CN109400773A - Catalytic component for olefinic polymerization and preparation method thereof and catalyst and olefine polymerizing process for olefinic polymerization - Google Patents
Catalytic component for olefinic polymerization and preparation method thereof and catalyst and olefine polymerizing process for olefinic polymerization Download PDFInfo
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- CN109400773A CN109400773A CN201710711261.8A CN201710711261A CN109400773A CN 109400773 A CN109400773 A CN 109400773A CN 201710711261 A CN201710711261 A CN 201710711261A CN 109400773 A CN109400773 A CN 109400773A
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Abstract
The present invention relates to field of olefin polymerisation, disclose a kind of catalytic component for olefinic polymerization and preparation method thereof and catalyst and olefine polymerizing process for olefinic polymerization, the preparation method includes: that catalyst carrier, titanium compound and optional internal electron donor compound are reacted, the catalyst carrier is prepared as method comprising the following steps: (1) by general formula be MgXY magnesium halide, general formula be ROH alcohol compound, carboxylic acid compound and optional inert liquid medium shown in formula (1) mix, emulsification；(2) emulsification product for obtaining step (1) and oxirane compound haptoreaction shown in formula (2).The catalytic activity of the catalyst of the catalytic component obtained containing the preparation method is high, also, the distribution of particles form of the olefin polymerization powder obtained using the catalyst preparation is preferable, and the stability of product preparation is good.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular, to a kind of catalytic component and its system for olefinic polymerization
Preparation Method, catalyst for olefinic polymerization and olefinic polymerization side containing the catalytic component for olefinic polymerization
Method.
Background technique
It is well known that its performance is substantially better than when the Ziegler-Natta catalyst of magnesium chloride load is used for propylene polymerization
The catalyst that other carriers are loaded.It therefore, is by the way that halogenated titanium is loaded in activation chlorine mostly for the catalyst of olefinic polymerization
Change on magnesium.Currently, activated magnesium chloride is usually by anhydrous MgCl2It is reacted at high temperature with alcohol after generating alcohol adduct again by de-
Alcohol is made.In order to obtain spherical alcohol adduct, spray drying, misting cooling, high pressure extrusion, high-speed stirred, mulser method can be passed through
And the methods of high-gravity rotating bed method preparation.Specific such as patent WO99/44009 and US4399054 is stirred by height under high temperature
Quenching forming preparation after emulsified magnesium chloride alcohol adduct system.
At one of preparation method of above-mentioned magnesium chloride spherical shape alcohol adduct what is common is that solidifying high temperature by cryogenic quenching
Alcohol adduct melt, it is larger to the consumption of the energy, and preparation process is complicated, must multiple reactors joint preparations, and it is obtained
Adduct particle diameter distribution it is wider.In order to solve this problem, CN102040683A propose it is a kind of by magnesium halide alcohol adduct with
Oxirane compound reacts to prepare carrier.It is all by magnesium halide alcohol but in the method used in existing document
After polymer melt dispersion, oxirane compound is directly added into the system, or magnesium halide alcohol adduct melting is divided
It is added directly into the reactor containing oxirane compound after dissipating.Due to the property of high-viscous liquid, experiment condition is not easily-controllable
System, this method prepare unstable result, are easy to happen carrier adhesion phenomenon, the disadvantage for causing carrier molding effect bad.Therefore,
Need to be added other surfactants, such as SPAN 80, SPAN 85 during the preparation process.The addition of these substances, not only increases
Add cost, and had an adverse effect to the recovery processing of by-product, also increases the cost of recycling post-processing.
Summary of the invention
The purpose of the invention is to overcome, the olefin polymerization catalysis preparation method of the prior art is complicated, activity is low, material
The problem of grain poor morphology, provide a kind of catalytic component for olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and olefine polymerizing process.
To achieve the goals above, the present inventor in a large amount of experimentation it has surprisingly been found that, using contain general formula R1
(COOH) catalyst carrier that the raw material of compound shown in is prepared is in olefin polymerization catalysis, catalyst can be showed
Preferable catalytic activity out, it is preferable using the olefin polymerization powder particles distributional pattern of the catalyst preparation.
