CN109206546A - 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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- CN109206546A CN109206546A CN201710528522.2A CN201710528522A CN109206546A CN 109206546 A CN109206546 A CN 109206546A CN 201710528522 A CN201710528522 A CN 201710528522A CN 109206546 A CN109206546 A CN 109206546A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
The present invention relates to polymer arts, disclose a kind of catalyst support used for olefinic polymerization and its preparation method and application, preparation method therein includes: 1) optionally to react magnesium compound, the first alcohol compound and oxirane compound in the presence of inert liquid medium, obtains solid matter；2) solid matter is dissolved in the second alcohol compound and is emulsified, obtain fluidized mixture matter；3) the fluidized mixture matter is mixed and is reacted with silica gel, obtain the fluidized mixture matter containing silica gel；4) the fluidized mixture matter containing silica gel is solidified by spraying mode, obtains the catalyst support used for olefinic polymerization.Preparation method of the invention is avoided that the obstruction of spraying machine, catalyst support used for olefinic polymerization obtained is not susceptible to that adhesion, pattern is good and particle size is adjustable, the catalytic activity with higher of the catalyst for olefines polymerizing as made from the catalyst carrier, and the olefin polymer of high heap density can be obtained.
Description
Technical field
The present invention relates to polymer arts, and in particular to a kind of preparation method of catalyst support used for olefinic polymerization, by this
Catalyst support used for olefinic polymerization made from preparation method and the catalyst support used for olefinic polymerization are in olefinic polymerization catalysis
Application in agent.
Background technique
It is well known that the Ziegler-Natta catalyst of chlorination magnesium alcoholate load is poly- for alkene (especially propylene)
When conjunction, performance is substantially better than the catalyst that other carriers are loaded.The catalyst is also most extensive currently used for olefinic polymerization
Industrial catalyst.
In order to obtain spherical chlorination magnesium alcoholate carrier, can be squeezed out by spray drying, misting cooling, high pressure, high-speed stirring
It mixes, the preparation of the methods of mulser method and high-gravity rotating bed method, such as disclose can by WO1999044009A1 and US4399054
Then to carry out quenching and form spherical alcohol adduct by high-speed stirred emulsified magnesium chloride alcohol adduct system under high temperature.However the mistake
Journey needs pyroreaction and chilling step, this is not only larger to the consumption of the energy, preparation process is complicated, need multiple reactors into
Row joint preparation, and the particle diameter distribution of obtained chlorination magnesium alcoholate is wider.In order to solve this problem, CN102040683A
A kind of method reacted by magnesium halide alcohol adduct with oxirane compound to prepare carrier is disclosed, i.e., by magnesium halide alcohol
After polymer melt dispersion, oxirane compound is added；It will be either added directly into after magnesium halide alcohol adduct melting dispersion
In reactor containing oxirane compound；However, using this method preparation catalyst carrier, that there are preparation process is unstable,
It is easy to happen carrier adhesion, and the disadvantage that carrier molding effect is bad.
The time that spray shaping method preparation catalyst carrier has the advantages that material is dried is short, general only to need
Several seconds to tens seconds, due to being atomized into the droplet of tens microns of sizes, the specific surface area of unit mass was larger, and moisture evaporation is fast,
The performance of catalyst can be improved to a certain extent；By changing operating condition, select atomizer appropriate, it is easily adjustable or
Control the quality index of product, such as particle diameter and size distribution；It is dry according to requiring powdery product can be made in product
After do not need to be crushed, shorten process flow, easily realize automation and improve operating condition.But the prior art is being adopted
With spray system for that usually material can be made to cause to block at the nozzle of spraying machine when catalyst support used for olefinic polymerization, specifically
Ground, the material reaction for preparing catalyst carrier will form liquid-solid two-phase system, since the partial size of suspended solid is larger, and be easy to produce
Therefore raw liquid-solid two-phase separation in pipe conveying procedure and conveys this system and enters nozzle and be all easy to cause to block.This is greatly
Affect the lasting progress of catalyst support used for olefinic polymerization preparation process.
