spray in 125 DEG C of white oils, and temperature of the fluidized mixture matter in the material conduit be 30 DEG C,
Temperature in the nozzle head is 130 DEG C.The carrier predecessor obtained in the white oil is washed with hexane
Wash 4 times, after vacuum drying 1h, obtain catalyst support used for olefinic polymerization Z2.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z2 is 32 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.9.Rule are compared using the particle morphology of observation by light microscope
It is whole, it is essentially all spherical, particle size distribution compares concentration, and there is no that irregular particle is deposited
.
During catalyst support used for olefinic polymerization Z2 is prepared, do not have at the nozzle head of the spraying machine
There is blockage phenomenon, 12g carrier Z2 are obtained.
Embodiment 3
The present embodiment be used to illustrating the preparation method of catalyst support used for olefinic polymerization of the present invention with
And the catalyst support used for olefinic polymerization prepared by methods described.
In the reactor of 1.6L, 0.08mol magnesium chlorides, 1.0mol ethanol and 0.35mol epoxies are added
Chloropropane, at 15 DEG C, stirring mixing, obtains fluidized mixture matter, using high-speed stirred (1800rpm)
Emulsifying is carried out to the fluidized mixture matter, and will using the spraying machine containing nozzle head and material conduit
Fluidized mixture matter after the emulsifying is sprayed in circulating nitrogen gas, and the fluidized mixture matter is described
Temperature in material conduit is 15 DEG C, and the temperature in the nozzle head is 120 DEG C.By the acquisition
Carrier predecessor hexane is washed 4 times, obtains catalyst support used for olefinic polymerization Z3 after vacuum drying 1h.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 30 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.Rule are compared using the particle morphology of observation by light microscope
It is whole, it is essentially all spherical, particle size distribution compares concentration, and there is no that irregular particle is deposited
.
During catalyst support used for olefinic polymerization Z3 is prepared, do not have at the nozzle head of the spraying machine
There is blockage phenomenon, 12g carrier Z3 are obtained.
Comparative example 2
In the reactor of 1.6L, 0.08mol magnesium chlorides, 1.0mol ethanol and 0.35mol epoxies are added
Chloropropane, at 90 DEG C, stirring mixing, obtains fluidized mixture matter, using high-speed stirred (1800rpm)
Emulsifying is carried out to the fluidized mixture matter, and will using the spraying machine containing nozzle head and material conduit
Fluidized mixture matter after the emulsifying is sprayed in circulating nitrogen gas, and the fluidized mixture matter is described
Temperature in material conduit is 90 DEG C, and the temperature in the nozzle head is 120 DEG C.By the acquisition
Carrier predecessor hexane is washed 4 times, obtains catalyst support used for olefinic polymerization after vacuum drying 1h
D-Z2。
During catalyst support used for olefinic polymerization D-Z2 is prepared, at the nozzle head of the spraying machine
There is three blockings, after cleaning shower nozzle, 7g carriers are obtained.
Embodiment 4
The present embodiment be used to illustrating the preparation method of catalyst support used for olefinic polymerization of the present invention with
And the catalyst support used for olefinic polymerization prepared by methods described.
In the reactor of 1.6L, 0.08mol magnesium chlorides, 1.6mol ethanol are added, is heated up under agitation
To 90 DEG C, after isothermal reaction 1h, 20 DEG C are cooled to, are subsequently adding 0.3mol epoxychloropropane, obtain
To fluidized mixture matter.Using the spraying machine containing nozzle head and material conduit by the fluidized mixture matter
Spray in 120 DEG C of white oils.Wherein, temperature of the fluidized mixture matter in the material conduit is
20 DEG C, the temperature in the nozzle head is 100 DEG C.The carrier predecessor obtained in the white oil is used
Hexane is washed 4 times, obtains catalyst support used for olefinic polymerization Z4 after vacuum drying 1h.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z4 is 34 microns, grain
Footpath distribution ((D90-D10)/D50) is 1.1.The particle shape of catalyst support used for olefinic polymerization Z4
Comparison is regular, is essentially all spherical, and particle size distribution compares concentration, and there is no abnormity
Particle is present.
During catalyst support used for olefinic polymerization Z4 is prepared, do not have at the nozzle head of the spraying machine
There is blockage phenomenon, 10g carrier Z4 are obtained.
Test case 1
This test case prepares olefinic polymerization using the catalyst support used for olefinic polymerization of above-mentioned offer of the invention
With catalyst, and alkene is prepared using the catalyst for olefines polymerizing for preparing.
(1) prepare catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, subzero 20 DEG C are cooled to, will
8 grams of the carrier Z1 obtained by embodiment 1 is added thereto, and at subzero 20 DEG C stirs 30min.
