CN106543315A - 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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- CN106543315A CN106543315A CN201510614090.8A CN201510614090A CN106543315A CN 106543315 A CN106543315 A CN 106543315A CN 201510614090 A CN201510614090 A CN 201510614090A CN 106543315 A CN106543315 A CN 106543315A
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Abstract
The present invention relates to field of olefin polymerisation, discloses a kind of catalyst support used for olefinic polymerization and its preparation method and application.The carrier has the structure shown in formula (I), wherein, R1For C1-C12Alkyl or C3-C12Cycloalkyl；X and Y are each independently selected from by halogen element, C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, and n is 2-m；In the carrier, the amount sum of the material of X and Y is not less than 3 with the amount ratio of the material of Mg.The above-mentioned catalyst support used for olefinic polymerization pattern for providing of the invention is preferable and is not susceptible to adhesion.
Description
Technical field
The present invention relates to field of olefin polymerisation, in particular it relates to a kind of catalyst support used for olefinic polymerization and
Its preparation method and application.
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.Should
The feature of method is to react at high temperature to obtain solid using epoxychloropropane with the alcohol adduct of melting.So
And, preparing catalyst carrier using the method, to there is preparation process unstable, is susceptible to carrier adhesion,
And the bad shortcoming of carrier molding effect, accordingly, it would be desirable to other surfactants are added in preparation process,
Such as stearic acid, span, quaternary ammonium compound etc..The addition of these materials, not only increases cost, and
Recycling to by-product has a negative impact, in addition, in the post processing of by-product is reclaimed, ethanol
It is more difficult with the recovery of epoxy compounds, which increases operating cost.
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 a kind of pattern preferably, be difficult to send out
Raw adhesion and the catalyst support used for olefinic polymerization of low production cost.
To achieve these goals, on the one hand, the present invention provides a kind of catalyst support used for olefinic polymerization,
The carrier has the structure shown in formula (I),
Wherein,
R1For C1-C12Alkyl or C3-C12Cycloalkyl；X and Y are each independently selected from by halogen unit
Element, C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n
For 2-m；
In the carrier, the amount sum of the material of X and Y is not less than 3 with the amount ratio of the material of Mg.
Second aspect, the present invention provide the preparation method of above-mentioned catalyst support used for olefinic polymerization, the method
Including：
1) by formula M gX2Shown magnesium halide, general formula R1Compound shown in OH and optional
Inert liquid medium carries out the first contact, then by the mixture obtained after the first contact and ethylene oxide
Compound carries out the second contact at not higher than 30 DEG C, obtains liquefied mixture；
2) by step 1) liquefied mixture that obtains is warming up to and is not less than 40 DEG C；
Wherein, in formula M gX2In, two X are identical or different, be each independently selected from by halogen element,
C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；In general formula R1In OH, R1
For C1-C12Alkyl or C3-C12Cycloalkyl；The oxirane compound has formula (II) institute
The structure shown,
Wherein, Y is selected from halogen element, C1-C14Alkyl or alkoxyl, C6-C14Aryl or aryloxy group group
Into group.
The third aspect, the present invention provide above-mentioned catalyst support used for olefinic polymerization and urge preparing olefin polymerization
Application in agent.
The above-mentioned catalyst support used for olefinic polymerization pattern for providing of the invention is preferable and is not susceptible to adhesion.
When preparing catalyst support used for olefinic polymerization using the said method of the present invention, it is only necessary to by halogenation
Magnesium, alcohol and oxirane compound mix at low temperature, after forming uniform solution, by simple liter
Temperature is obtained with the good carrier of pattern, has not only saved cost of material, need not also separate alcohols and ring
Oxidative ethane class compound, greatlys save operating cost.
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 that the catalyst support used for olefinic polymerization pattern optics that the preparation example 1 of the present invention is prepared shows
Micro mirror figure.
Fig. 2 is that the catalyst support used for olefinic polymerization pattern optics that the preparation example 2 of the present invention is prepared shows
Micro mirror figure.
Fig. 3 is the catalyst support used for olefinic polymerization pattern light that the contrast preparation example 1 of the present invention is prepared
Learn microscope 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.
In a first aspect, the invention provides a kind of catalyst support used for olefinic polymerization, the carrier has formula (I)
Shown structure,
Wherein,
R1For C1-C12Alkyl or C3-C12Cycloalkyl；X and Y are each independently selected from by halogen unit
Element, C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n
For 2-m；
In the carrier, the amount sum of the material of X and Y is not less than 3 with the amount ratio of the material of Mg.
In the present invention, in the structure shown in formula (I), preferred R1For C1-C10Alkyl or C3-C10
Cycloalkyl；X and Y are each independently selected from by chlorine, bromine, C1-C12Alkyl or alkoxyl, C6-C12
The group of aryl or aryloxy group composition；M is 0.1-1.9, and n is 2-m.