One aspect of the present invention provides a kind of preparation method of catalytic component for olefinic polymerization, wherein the preparation side
Method includes: that catalyst carrier, titanium compound and optional internal electron donor compound are reacted, and the catalyst carrier is by wrapping
The method for including following steps is prepared:
(1) by general formula be MgXY magnesium halide, general formula be ROH alcohol compound, carboxylic acid compound shown in formula (1) and
Optional inert liquid medium mixing, emulsification；
(2) emulsification product for obtaining step (1) and oxirane compound haptoreaction shown in formula (2)；
Wherein, in formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C6-C14Aryl, C1-C14Alkoxy
Or C6-C14Aryloxy group；In general formula R OH, R C1-C8Alkyl or C3-C8Naphthenic base；In formula (1), R1For hydrogen, C1-C10's
Alkyl or halogenated alkyl, the C of linear chain or branched chain3-C10Naphthenic base or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl,
C7-C10Alkaryl or haloalkylaryl or C7-C10Aralkyl or haloaralkyl；In formula (2), R2And R3It is respectively independent
Ground is hydrogen, C1-C5Linear chain or branched chain alkyl or C1-C5Linear chain or branched chain halogenated alkyl.
Second aspect of the present invention provides the catalyst group for olefinic polymerization being prepared by preparation method of the invention
Point.
Third aspect present invention provides a kind of catalyst for olefinic polymerization, wherein the catalyst contains:
(1) catalytic component for olefinic polymerization of the invention；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
Fourth aspect present invention provides a kind of olefine polymerizing process, wherein the olefine polymerizing process includes: in olefinic polymerization
Under the conditions of, by one or more alkene and the catalytic component for being used for olefinic polymerization of the invention, alkyl aluminum compound and can
The external donor compound contact of choosing carries out olefin polymerization.
The preparation method of catalytic component for olefinic polymerization of the invention is simple, urges containing what the preparation method obtained
The catalytic activity of the catalyst of agent component is high, also, the particle point of the olefin polymerization powder obtained using the catalyst preparation
Cloth form is preferable, and the stability of product preparation is good, moreover, reducing surfactant without using surfactant and production being secondary
Product nuisanceless disposal expense, save the cost.
Detailed description of the invention
Fig. 1 is the pattern optical microscope for the carrier for olefin polymerization catalyst that preparation example 1 of the invention is prepared；
Fig. 2 is the pattern optical microscope for the carrier for olefin polymerization catalyst that preparation example 2 of the invention is prepared；
Fig. 3 is the pattern optical microscopy for the carrier for olefin polymerization catalyst that comparison preparation example 1 of the invention is prepared
Figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of preparation method of catalytic component for olefinic polymerization, wherein the preparation side
Method includes: that catalyst carrier, titanium compound and optional internal electron donor compound are reacted, and the catalyst carrier is by wrapping
The method for including following steps is prepared:
(1) by general formula be MgXY magnesium halide, general formula be ROH alcohol compound, carboxylic acid compound shown in formula (1) and
Optional inert liquid medium mixing, emulsification；
(2) emulsification product for obtaining step (1) and oxirane compound haptoreaction shown in formula (2)；
Wherein, in formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C6-C14Aryl, C1-C14Alkoxy
Or C6-C14Aryloxy group；In general formula R OH, R C1-C8Alkyl or C3-C8Naphthenic base；In formula (1), R1For hydrogen, C1-C10's
Alkyl or halogenated alkyl, the C of linear chain or branched chain3-C10Naphthenic base or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl,
C7-C10Alkaryl or haloalkylaryl or C7-C10Aralkyl or haloaralkyl；In formula (2), R2And R3It is respectively independent
Ground is hydrogen, C1-C5Linear chain or branched chain alkyl or C1-C5Linear chain or branched chain halogenated alkyl.
In the present invention, under preferable case, in the magnesium halide that general formula is MgXY, X is chlorine or bromine, and Y is by chlorine, bromine, C1-C5's
Alkyl, C6-C10Aryl, C1-C5Alkoxy or C6-C10Aryloxy group.The C1-C5Alkyl include but is not limited to methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl；The C1-C5Alkoxy include but
It is not limited to methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, different
Amoxy；The C6-C10Aryl include but is not limited to phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, trimethylbenzene
Base；The C6-C10Aryloxy group include but is not limited to phenoxy group, methylphenoxy, ethyl phenoxy group, dimethyl phenoxy, three
Methylphenoxy.In more preferred situation, the magnesium halide that general formula is MgXY is magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination
At least one of isopropoxy magnesium and chlorination n-butoxy magnesium.