Therefore, to solve the above-mentioned problems, need to develop a kind of new catalyst support used for olefinic polymerization and its preparation side
Method.
Summary of the invention
The present inventor has found under study for action, anti-in halogen-containing magnesium compound, alcohol and oxirane compound
After solid should being formed, after the solid being obtained by filtration is dissolved in alcohol, tiny silica gel particle is added, obtained carrier precursor solution
It is introduced by Sprayable when being solidified in spraying machine, the obstruction of pipeline and atomizer will not be caused, to be conducive to make
The lasting progress of standby technique, and obtain that pattern is good and the adjustable catalyst support used for olefinic polymerization of particle size simultaneously.For
This, the present invention provides a kind of preparation methods of catalyst support used for olefinic polymerization, and the alkene as made from the preparation method
Catalyst for polymerization carrier, the present invention also provides the catalyst support used for olefinic polymerization answering in olefin polymerization catalysis
With.
According to the first aspect of the invention, the present invention provides a kind of preparation method of catalyst support used for olefinic polymerization, should
Preparation method includes:
1) by magnesium compound, the first alcohol compound and oxirane compound optionally in the presence of inert liquid medium
Under reacted, obtain solid matter；
2) solid matter is dissolved in the second alcohol compound and is emulsified, obtain fluidized mixture matter；
3) the fluidized mixture matter is mixed and is reacted with silica gel, obtain the fluidized mixture matter containing silica gel；
4) the fluidized mixture matter containing silica gel is solidified by spraying mode, obtains the catalyst for olefines polymerizing and carries
Body；Wherein,
The general formula of the magnesium compound is MgXY, and X is halogen, and Y is selected from halogen or substituted or unsubstituted following group
One of: C1~C14Alkyl, C1~C14Alkoxy, C6~C14Aryl, C6~C14Aryloxy group；
The general formula of first alcohol compound is R1OH, R1For C1~C8Alkyl or C3~C8Naphthenic base；
The general formula of second alcohol compound is R8OH, R8For C1~C4Alkyl；
Shown in the structure of the oxirane compound such as formula (I):
In formula (I), R2And R3It is each independently selected from substituted or unsubstituted C1~C5Alkyl.
According to the second aspect of the invention, the present invention provides catalyst for olefines polymerizing made from above-mentioned preparation method and carries
Body.
According to the third aspect of the invention we, the present invention provides above-mentioned catalyst support used for olefinic polymerization in olefinic polymerization catalysis
Application in agent.
Preparation method of the invention by carrying out special dissolution process to reaction product, avoid spraying machine pipeline and
The first-class obstruction of atomizer, thus be conducive to the lasting progress of preparation process, moreover, surfactant is not used in preparation,
Reduce production cost；Along with the addition of silica gel, it can be prepared and be not susceptible to that adhesion, pattern is good and particle size can
The catalyst support used for olefinic polymerization of tune；The catalyst being prepared by catalyst support used for olefinic polymerization of the invention is in alkene
Have the characteristics that catalytic activity is high in polymerization reaction, while the higher polymer powders of heap density can be obtained.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with specific embodiment, the present invention will be described in detail, these realities
It applies mode and only serves illustrative, be not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of preparation method of catalyst support used for olefinic polymerization,
The preparation method includes:
1) by magnesium compound, the first alcohol compound and oxirane compound optionally in the presence of inert liquid medium
Under reacted, obtain solid matter；
2) solid matter is dissolved in the second alcohol compound and is emulsified, obtain fluidized mixture matter；
3) the fluidized mixture matter is mixed and is reacted with silica gel, obtain the fluidized mixture matter containing silica gel；
4) the fluidized mixture matter containing silica gel is solidified by spraying mode, obtains the catalyst for olefines polymerizing and carries
Body；Wherein,
The general formula of the magnesium compound is MgXY, and X is halogen, and Y is selected from halogen or substituted or unsubstituted following group
One of: C1~C14Alkyl, C1~C14Alkoxy, C6~C14Aryl, C6~C14Aryloxy group；
The general formula of first alcohol compound is R1OH, R1For C1~C8Alkyl or C3~C8Naphthenic base；
The general formula of second alcohol compound is R8OH, R8For C1~C4Alkyl；
Shown in the structure of the oxirane compound such as formula (I):
In formula (I), R2And R3It is each independently selected from substituted or unsubstituted C1~C5Alkyl.