In the present invention, in the structure shown in formula (I), more preferred R1For C1-C8Alkyl or
C3-C8Cycloalkyl；X and Y are each independently selected from by chlorine, bromine, C1-C10Alkyl or alkoxyl,
C6-C10The group of aryl or aryloxy group composition；M is 0.1-1.9, and n is 2-m.
In the present invention, in the structure shown in formula (I), particularly preferred R1For C1-C6Alkyl or
C3-C6Cycloalkyl；X and Y are each independently selected from by chlorine, bromine, C1-C8Alkyl or alkoxyl,
C6-C10The group of aryl or aryloxy group composition；M is 0.1-1.9, and n is 2-m.
A kind of preferred embodiment of the invention, in the structure shown in formula (I), R1
For methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isoamyl
Base, n-hexyl, cyclopropyl, methylcyclopropyl groups, ethyl cyclopropyl, cyclopenta, methylcyclopentyl or ring
Hexyl；X and Y are each independently selected from by chlorine, bromine, methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, methoxyl group, ethyoxyl, positive third
Epoxide, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy,
Positive hexyloxy, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, trimethylphenyl, phenoxy group,
Methylphenoxy, ethyl phenoxy group, dimethyl phenoxy, trimethylbenzene epoxide；M is 0.1-1.9, n
For 2-m.
In the present invention, the amount sum of the material of X and Y and Mg elements more preferably in the carrier
Material amount ratio be 3-4.
In the present invention, it is preferred to the infrared spectrogram of the carrier includes following characteristics peak：605±
10cm-1；1154±10cm-1, 1284 ± 10cm-1, 1058 ± 10cm-1, 747 ± 10cm-1, 894 ±
10cm-1, 1211 ± 10cm-1。
, according to the invention it is preferred to the average particulate diameter of the carrier is 10-100 microns, particle diameter distribution
Less than 1.2.In the case of more preferably, the average particulate diameter of the carrier is 30-90 microns, particle diameter
Distribution is less than or equal to 0.9.This preferably with more preferred embodiment in, urged by the olefin polymerization
Catalyst prepared by agent carrier can obtain the olefin polymer with more high-bulk-density.In the present invention
In, the average particulate diameter and particle diameter distribution of the catalyst support used for olefinic polymerization can adopt Master
2000 laser particle analyzers of Sizer (being manufactured by Malvern Instruments Ltd) are measured.
Second aspect, the invention provides the preparation method of above-mentioned catalyst support used for olefinic polymerization, the party
Method includes：
1) by formula M gX2Shown magnesium halide, general formula R1Compound shown in OH and optional
Inert liquid medium carries out the first contact, then by the mixture obtained after the first contact and ethylene oxide
Compound carries out the second contact at not higher than 30 DEG C, obtains liquefied mixture；
2) by step 1) liquefied mixture that obtains is warming up to and is not less than 40 DEG C；
Wherein, in formula M gX2In, two X are identical or different, be each independently selected from by halogen element,
C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；In general formula R1In OH, R1
For C1-C12Alkyl or C3-C12Cycloalkyl；The oxirane compound has formula (II) institute
The structure shown,
Wherein, Y is selected from halogen element, C1-C14Alkyl or alkoxyl, C6-C14Aryl or aryloxy group group
Into group.
In the present invention, described " and optional inert liquid medium " refers to the inert liquid medium
There may be or do not exist, that is to say, that can need or be not required in first contact of the present invention
Want inert liquid medium.
In the present invention, formula M gX2Shown magnesium halide, general formula R1Compound shown in OH
It is for obtaining the carrier of aforesaid kind of the present invention with the concrete species of oxirane compound, because
This, the kind of carrier that those skilled in the art can be as needed selects different types of MgX2Shown
Magnesium halide, general formula R1Compound and oxirane compound shown in OH.
According to the present invention, formula is MgX2Magnesium halide, formula be R1The compound of OH, structure are such as
The consumption of the oxirane compound shown in formula (II) can be according to expected catalyst for olefines polymerizing
The composition of carrier carries out appropriate selection.In the present invention, relative to 1mol formula Ms gX2Shown
Magnesium halide, the preferably general formula R1The consumption of the compound shown in OH be 4-30mol, the epoxy second
The consumption of alkyl compound is 1-10mol.
In the case of more preferably, in the present invention, relative to 1mol formula Ms gX2Shown magnesium halide,
The general formula R1The consumption of the compound shown in OH is 10-25mol, the oxirane compound
Consumption is 3-6mol.
According to the present invention, the minor amount of water in above-mentioned each reactant can also participate in forming olefin polymerization catalysis
The reaction of agent carrier.