Then, start to be to slowly warm up to 110 DEG C, in temperature-rise period, add the phthalic acid two of 1.5mL different
Butyl ester, filters off liquid after maintaining 30min at 110 DEG C.Then, titanium tetrachloride is added to wash 2 times,
Finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing C1.
(3) propylene polymerization
In the rustless steel autoclave of a 5L, purged using stream of nitrogen gas, then in nitrogen
The hexane solution of triethyl aluminum of 1mmol is introduced in gas air-flow, and (concentration of triethyl aluminum is
0.5mmol/mL), the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and
The hydrogen and the liquid propene of 2.5L of catalyst C1,1.5L (normal volume) of 10mg.It is warming up to
70 DEG C, and react 1 hour at such a temperature, cooling bleeds off pressure, and discharging is dried to obtain polypropylene powder.
As a result, the heap density of the polypropylene powder that this test case is prepared is 0.41g/cm3, additionally,
The polypropylene powder particle shape is good, is substantially not present special-shaped material.
Test case 2
This test case prepares olefinic polymerization using the catalyst support used for olefinic polymerization of above-mentioned offer of the invention
With catalyst, and alkene is prepared using the catalyst for olefines polymerizing for preparing.
This test case using carrying out with 1 identical method of test case, except that, gather alkene is prepared
The carrier used during catalysts is the carrier Z2 prepared in embodiment 2, obtains catalyst C2.
The process of the propylene polymerization in this test case is identical with test case 1, except that, institute
The catalyst for using is the above-mentioned catalyst C2 for preparing rather than catalyst C1.
Remaining is identical with test case 1.
As a result, the heap density of the polypropylene powder that this test case is prepared is 0.42g/cm3, additionally,
The polypropylene powder particle shape is good, is substantially not present special-shaped material.
Test case 3
This test case prepares olefinic polymerization using the catalyst support used for olefinic polymerization of above-mentioned offer of the invention
With catalyst, and alkene is prepared using the catalyst for olefines polymerizing for preparing.
This test case using carrying out with 2 identical method of test case, except that, gather alkene is prepared
The carrier used during catalysts is the carrier Z3 prepared in embodiment 3, obtains catalyst C3.
The process of the propylene polymerization in this test case is identical with test case 2, except that, institute
The catalyst for using is the above-mentioned catalyst C3 for preparing rather than catalyst C2.
Remaining is identical with test case 2.
As a result, the heap density of the polypropylene powder that this test case is prepared is 0.43g/cm3, additionally,
The polypropylene powder particle shape is good, is substantially not present special-shaped material.
Test case 4
This test case prepares olefinic polymerization using the catalyst support used for olefinic polymerization of above-mentioned offer of the invention
With catalyst, and alkene is prepared using the catalyst for olefines polymerizing for preparing.
This test case using carrying out with 1 identical method of test case, except that, gather alkene is prepared
The carrier used during catalysts is the carrier Z4 prepared in embodiment 4, obtains catalyst C4.
The process of the propylene polymerization in this test case is identical with test case 1, except that, institute
The catalyst for using is the above-mentioned catalyst C4 for preparing rather than catalyst C1.
Remaining is identical with test case 1.
As a result, the heap density of the polypropylene powder that this test case is prepared is 0.40g/cm3, additionally,
The polypropylene powder particle shape is good, is substantially not present special-shaped material.
Test case 5
This test case using carrying out with 1 identical method of test case, except that, gather alkene is prepared
The carrier used during catalysts is the carrier D-Z1 prepared in comparative example 1, obtains catalyst
D-C1。
The process of the propylene polymerization in this test case is identical with test case 1, except that, institute
The catalyst for using is the above-mentioned catalyst D-C1 for preparing rather than catalyst C1.
Remaining is identical with test case 1.
As a result, the heap density of the polypropylene powder that this test case is prepared is 0.38g/cm3, additionally,
The polypropylene powder particle shape is irregular.
Test case 6
This test case using carrying out with 3 identical method of test case, except that, gather alkene is prepared
The carrier used during catalysts is the carrier D-Z2 prepared in comparative example 2, obtains catalyst
D-C2。
The process of the propylene polymerization in this test case is identical with test case 3, except that, institute
The catalyst for using is the above-mentioned catalyst D-C2 for preparing rather than catalyst C3.
Remaining is identical with test case 3.
As a result, the heap density of the polypropylene powder that this test case is prepared is 0.37g/cm3, additionally,
The polypropylene powder particle shape is irregular.