In the present invention, general formula or chemical structural formula represent corresponding compound and can be selected from least one therein.
In the present invention, the substituted group (alkyl, alkoxy, aryl, aryloxy group) being previously mentioned refers on the group
Hydrogen atom is replaced by halogen etc..
In the present invention, halogen is selected from fluorine, chlorine, bromine or iodine.
In addition, alkyl, alkoxy that the present invention mentions may each be linear chain or branched chain.
Under preferable case, in formula M gXY, X is chlorine or bromine, and Y is selected from chlorine, bromine or substituted or unsubstituted following group
One of: C1~C5Alkyl, C1~C5Alkoxy, C6~C10Aryl, C6~C10Aryloxy group.
In the present invention, substituted or unsubstituted C1~C5The example of alkyl can include but is not limited to: methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, chloromethyl, bromine first
Base, chloroethyl, chloropropyl or bromopropyl.
Substituted or unsubstituted C1~C5The example of alkoxy can include but is not limited to: methoxyl group, ethyoxyl, propoxyl group,
Isopropoxy, butoxy, isobutoxy, chloroethoxy, chloropropanol oxygen radical or bromine propoxyl group.
Substituted or unsubstituted C6~C10The example of aryl can include but is not limited to: phenyl, o-tolyl, toluene
Base, p-methylphenyl, adjacent ethylbenzene, ethylbenzene, to ethylbenzene, naphthalene or bromophenyl.
Substituted or unsubstituted C6~C10The example of aryloxy group can include but is not limited to: phenoxy group or naphthoxy.
It is highly preferred that the magnesium compound be selected from magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and
At least one of chlorination n-butoxy magnesium.The angle being easy to get from raw material, the further preferred magnesium compound are chlorination
Magnesium.
According to the present invention, general formula R1In OH, R1Example can include but is not limited to: methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, isobutyl group, n-pentyl, isopentyl, cyclopropyl, cyclopenta, methylcyclopropyl groups, Dimethvlcvclopropvl, cyclohexyl,
Methylcyclopentyl or 2- ethylhexyl.
Under preferable case, general formula R1In OH, R1For C1~C8Alkyl.
It is highly preferred that first alcohol compound is selected from ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, different
At least one of amylalcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
Under preferable case, in formula (I), R2And R3It each is selected from substituted or unsubstituted C1~C3Alkyl.
It is highly preferred that the oxirane compound is selected from propylene oxide, epoxy butane, epoxychloropropane, epoxy chlorine
At least one of butane, epoxy bromopropane and epoxy bromobutane.
It is described " optionally in the presence of inert liquid medium " to refer to catalyst for olefines polymerizing of the invention in the present invention
Carrier reacts under the conditions of can be existing for the inert liquid medium, can also react in the presence of no inert liquid medium；
That is, can be added or be added without inert liquid medium in step 1) of the invention.
In the present invention, the inert liquid medium can be silicone oil and/or inert hydrocarbon solvent.
Under preferable case, the inert liquid medium be selected from kerosene, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil,
At least one of Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
According to the present invention, in step 1), the dosage for preparing the above-mentioned each component of catalyst support used for olefinic polymerization can be
It is selected and is changed in larger range, and can refer to the prior art and selected.
Under preferable case, in terms of every mole of magnesium compound, the dosage of first alcohol compound is 4~30mol, described
The dosage of oxirane compound is 1~10mol.
It is highly preferred that the dosage of first alcohol compound is 6~20mol, the ring in terms of every mole of magnesium compound
The dosage of oxidative ethane class compound is 2~6mol.