In the present invention, under preferable case, in general formula R OH, R C1-C8Alkyl；In more preferable situation, general formula ROH
Alcohol compound be ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2- second
At least one of base hexanol.
In the present invention, under preferable case, in formula (1), R1For hydrogen or C1-C3Alkyl or halogenated alkyl；It is highly preferred that formula
(1) carboxylic acid compound shown in is at least one of formic acid, acetic acid, propionic acid and butyric acid.
In the present invention, under preferable case, in formula (2), R2And R3It is each independently hydrogen, C1-C3Alkyl or C1-C3Halogen
Substituted alkyl；It is further preferred that oxirane compound shown in formula (2) be ethylene oxide, propylene oxide, epoxy butane,
At least one of epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane.
In the present invention, it is appropriate that the dosage of each raw material can be carried out according to the composition of expected catalyst support used for olefinic polymerization
Selection.Under preferable case, by 1mol general formula for the magnesium halide of MgXY on the basis of, general formula be ROH alcohol compound dosage
For 4-30mol, the dosage of carboxylic acid compound shown in formula (1) is 0.001-1.5mol, ethylene oxide chemical combination shown in formula (2)
The dosage of object is 1-10mol.It is highly preferred that by 1mol general formula for the magnesium halide of MgXY on the basis of, general formula be ROH alcohols chemical combination
The dosage of object is 6-20mol, and the dosage of carboxylic acid compound shown in formula (1) is 0.01-1mol, ethylene oxide shown in formula (2)
The dosage of class compound is 2-6mol.
In the present invention, " the optional inert liquid medium " refers to that the inert liquid medium may exist or not deposit
?.In the presence of the inert liquid medium, the dosage of the inert liquid medium can be the halogen of MgXY according to general formula
Change the dosage of magnesium to select.Generally, shown in the 1mol formula M gXY on the basis of magnesium halide, the use of the inert liquid medium
Amount can be 0.8-10L, preferably 2-8L.The inert liquid medium can for it is commonly used in the art it is various not with reactant and
Chemically interactive liquid medium occurs for reaction product.Such as: the inert liquid medium can be silicone oil and/or inert liquid
Body hydrocarbon solvent.Specifically, the inert liquid medium is preferably kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, second
At least one of base silicone oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil are a variety of.Inert liquid of the present invention
Body medium is particularly preferably white oil.
In the present invention, the condition of the emulsification in step (1) is not particularly limited, as long as the condition makes raw material sufficiently anti-
It should.Preferably, in step (1), the condition of the emulsification includes: that temperature is 50-120 DEG C, preferably 60-90 DEG C；Time
It is 0.5-5 hours, preferably 0.5-3 hours.
It, can be using the mixture cream for obtaining step (1) well known to a person skilled in the art various methods in the present invention
Change.For example, the mixture can be carried out low velocity shear or high speed shear, to be emulsified.The low velocity shear stirs
Mixing rate is usually 400-800 revs/min.The method of the high speed shear is known to those skilled in the art, such as
High-speed mixing method disclosed in CN1151183C is (that is, by the solution containing liquid halogenated magnesium adduct with 2000-5000 revs/min
Speed be stirred).Further, it is also possible to which the method referring to following patent disclosure emulsifies the liquefied mixture:
CN1267508C is disclosed to carry out the rotation dispersion (speed of rotation for the solution containing liquid halogenated magnesium adduct in hypergravity bed
Degree can be 100-3000 revs/min)；The disclosed solution of liquid halogenated magnesium adduct that will contain of CN1463990A is in mulser
In exported with 1500-8000 revs/min of speed；US6020279 is disclosed will to contain liquid halogenated magnesium adduction by spray-on process
The emulsifying soln of object.
In the present invention, in step (2), the catalytic condition is preferably included: temperature is 50-120 DEG C, preferably
60-90℃；Time is 20-60 minutes, preferably 20-50 minutes.