According to the present invention, in step 1) in, for by formula M gX2Shown magnesium halide, general formula R1OH
Shown compound and optional inert liquid medium carry out the condition of the first contact and are not particularly limited,
As long as the condition causes formula M gX2Shown magnesium halide and general formula R1Compound shown in OH is abundant
Reaction., according to the invention it is preferred to the condition of first contact includes：Temperature is 80-120 DEG C；
More preferably 80-100 DEG C.It is preferred that the condition of first contact includes：Time is 0.5-5h；More
Preferably 0.5-3h.
According to the present invention, in step 1) in, by the mixture obtained after the first contact and ethylene oxide
When compound carries out the second contact below 30 DEG C, preferably carry out under agitation.
In the present invention, by formula M gX2Shown magnesium halide, general formula R1Compound shown in OH with
It is and optional inert liquid medium carries out the temperature of gained mixture after the first contact usually above 30 DEG C, excellent
The mixture of acquisition and oxirane compound are carried out into the second contact again after being selected in cooling.
In the present invention, it is preferred to the condition of second contact includes：Temperature is 0-28 DEG C, and the time is
0.1-2h。
Under preferable case, in the present invention, in step 2) in, by step 1) mixing of the liquid that obtains
Thing is warming up to 40-120 DEG C.
According to the present invention, in step 2) in, by step 1) liquefied mixture that obtains is warming up to 40 DEG C
More than condition can be the existing various conditions that can form catalyst support used for olefinic polymerization, example
Such as, heating rate can be controlled, and preferred heating rate is 0.0001-15 DEG C/min, from economic angle
Degree and the final particle shape control aspect of resulting carrier consider that heating rate is particularly preferably 1-6 DEG C/min.
As it was previously stated, in step 2) in, preferably by step 1) liquefied mixture that obtains is warming up to
40-120 DEG C, more preferably by step 1) liquefied mixture that obtains is warming up to 50-90 DEG C.Especially,
It is preferred that being 1-60 minutes in the time of staying of the outlet temperature of the intensification, the more preferably time of staying is
15-50 minutes.The time of staying of the outlet temperature of intensification of the present invention is namely in outlet temperature
Temperature retention time.
According to the present invention, the consumption of the optional inert liquid medium can be according to formula M gX2It is shown
Magnesium halide consumption selecting.Usually, with 1mol formula Ms gX2On the basis of shown magnesium halide,
The consumption of the inert liquid medium can be 0.8-10L, preferably 2-8L.The inert liquid medium
Can be commonly used in the art various chemically interactive liquid does not occur with reactant and product
Medium.For example：The inert liquid medium can be silicone oil and/or inert fluid varsol.Specifically,
The inert liquid medium is preferably kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl
It is at least one or more of in silicone oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.This
The bright inert liquid medium is particularly preferably white oil.
In the present invention, the instantiation of oxirane compound of the structure as shown in formula (II) can be with
For but be not limited to：One kind in epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide
Or it is various.
According to the present invention, general formula R1The instantiation of the compound shown in OH can be but be not limited to：Second
Alcohol, propanol, isopropanol, n-butyl alcohol, isobutanol, amylalcohol, isoamyl alcohol, hexanol, n-octyl alcohol and 2-
One or more in ethyl hexanol.
In the present invention, formula M gX2The instantiation of shown magnesium halide can be but be not limited to：Chlorine
Change the one kind in magnesium, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium
Or it is various.From the ready availability angle of raw material, preferably magnesium chloride.
According to the present invention, the method can also be included through step 2) product that obtains carries out solid-liquid point
From washing and be dried solid product.The solid-liquid separation can be existing various can realize
The method of solid phase and liquid phase separation, such as sucking filtration, filter pressing or centrifugation are under preferable case, described solid
The detached method of liquid is filter press technique.The present invention is not particularly limited to the condition of filter pressing, to fill as far as possible
Realize that solid phase is separated with liquid phase with dividing to be defined.The washing can adopt well known to a person skilled in the art
The solid product for obtaining is washed by method, for example can be using inert hydrocarbon solvent (for example：Pentane,
Hexane, heptane, petroleum ether and gasoline) solid product to obtaining washs.The present invention is for described
Dry condition is not particularly limited, for example：The temperature of the drying can be 20-70 DEG C, described dry
The dry time can be 0.5-10 hours.According to the present invention, the drying can be in normal pressure or reduced pressure
Under carry out.
The third aspect, the present invention provide above-mentioned catalyst support used for olefinic polymerization and urge preparing olefin polymerization
Application in agent.
In the present invention, in the application for preparing catalyst for olefines polymerizing, preferably by above-mentioned olefinic polymerization
Further reacted with titanium source and internal electron donor compound with catalyst carrier, can obtain being suitable to make
For the catalyst that alkene (particularly propylene) is polymerized, i.e. catalyst for olefines polymerizing.