The condition that the present invention reacts each component in step 1) is not particularly limited, as long as enabling to magnesium chemical combination
Object, the first alcohol compound and oxirane compound react to form solid matter.It is described anti-under preferable case
The condition answered includes: that temperature is 70~90 DEG C, and the time is 0.2~5h.
Preferably, second alcohol compound can be selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol and isobutanol
At least one of.
According to the present invention, in terms of every mole of magnesium compound, the dosage of second alcohol compound is 4~30mol, preferably
For 6~20mol.
In the present invention, the mixture in step 2) dissolved with solid matter can be emulsified using well known any method
Obtain the fluidized mixture matter.
Specifically, obtained mixture can be subjected to high speed shear, its emulsification is made to obtain the fluidized mixture matter, institute
State high speed shear method be it is known in the art, for example, mixture is stirred with 2000~5000 revs/min of speed
It mixes.Further, it is also possible to which the method referring to disclosed in the following prior art emulsifies mixture solution: disclosed in CN1267508C
By the solution containing liquid halogenated magnesium adduct carried out in hypergravity bed rotation dispersion (speed of rotation can for 100~
3000 revs/min)；CN1463990A it is disclosed by the solution containing liquid halogenated magnesium adduct in mulser with 1500~
8000 revs/min of speed output；US6020279 is disclosed newborn by the solution containing liquid halogenated magnesium adduct by spray-on process
Change.
According to the present invention, in step 3), silica gel is added in fluidized mixture matter, can play and adjust fluidized mixture matter
The effect of viscosity combines this adjustment effect with spray-on process, and having widened each parameter regulation of spray-on process itself obtained can urge
The range of agent carrier particles size keeps the catalyst carrier scope of application obtained wider.
The main ingredient of the silica gel is silica, and specific surface area (BET method measurement) can be 10~1000m2/ g, hole
Holding (BET method measurement) can be 0.1~4cm3/ g, average particle size (laser particle analyzer measurement) can be 1~500 μm.
Under preferable case, the specific surface area of the silica gel is 100~600m20.2~2cm of/g, Kong Rongwei3/ g, average particle size
It is 1~100 μm.
According to the present invention, the mass ratio of the silica gel and magnesium compound can be 0.2~100, preferably 0.5~10.
In the present invention, it is 40 that the silica gel, which may include: temperature with the mixed reaction condition of fluidized mixture matter,
~70 DEG C, the time is 0.5~3h.
In the present invention, the fluidized mixture matter containing silica gel, which is carried out cured condition by spraying mode, to be
The various conditions for being capable of forming catalyst support used for olefinic polymerization in the prior art.
The cured process carries out in spraying machine, comprising: the fluidized mixture matter containing silica gel is passed through material
Conduit is led in nozzle head, is sprayed by the nozzle head to being solidified in the spraying machine tower body containing inert media.
Temperature of the fluidized mixture matter containing silica gel in the material conduit is -50 DEG C to 50 DEG C, in the spray
Temperature in mouth is 80~170 DEG C.
Under preferable case, temperature of the fluidized mixture matter containing silica gel in the material conduit is 0~50 DEG C,
Temperature in the nozzle head is 120~170 DEG C.
Normally, the temperature of inert media is 60~200 DEG C, preferably 90~150 DEG C in the spraying machine.
In the present invention, the inert media may include inert gas medium and inert liquid medium, to the indifferent gas
There is no particular limitation for the type of body medium, for example, the inert gas medium can for nitrogen, helium, carbon dioxide or its
Its suitable gas.
Above-mentioned inert liquid medium can for it is commonly used in the art it is various not with the fluidized mixture matter containing silica gel
The liquid medium of chemical action occurs.Its type that can be selected from inert liquid medium cited by step 1), preferably white oil.
In the present invention, the dosage of inert liquid medium can be selected according to the dosage of magnesium compound in spraying machine.Generally
In the case of, in terms of every mole of magnesium compound, the dosage of the inert liquid medium can be 0.8~10L, preferably 2~8L.