As can be seen from the above results, carried using the olefin polymerization catalysis that the method for the present invention is prepared
The particle shape of body is not in irregular particle preferably, substantially, and the catalysis prepared with the carrier of gained
When agent is used for alkene (particularly propylene) polymerization, the good appearance substantially without opposite sex material of polymerization activity, system
The heap density of the standby polymer product for obtaining is substantially high compared with prior art, 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
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of preparation method of catalyst support used for olefinic polymerization, it is characterised in that the method includes：
1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound and formula shown in OH
(I) oxirane compound and optional inert liquid medium shown in enters at not higher than 35 DEG C
Row mixing, obtains fluidized mixture matter；
2) by step 1) the fluidized mixture matter that obtains solidified by way of spraying；
Wherein, in formula M gXY, X is halogen element, and Y is selected from halogen element, C1-C14Alkyl,
C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C8Alkyl or C3-C8Cycloalkyl；The oxirane
Shown in the structure of class compound such as formula (I)：
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or haloalkyl.
2. method according to claim 1, wherein, the process of the solidification is with atomization spray
Implement in the spraying machine of mouth, the atomizer contains material conduit and nozzle head, the fluidized mixture
Matter is caused in the nozzle head by the material conduit, and is sprayed to spraying machine by the nozzle head
The tower body containing inert media in solidified, the fluidized mixture matter is in the material conduit
Temperature is that between subzero 50 DEG C to 50 DEG C above freezing and the fluidized mixture matter is in the nozzle head
Temperature be 80-170 DEG C.
3. method according to claim 1, wherein, the inert liquid medium be silicone oil and/or
Inert fluid varsol；It is preferred that
The inert liquid medium is kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl
At least one in silicone oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
4. the method according to any one in claim 1-3, wherein, by formula M gXY institute
The magnesium halide for showing and general formula R1Alcohol compound shown in OH and the ethylene oxide shown in logical formula (I)
Compound and optional inert liquid medium include the step of mixing at not higher than 35 DEG C：First will be logical
Magnesium halide, general formula R shown in formula MgXY1Alcohol compound and the optional inertia shown in OH
Liquid medium carries out the first contact, after then contact first the mixture that obtains with shown in logical formula (I)
Oxirane compound carry out the second contact.
5. method according to claim 4, wherein, the condition of first contact includes：Temperature
Between spending for 60 DEG C to 150 DEG C, the time is 0.5-5h；It is preferred that
The condition of second contact includes：Temperature is that between subzero 30 DEG C to 35 DEG C above freezing the time is
0.1-4h。
6. the method according to any one in claim 1-3, wherein, relative to described in 1mol
Magnesium halide shown in formula M gXY, the general formula R1The consumption of the alcohol compound shown in OH is
4-30mol, the consumption of the oxirane compound shown in the logical formula (I) is 1-10mol；It is preferred that
Relative to the magnesium halide described in 1mol shown in formula M gXY, the general formula R1Alcohol shown in OH
The consumption of class compound be 6-20mol, the consumption of the oxirane compound shown in the logical formula (I)
For 2-6mol.
7. the method according to any one in claim 1-3, wherein, in formula M gXY,
X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C5Alkyl, C1-C5Alkoxyl, C6-C10Virtue
Base or C6-C10Aryloxy group composition group；It is preferred that
Magnesium halide shown in formula M gXY selected from magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium,
The group of chlorination isopropoxy magnesium and chlorination n-butoxy magnesium composition.
8. the method according to any one in claim 1-3, wherein, in general formula R1In OH,
R1For C1-C8Alkyl；It is preferred that
The general formula R1Alcohol compound shown in OH selected from ethanol, propanol, isopropanol, n-butyl alcohol,
The group of isobutanol, amylalcohol, isoamyl alcohol, hexanol, n-octyl alcohol and 2-Ethylhexyl Alcohol composition.
9. the method according to any one in claim 1-3, wherein, in formula (I), R2
And R3Hydrogen, C are stood alone as each1-C3Alkyl or haloalkyl；It is preferred that
Oxirane compound shown in formula (I) is selected from oxirane, expoxy propane, epoxy fourth
The group of alkane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide composition.
10. the olefin polymerization catalysis that the method by described in any one in claim 1-9 is prepared
Agent carrier.
11. carriers according to claim 10, wherein, the average particulate diameter of the carrier is
10-100 microns, particle diameter distribution are less than 1.2；It is preferred that
The average particulate diameter of the carrier is 30-70 microns, and particle diameter distribution is 0.7-0.9.
Catalyst support used for olefinic polymerization described in 12. claim 10 or 11 is preparing olefin polymerization
Application in catalyst.
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| CN109206546A (en) * | 2017-07-01 | 2019-01-15 | 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 |
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