In the present invention, the preparation method it is also preferable to include: after the haptoreaction, to reaction product carry out solid-liquid
Separation, and the solid phase isolated is washed and dried.The separation of solid and liquid, which can be, existing various can be realized solid phase
It with the method for liquid phase separation, such as filters, filters pressing or centrifuge separation, under preferable case, the method for the separation of solid and liquid is filters pressing
Method.The present invention is not particularly limited the condition of filters pressing, be subject to as far as possible fully realize solid phase and liquid phase separation.Institute
Obtained solid product can be washed using well known to a person skilled in the art methods by stating washing, such as can be used lazy
Property hydrocarbon solvent (such as: pentane, hexane, heptane, petroleum ether and gasoline) obtained solid product is washed.The present invention couple
It is not particularly limited in the condition of the drying, such as: the temperature of the drying can be 20-70 DEG C, the time of the drying
It can be 0.5-10 hours.According to the present invention, the drying can carry out under normal pressure or reduced pressure.
In the present invention, the average grain diameter of the carrier for olefin polymerization catalyst is 10-100 microns, and particle diameter distribution is small
In 1.2；Preferably, the average grain diameter of the carrier for olefin polymerization catalyst is 30-90 microns, and particle diameter distribution is less than or equal to
0.9；It is further preferred that the average grain diameter of the carrier for olefin polymerization catalyst is 30-70 microns, particle diameter distribution is
0.7-0.9." particle diameter distribution " refers to the value of (D90-D10)/D50.Average of the carrier for olefin polymerization catalyst
Grain diameter and particle diameter distribution can be (raw by Malvern Instruments Ltd using 2000 particle size analyzer of Masters Sizer
Produce manufacture) it is measured.
After the carrier for olefin polymerization catalyst of the invention is dissolved in inorganic acid, resulting mixture is examined through gas-chromatography
Survey contains carboxylic acid.
In the present invention, the titanium compound can be conventional use of during preparing the catalyst for olefinic polymerization
Various titanium compounds.In general, the titanium compound is general formula Ti (ORa)4-mXmCompound, wherein RaFor C1-C14Aliphatic hydrocarbon
Base, X F, Cl or Br, m are the integer of 1-4；The titanium compound is preferably titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, three fourths
Oxygroup titanium chloride, dibutoxy titanium chloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy titanium chloride and
One of ethyoxyl titanium trichloride is a variety of.
In the present invention, " the optional internal electron donor compound " refers to that the internal electron donor compound may exist
Or it is not present.The internal electron donor compound can be routinely to use during preparing the catalyst for olefinic polymerization
Various internal electron donor compounds, such as can be one of carboxylate, alcohol ester, ether, ketone, nitrile, amine and silane or a variety of,
Preferably one of unitary or polyhydric aliphatic race carboxylate, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether
Or it is a variety of.In the present invention, the unitary or polyhydric aliphatic race carboxylate, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and
The specific kind of selection of binary ether can refer to the prior art and be selected, and the present invention is no longer described in detail herein.
In the present invention, the titanium compound in terms of titanium elements, the carrier for olefin polymerization catalyst in terms of magnesium elements
Weight ratio with internal electron donor compound can be 1:5-15:2-15, preferably 1:6-13:3-12.
In the present invention, the carrier for olefin polymerization catalyst, titanium compound and optional internal electron donor compound it is anti-
There is no particular limitation for the condition answered, and under preferable case, the condition of the reaction may include: that reaction temperature is 80-130 DEG C,
Reaction time is 0.5-10 hours.
Second aspect of the present invention provides the catalyst group for olefinic polymerization being prepared by preparation method of the invention
Point.
Third aspect present invention provides a kind of catalyst for olefinic polymerization, wherein the catalyst contains:
(1) catalytic component for olefinic polymerization of the invention；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
" the optional external donor compound " refers to that external donor compound may exist or be not present.
The catalyst contains the catalytic component for olefinic polymerization of the invention, and therefore, the catalyst exists
When as olefin polymerization, the heap density for the polymer polymerizeing also is improved, while the form of polymer beads is good
It is good, and catalytic activity is high.
In the present invention, in the catalyst for olefinic polymerization, alkyl aluminum compound in terms of aluminium and in terms of titanium
The molar ratio of catalytic component for olefinic polymerization can be 1-2000:1, preferably 20-500:1；The external electron donor
The molar ratio of compound and alkyl aluminum compound can be 0.005-0.5:1, preferably 0.01-0.4:1.