According to the present invention, step 1) and step 4) can also include: by products therefrom after the solid matter or solidification into
Row is separated by solid-liquid separation.
The separation of solid and liquid can be the various methods that can be realized solid phase and liquid phase separation in the prior art, such as take out
Filter, filters pressing or centrifuge separation.Under preferable case, described be separated by solid-liquid separation uses filter press technique.The present invention does not have the condition of filter press technique
Particularly limit, be subject to as far as possible fully realize solid phase and liquid phase separation.
In addition, after separation of solid and liquid, may also include washing and drying steps in step 4).
The inert hydrocarbon solvents such as pentane, hexane, heptane, petroleum ether or gasoline can be used in the washing.
Generally, the temperature of the drying is 20~70 DEG C, and the time is 0.5~10 hour, and the drying can be in normal pressure
Or it is carried out under reduced pressure.
According to the present invention, it in the preparation of the catalyst support used for olefinic polymerization, participates in micro in each raw material of preparation
Water can also participate in reaction.The minor amount of water may be from the water in synthesis material or reaction medium institute band.
According to the second aspect of the invention, the present invention provides the loads of catalyst for olefines polymerizing made from above-mentioned preparation method
Body.
The addition of silica gel can change the partial size adjustable extent and its specific surface property of catalyst carrier in the present invention, change
It is apt to its copolymerization performance.
Specifically, the average grain diameter of the catalyst support used for olefinic polymerization is 1~100 μm, and particle diameter distribution is less than 1.5.
The particle shape of the catalyst carrier is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no irregular particle.
The average grain diameter of the catalyst support used for olefinic polymerization is preferably 3~80 μm, and particle diameter distribution is preferably small
In 1.0.
According to the third aspect of the invention we, the present invention provides the catalyst support used for olefinic polymerization urges in olefinic polymerization
Application in agent.
The olefin polymerization catalysis generally includes major catalyst and optional co-catalyst (such as alkyl aluminum compound)
With optional external donor compound (such as organo-silicon compound), the catalyst carrier specifically can be used as the load of major catalyst
Body uses.The method for preparing the major catalyst is known in the art, such as by the catalyst carrier and titanium source and interior is given
Electron compound carries out haptoreaction, and the present invention repeats no more this.
In addition, when the olefin polymerization catalysis prepared using catalyst carrier of the invention is in olefin polymerization,
Polymerization activity with higher, and the olefin polymer powder of high-bulk-density can be made, the condition of polymerization reaction can also refer to
The prior art is selected, this is not particularly limited in the present invention.
The present invention will be described in detail by way of examples below.
In following embodiment, comparative example, Application Example and Comparison study example:
1, the average grain diameter and particle diameter distribution of catalyst support used for olefinic polymerization: Masters Sizer 2000 is used
Particle size analyzer (being manufactured by Malvern Instruments Ltd) is measured.
2, the apparent form of catalyst support used for olefinic polymerization: pass through the optical microscopy of model Eclipse E200
(being purchased from Nikon company) is observed.
3, it the heap density of polyolefine powder: is measured using method as defined in GB/T 1636-2008.
Embodiment 1
The present embodiment is used to illustrate that the preparation method of catalyst support used for olefinic polymerization of the invention and alkene obtained to be poly-
Catalysts carrier.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.6mol ethyl alcohol is added, is warming up to 90 DEG C under stiring, constant temperature
After reaction 1 hour, epoxychloropropane 0.48mol is added, 1.5mol second is added in filters pressing after reaction 0.5 hour in solid matter
Alcohol, using high-speed stirred (2800rm) carry out emulsification form fluidized mixture matter, by 10g silica gel (W.R.Grace, 955, Kong Rong
1.1~1.8cm3/ g, 245~375m of specific surface area2/ g) it is added in above-mentioned fluidized mixture matter, the hybrid reaction 2 at 50 DEG C
Hour, the fluidized mixture matter containing silica gel is obtained, reusing will be described containing silica gel containing the spraying machine of nozzle head and material conduit
Fluidized mixture matter spray into spraying machine tower body in 100 DEG C of circulating nitrogen gas, the fluidized mixture matter is led in the material
Temperature in pipe is 15 DEG C, and the temperature in the nozzle head is 120 DEG C.Obtained cured product is washed 4 times with hexane, very
After the dry 1h of sky, catalyst carrier Z1 is obtained.
In the preparation process of catalyst carrier Z1, there is no cloggings at the nozzle head of the spraying machine, there are
To 20g catalyst carrier Z1.
The average grain diameter (D50) of the catalyst carrier Z1 is 12 microns, and particle diameter distribution ((D90-D10)/D50) is 0.9,
By optical microphotograph sem observation, the particle shape of catalyst carrier Z1 is more regular, and surface is smooth, is essentially all spherical shape,
Concentration is compared in particle size distribution, and there is no that irregular particle exists.
Embodiment 2
The present embodiment is used to illustrate that the preparation method of catalyst support used for olefinic polymerization of the invention and alkene obtained to be poly-
Catalysts carrier.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.4mol ethyl alcohol is added, is warming up to 90 DEG C under stiring, constant temperature
After reaction 1.5 hours, epoxychloropropane 0.35mol is added, 1.6mol ethyl alcohol is added in filters pressing after reaction 0.5 hour, using high speed
Stirring (2800rm) carries out emulsification and forms fluidized mixture matter, and by 10g silica gel, (PQ Corporation, MS3050, hole holds 2.4
~3.7cm3/ g, 410~620m of specific surface area2/ g) it is added in above-mentioned fluidized mixture matter, hybrid reaction 2 is small at 60 DEG C
When, it obtains the fluidized mixture matter containing silica gel, reuses the spraying machine containing nozzle head and material conduit for described containing silica gel
Fluidized mixture matter sprays into spraying machine tower body in 120 DEG C of white oil, and the fluidized mixture matter is in the material conduit
Temperature is 15 DEG C, and the temperature in the nozzle head is 120 DEG C.Obtained cured product is washed 4 times with hexane, is dried in vacuo
After 1h, catalyst carrier Z2 is obtained.
In the preparation process of catalyst carrier Z2, there is no cloggings at the nozzle head of the spraying machine, there are
To 21g carrier Z2.
The average grain diameter (D50) of the catalyst carrier Z2 is 15 microns, and particle diameter distribution ((D90-D10)/D50) is 0.8,
By optical microphotograph sem observation, the particle shape of catalyst carrier Z2 is more regular, and surface is smooth, is essentially all spherical shape,
Concentration is compared in particle size distribution, and there is no that irregular particle exists.
Application Example 1
(1) preparation of catalyst for olefines polymerizing
In the reaction flask of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -20 DEG C, 8g is made by embodiment 1
Z1 is added thereto, and stirs 30min at -20 DEG C；Then, start to be to slowly warm up to 110 DEG C, 1.5mL is added in temperature-rise period
Diisobutyl phthalate, at 110 DEG C maintain 30min after filter off liquid；The titanium tetrachloride for being separately added into 90mL again is washed
It washs 2 times, is finally washed 3 times with hexane, obtain catalyst for olefines polymerizing C1 after dry.
(2) propylene polymerization
In the stainless steel autoclave of 5L, is purged using stream of nitrogen gas, then introduced in stream of nitrogen gas
The methylcyclohexyl diformazan of the hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of 1mmol triethyl aluminum, 0.05mmol
The hydrogen of catalyst C1,1.5L (normal volume) of oxysilane, the anhydrous hexane of 10mL and 10mg and the liquid propene of 2.5L；
70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharge drying, obtains polypropylene powder.
In this application embodiment, the activity of catalyst is 26.8kgPP/gcat, gained polypropylene in propylene polymerization
The heap density of powder is 0.3g/cm3, in addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Application Example 2
In this application embodiment, the preparation process of catalyst for olefines polymerizing is identical as Application Example 1, and difference exists
In the catalyst support used for olefinic polymerization used obtains catalyst C2 for Z2.