In the present invention, the alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art.For example, described
Alkyl aluminum compound can be triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chlorine
Diisobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, one aluminium ethide of dichloro, one aluminium isobutyl of dichloro, dichloro one are just
One of one n-hexyl aluminium of butyl aluminium and dichloro is a variety of.
In the present invention, the external donor compound can be various external donor compounds commonly used in the art,
For example, the external electron donor can be one of carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organic phosphorus compound and silicon compound
Or it is a variety of；Preferably, the external electron donor is with general formula R4 aR5 bSi(OR6)cSilicon compound, wherein a and b are respectively
0, an integer of 1 or 2, c be 1-3 integer, and a+b+c's and be 4, R4、R5、R6It is each independently C1-C18Substitution or do not take
The alkyl in generation；It is highly preferred that a and b are respectively 1, c 2, R4、R5It is each independently C3-C10Substituted or unsubstituted alkyl,
R6For C1-C10Substituted or unsubstituted alkyl.Specifically, the example of the organo-silicon compound can be but be not limited to: ring
Hexyl methyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, diisobutyl dimethoxy
Base silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl
Piperidyl -2- t-butyldimethoxysilane and (the fluoro- 2- propyl of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilane and
(the fluoro- 2- propyl of 1,1,1- tri-)-methyl dimethoxysilane.
Fourth aspect present invention provides a kind of olefine polymerizing process, wherein the olefine polymerizing process includes: in olefinic polymerization
Under the conditions of, by one or more alkene and the catalytic component for being used for olefinic polymerization of the invention, alkyl aluminum compound and can
The external donor compound contact of choosing carries out olefin polymerization.
The olefine polymerizing process of the invention is by using the catalyst according to the present invention for olefinic polymerization
Component can prepare the polymer that particle shape is good, heap density is high.The olefine polymerizing process of the invention is poly- for alkene
Conjunction condition and used alkene are not particularly limited.
The alkene for example can be ethylene, propylene, 1- butylene, 2- butylene, 2-methyl-1-butene alkene, 3- methyl-1-fourth
One of alkene, 2- methyl-2-butene, 1- amylene, 2- amylene, 1- hexene and styrene are a variety of, preferably ethylene, propylene,
One of 1- butylene, 2- butylene and styrene are a variety of.
In the present invention, the olefinic polymerization can carry out according to conventional methods in the art.For example, the olefinic polymerization can
Think bulk polymerization, gas-phase polymerization or slurry polymerization.The condition of the olefinic polymerization can be the normal condition of this field, example
Such as, polymerization temperature can be 0-150 DEG C, preferably 60-90 DEG C；Polymerization pressure can be normal pressure or pressurization.
The present invention will be described in detail by way of examples below.In following embodiment and comparative example,
1, the average grain diameter and particle diameter distribution of carrier for olefin polymerization catalyst use Masters Sizer2000 granularity
Instrument (being manufactured by Malvern Instruments Ltd) is measured；
2, the apparent form of carrier for olefin polymerization catalyst and polyolefine powder is by being commercially available from the model of Nikon company
The optical microscopy of Eclipse E200 is observed；
3, the heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
Preparation example 1
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 0.96mol ethyl alcohol, anhydrous acetic acid 0.017mol (1ml) is added,
Epoxychloropropane 0.48mol is added after being warming up to 90 DEG C, reaction 1 hour in stirring, reacts filters pressing after half an hour, hexane washing
5 times.Vacuum drying, obtains catalyst support used for olefinic polymerization Z1.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 50 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.9.Particle morphology using optical microphotograph sem observation is as shown in Figure 1.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z1 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
After product is dissolved in dilute sulfuric acid, products therefrom is tested through gas chromatography-mass spectrum, contains acetic acid.
Preparation example 2
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 0.48mol ethyl alcohol, 0.01mol propionic acid is added, stirs, heating
To 60 DEG C, after reaction 0.5 hour, epoxychloropropane 0.16mol is added, reacts filters pressing after 20min, hexane washs 5 times.Vacuum is dry
It is dry, obtain catalyst support used for olefinic polymerization Z2.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 75 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 2.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z2 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
After product is dissolved in dilute sulfuric acid, products therefrom is tested through gas chromatography-mass spectrum, contains propionic acid.