Propylene polymerization process is identical as Application Example 1, the difference is that, the catalyst used is C2.
In this application embodiment, the activity of catalyst is 27.6kgPP/gcat, gained polypropylene in propylene polymerization
The heap density of powder is 0.32g/cm3, in addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Comparative example 1
The preparation process of the catalyst support used for olefinic polymerization difference from example 1 is that, do not include filters pressing
And the operation of 1.5mol ethyl alcohol is added in solid matter, remaining operation is same as Example 1, and catalyst carrier D- is prepared
Z1。
In the preparation process of catalyst carrier D-Z1, occur to block twice at the nozzle head of the spraying machine, cleaning spray
15g carrier D-Z1 is obtained after head.
The average grain diameter (D50) of D-Z1 is 40 microns, and particle diameter distribution ((D90-D10)/D50) is 1.6, by optical microscopy
Observation, the particle shape of D-Z1 is more mixed and disorderly, is contaminated with irregular shape in spherical shape, particle size distribution range is wider.
Comparative example 2
The preparation process of the catalyst support used for olefinic polymerization difference from example 1 is that, do not include filters pressing
And the operation of 1.5mol ethyl alcohol is added in solid matter, and it is also added without silica gel and is mixed and reacted, remaining operation and implementation
Example 1 is identical, and catalyst carrier D-Z2 is prepared.
In the preparation process of catalyst carrier D-Z2, occur to block three times at the nozzle head of the spraying machine, cleaning spray
13g carrier D-Z2 is obtained after head.
The average grain diameter (D50) of D-Z2 is 25 microns, and particle diameter distribution ((D90-D10)/D50) is 1.5, by optical microscopy
Observation, the particle shape of D-Z2 is more mixed and disorderly, is contaminated with irregular shape in spherical shape, particle size distribution range is wider.
Comparison study example 1
In this application comparative example, the preparation process of catalyst for olefines polymerizing is identical as Application Example 1, and difference exists
In the catalyst carrier used obtains catalyst D-C1 for D-Z1.
Propylene polymerization process is identical as Application Example 1, the difference is that, the catalyst used is D-C1.
In this application embodiment, the activity of catalyst is 24.1kgPP/gcat, gained polypropylene in propylene polymerization
The heap density of powder is 0.26g/cm3, in addition, the polypropylene powder particle shape is irregular.
Comparison study example 2
In this application comparative example, the preparation process of catalyst for olefines polymerizing is identical as Application Example 1, and difference exists
In the catalyst carrier used obtains catalyst D-C2 for D-Z2.
Propylene polymerization process is identical as Application Example 1, the difference is that, the catalyst used is D-C2.
In this application embodiment, the activity of catalyst is 24.8kgPP/gcat, gained polypropylene in propylene polymerization
The heap density of powder is 0.27g/cm3, in addition, the polypropylene powder particle shape is irregular.
It can be seen that from above experimental result and carried using catalyst for olefines polymerizing made from preparation method of the invention
The particle shape of body preferably, be substantially not in irregular particle, and will be using the catalysis of obtained catalyst carrier preparation
The appearance that when agent polymerize for alkene (especially propylene), polymerization activity is high, polyolefine powder is substantially without opposite sex material, is prepared
Polymer heap density it is significantly higher, great prospects for commercial application.
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed embodiment.Without departing from the scope and spirit of illustrated embodiment, for the art
Many modifications and changes are obvious for those of ordinary skill.
Claims (10)
1. a kind of preparation method of catalyst support used for olefinic polymerization, which is characterized in that the preparation method includes:
1) by magnesium compound, the first alcohol compound and oxirane compound optionally in the presence of inert liquid medium into
Row reaction, obtains solid matter；
2) solid matter is dissolved in the second alcohol compound and is emulsified, obtain fluidized mixture matter；
3) the fluidized mixture matter is mixed and is reacted with silica gel, obtain the fluidized mixture matter containing silica gel；
4) the fluidized mixture matter containing silica gel is solidified by spraying mode, obtains the catalyst support used for olefinic polymerization；
Wherein,
The general formula of the magnesium compound is MgXY, and X is halogen, and Y is selected from halogen or substituted or unsubstituted following group
It is a kind of: C1~C14Alkyl, C1~C14Alkoxy, C6~C14Aryl, C6~C14Aryloxy group；
The general formula of first alcohol compound is R1OH, R1For C1~C8Alkyl or C3~C8Naphthenic base；
The general formula of second alcohol compound is R8OH, R8For C1~C4Alkyl；
Shown in the structure of the oxirane compound such as formula (I):
In formula (I), R2And R3It is each independently selected from substituted or unsubstituted C1~C5Alkyl.
2. preparation method according to claim 1, wherein in formula M gXY, X is chlorine or bromine, and Y is selected from chlorine, bromine, Huo Zhequ
One of generation or unsubstituted following group: C1~C5Alkyl, C1~C5Alkoxy, C6~C10Aryl, C6~C10Aryloxy group；
Preferably, the magnesium compound is being selected from magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination just
At least one of butoxy magnesium.
3. preparation method according to claim 1, wherein in terms of every mole of magnesium compound, first alcohol compound
Dosage be 4~30mol, the dosage of the oxirane compound is 1~10mol；
Preferably, in terms of every mole of magnesium compound, the dosage of first alcohol compound is 6~20mol, the ethylene oxide
The dosage of class compound is 2~6mol.
4. preparation method according to claim 1, wherein second alcohol compound be selected from methanol, ethyl alcohol, propyl alcohol,
At least one of isopropanol, n-butanol and isobutanol.
5. preparation method according to claim 1 or 4, wherein in terms of every mole of magnesium compound, the second alcohols chemical combination
The dosage of object is 4~30mol, preferably 6~20mol.
6. preparation method according to claim 1, wherein the specific surface area of the silica gel is 10~1000m2/ g, Kong Rongwei
0.1~4cm3/ g, average particle size are 1~500 μm；
Preferably, the specific surface area of the silica gel is 100~600m20.2~2cm of/g, Kong Rongwei3/ g, average particle size are 1~100
μm。
7. preparation method according to claim 1 or 6, wherein the mass ratio of the silica gel and magnesium compound be 0.2~
100 ︰ 1, preferably 0.5~10 ︰ 1.
8. preparation method according to claim 1, wherein the cured process carries out in spraying machine, comprising: by institute
It states the fluidized mixture matter containing silica gel to lead in nozzle head by material conduit, is sprayed by the nozzle head to containing inertia and be situated between
Solidified in the spraying machine tower body of matter；
Temperature of the fluidized mixture matter containing silica gel in the material conduit is -50 DEG C to 50 DEG C, in the nozzle head
In temperature be 80~170 DEG C.
9. catalyst support used for olefinic polymerization made from preparation method described in any one of claim 1~8.
10. application of the catalyst support used for olefinic polymerization as claimed in claim 9 in olefin polymerization catalysis.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149523A (en) * | 2020-09-05 | 2022-03-08 | 中国石油化工股份有限公司 | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020028743A1 (en) * | 1997-02-17 | 2002-03-07 | Luciano Luciani | Carrier for olefin polymerization catalysts |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN106543300A (en) * | 2015-09-23 | 2017-03-29 | 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 |
-
2017
- 2017-07-01 CN CN201710528522.2A patent/CN109206546B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020028743A1 (en) * | 1997-02-17 | 2002-03-07 | Luciano Luciani | Carrier for olefin polymerization catalysts |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN106543300A (en) * | 2015-09-23 | 2017-03-29 | 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149523A (en) * | 2020-09-05 | 2022-03-08 | 中国石油化工股份有限公司 | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof |
| CN114149523B (en) * | 2020-09-05 | 2022-11-18 | 中国石油化工股份有限公司 | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof |
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