Preparation example 3
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.6mol ethyl alcohol, 1mol butyric acid is added, stirring is warming up to 80
DEG C, after reaction 3 hours, epoxychloropropane 0.32mol is added, reacts filters pressing after 50min, hexane washs 5 times.Vacuum drying, obtains
To catalyst support used for olefinic polymerization Z3.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 46 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Using the particle morphology of optical microphotograph sem observation, the particle shape of catalyst support used for olefinic polymerization Z3
More regular, surface is smooth, is essentially all spherical shape, particle size distribution compares concentration, and there is no irregular particle
In the presence of.
After product is dissolved in dilute sulfuric acid, products therefrom is tested through gas chromatography-mass spectrum, contains butyric acid.
Preparation example 4
Catalyst support used for olefinic polymerization is prepared according to the method for preparation example 1, unlike, using the penta of same molar
Acid replaces anhydrous acetic acid.Obtain catalyst support used for olefinic polymerization Z4.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 82 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.9.Using the particle morphology of optical microphotograph sem observation, the particle shape of catalyst support used for olefinic polymerization Z4
More regular, surface is smooth, is essentially all spherical shape, particle size distribution compares concentration, and there is no irregular particle
In the presence of.
After product is dissolved in dilute sulfuric acid, products therefrom is tested through gas chromatography-mass spectrum, contains valeric acid.
Compare preparation example 1
Catalyst support used for olefinic polymerization is prepared according to the method for preparation example 1, unlike, anhydrous acetic acid is not added.It obtains
Catalyst support used for olefinic polymerization D-Z1.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization D-Z1 is 100 microns, particle diameter distribution
((D90-D10)/D50) is 1.6.Particle morphology using optical microphotograph sem observation is as shown in Figure 3.It can be seen from the figure that alkene
There are a large amount of irregular particles in polymerized hydrocarbon catalyst carrier D-Z1, and surface is more coarse.
Embodiment 1
(1) preparation of catalyst component for olefin
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, subzero 20 DEG C are cooled to, by 40 grams by making
The catalyst support used for olefinic polymerization Z1 that standby example 1 obtains is added thereto, and stirs 30min at subzero 20 DEG C.Later, it opens
Beginning is to slowly warm up to 110 DEG C, and the diisobutyl phthalate of 1.5mL is added in temperature-rise period, maintains at 110 DEG C
Liquid is filtered off after 30min.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain olefinic polymerization after dry
With catalytic component C1.
(2) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
The hydrogen and 2.5L of catalyst component for olefin C1,1.5L (normal volume) of silane, the anhydrous hexane of 10mL and 10mg
Liquid propene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharging is dried to obtain polypropylene powder.
The catalytic activity of catalyst is 36.9kgPP/gcat, and the heap density of gained polypropylene powder is 0.44g/cm3,
In addition, the polypropylene powder particle shape is good, abnormity material (aspheric moulding mixture) is substantially not present.
Embodiment 2
Polypropylene powder is prepared according to the method for embodiment 1, unlike, the alkene obtained using preparation example 2 is poly-
It closes catalyst carrier Z2 and replaces Z1, obtain polypropylene powder.
The catalytic activity of catalyst is 36.6kgPP/gcat, and the heap density of the polypropylene powder is 0.44g/cm3, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Embodiment 3
Polypropylene powder is prepared according to the method for embodiment 1, unlike, the alkene obtained using preparation example 3 is poly-
It closes catalyst carrier Z3 and replaces Z1, obtain polypropylene powder.
The catalytic activity of catalyst is 37.0kgPP/gcat, and the heap density of the polypropylene powder is 0.45g/cm3, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Embodiment 4
Polypropylene powder is prepared according to the method for embodiment 1, unlike, the alkene obtained using preparation example 4 is poly-
It closes catalyst carrier Z4 and replaces Z1, obtain polypropylene powder.
The catalytic activity of catalyst is 36.1kgPP/gcat, and the heap density of the polypropylene powder is 0.43g/cm3, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Comparative example 1
Polypropylene powder is prepared according to the method for embodiment 1, the difference is that, the alkene obtained using comparison preparation example 1
Polymerized hydrocarbon catalyst carrier D-Z1 replaces Z1, obtains polypropylene powder.
The catalytic activity of catalyst is 32.2kgPP/gcat, and the heap density of the polypropylene powder is 0.38g/cm3, this
It outside, is all special-shaped material in the polypropylene powder particle, mobility is bad.
By example made above, the result of embodiment and comparative example compare it can be seen from using preparation of the invention catalysis
Catalytic activity of agent component when for olefinic polymerization is relatively high, and the form of obtained polypropylene powder is good, heap density is high.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of preparation method of the catalytic component for olefinic polymerization, which is characterized in that the preparation method includes: catalyst
Carrier, titanium compound and optional internal electron donor compound reacted, and the catalyst carrier is by including the following steps
Method is prepared:
(1) by general formula be MgXY magnesium halide, general formula be ROH alcohol compound, carboxylic acid compound shown in formula (1) and optional
Inert liquid medium mixing, emulsification；
(2) emulsification product for obtaining step (1) and oxirane compound haptoreaction shown in formula (2)；
Wherein, in formula M gXY, X is halogen, and Y is halogen, C1-C14Alkyl, C6-C14Aryl, C1-C14Alkoxy or C6-
C14Aryloxy group；In general formula R OH, R C1-C8Alkyl or C3-C8Naphthenic base；In formula (1), R1For hydrogen, C1-C10Straight chain
Or alkyl or halogenated alkyl, the C of branch3-C10Naphthenic base or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10
Alkaryl or haloalkylaryl or C7-C10Aralkyl or haloaralkyl；In formula (2), R2And R3It is each independently
Hydrogen, C1-C5Linear chain or branched chain alkyl or C1-C5Linear chain or branched chain halogenated alkyl.
2. preparation method according to claim 1, wherein in general formula R OH, R C1-C8Alkyl；In formula (1), R1For hydrogen
Or C1-C3Alkyl or halogenated alkyl；In formula (2), R2And R3It is each independently hydrogen, C1-C3Alkyl or C1-C3Alkyl halide
Base；X is chlorine or bromine；Y is chlorine, bromine, C1-C5Alkyl, C6-C10Aryl, C1-C5Alkoxy or C6-C10Aryloxy group.
3. preparation method according to claim 1 or 2, wherein by 1mol general formula for the magnesium halide of MgXY on the basis of, general formula
Dosage for the alcohol compound of ROH is 4-30mol, and the dosage of carboxylic acid compound shown in formula (1) is 0.001-1.5mol, formula
(2) dosage of oxirane compound shown in is 1-10mol.
4. preparation method according to claim 3, wherein by 1mol general formula for the magnesium halide of MgXY on the basis of, general formula is
The dosage of the alcohol compound of ROH is 6-20mol, and the dosage of carboxylic acid compound shown in formula (1) is 0.01-1mol, formula (2) institute
The dosage of the oxirane compound shown is 2-6mol.
5. preparation method according to claim 1 or 2, wherein in step (1), the condition of the emulsification includes: that temperature is
50-120 DEG C, preferably 60-90 DEG C；Time is 0.5-5 hours, preferably 0.5-3 hours.
6. preparation method according to claim 1 or 2, wherein in step (2), the catalytic condition includes: temperature
Degree is 50-120 DEG C, preferably 60-90 DEG C；Time is 20-60 minutes, preferably 20-50 minutes.
7. preparation method according to claim 1 or 2, wherein the preparation method further include: the haptoreaction terminates
Afterwards, reaction product is separated by solid-liquid separation, and the solid phase isolated is washed and dried.
8. preparation method according to claim 1 or 2, wherein the average grain diameter of the catalyst carrier is 10-
100 microns, particle diameter distribution is less than 1.2；
Preferably, the average grain diameter of the catalyst carrier is 30-90 microns, and particle diameter distribution is less than or equal to 0.9.
9. the catalytic component for olefinic polymerization that the preparation method as described in claim 1-8 is prepared.
10. a kind of catalyst for olefinic polymerization, which is characterized in that the catalyst contains:
(1) catalytic component as claimed in claim 9 for olefinic polymerization；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
11. a kind of olefine polymerizing process, which is characterized in that the olefine polymerizing process include: under olefin polymerization conditions, will be a kind of
Or a variety of alkene and it is as claimed in claim 9 for the catalytic component of olefinic polymerization, alkyl aluminum compound and it is optional outside
The contact of electron donor compound carries out olefin polymerization.
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