In the present invention, it is preferred to the titanium source in terms of titanium elements, the carrier in terms of magnesium elements and interior
The weight ratio of electron donor compound is 1：5-15：2-15；More preferably 1：6-13：3-12.
In the present invention, the internal electron donor compound can be the mistake for preparing catalyst for olefines polymerizing
Conventional use of various internal electron donor compounds in journey, the preferably internal electron donor compound are carboxylic acid
At least one in ester, alcohol ester, ether, ketone, nitrile, amine and silane；The more preferred internal electron donor
Compound be unitary or polyhydric aliphatic race carboxylate, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and
At least one in binary ether.In the present invention, the unitary or polyhydric aliphatic race carboxylate, unitary or many
The specific kind of selection of first aromatic carboxylic acid esters, binary alcohol esters and binary ether can refer to prior art and enter
Row is selected, and here of the present invention is no longer described in detail.
According to the present invention, the titanium source can be prepare catalyst for olefines polymerizing during routinely use
Various titanium-containing compounds.In step 2) in, the preferably titanium source has formula Ti (ORn)4-mXmInstitute
The structure shown, wherein, RnFor C1-C14Aliphatic group, X is F, Cl or Br, and m is whole for 1-4
Number；In the case of more preferably, the titanium source is titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, three fourth oxygen
Base titanium chloride, dibutoxy titanium chloride, butoxy titanous chloride., triethoxy titanium chloride, diethoxy
At least one in base titanium chloride and ethyoxyl titanous chloride..
In the present invention, it is described by above-mentioned catalyst support used for olefinic polymerization further with titanium source and interior electron
There is no particular limitation for the condition reacted by body compound, and under preferable case, the condition of the reaction can be with
Including：Reaction temperature is 80-130 DEG C, and the response time is 0.5-10 hours.
In the present invention, it is preferred to titanium source and the catalyst support used for olefinic polymerization are first carried out at low temperature
Contact mixing, it is then slow again to heat up to reach above-mentioned reaction temperature.Those skilled in the art are understanding
Can be operated according to Conventional wisdom in the art after technical scheme, here of the present invention
Repeat no more.
Under preferable case, the present invention also provides a kind of catalyst for olefinic polymerization, and the catalyst contains：
Catalyst for olefines polymerizing of the present invention, alkyl aluminum compound and optional external electron donor chemical combination
Thing." the optional external donor compound " refers to that external donor compound can be present or not
It is present in the catalyst for olefinic polymerization of the present invention, that is to say, that of the present invention for alkene
The catalyst of polymerized hydrocarbon can contain or not contain external donor compound.
In the present invention, the composition of the catalyst for olefines polymerizing has been carried out detailed above
Description, will not be described here.
In the present invention, contain olefinic polymerization of the present invention in the catalyst for olefinic polymerization
With catalyst, therefore, the catalyst for olefinic polymerization according to the present invention is as olefinic polymerization
During the catalyst of reaction, the heap density of the polymer for obtaining that is polymerized is greatly improved.
And, the catalyst for olefinic polymerization of the invention is given for alkyl aluminum compound and outward
The species and consumption of electron compound is not particularly limited.
Usually, the alkyl aluminum compound in the catalyst for olefinic polymerization, in terms of aluminium element
Can be as 1-2000 with the mol ratio of the catalyst for olefines polymerizing counted with titanium elements：1, preferably
20-500：1；The external donor compound can be 0.005-0.5 with the mol ratio of alkyl aluminum compound：
1, preferably 0.01-0.4：1.
Catalyst for olefinic polymerization of the invention, the alkyl aluminum compound can be this area
Conventional various alkyl aluminum compounds.For example, the alkyl aluminum compound can be triethyl aluminum, three different
Butyl aluminum, three n-butylaluminums, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine
Di-n-butyl aluminum, a chlorine di-n-hexyl aluminum, one aluminium ethide of dichloro, one aluminium isobutyl of dichloro, dichloro one are just
One or more in one n-hexyl aluminum of butyl aluminum and dichloro.
Catalyst for olefinic polymerization of the invention, the external donor compound can be this
The conventional various external donor compounds in field, for example, the external donor compound can be carboxylic
One or more in acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and silicon compound；It is excellent
Selection of land, the external electron donor are with general formula R8 aR9 bSi(OR10)cSilicon compound, wherein, a and b
The integer of respectively 0,1 or 2, c for 1-3 integer, and a+b+c's and be 4, R8、R9、R10
It is each independently C1-C18Substituted or unsubstituted alkyl；It is highly preferred that a and b are respectively 1, c
For 2, R8、R9It is each independently C3-C10Substituted or unsubstituted alkyl, R10For C1-C10's
Substituted or unsubstituted alkyl.Specifically, the example of the organo-silicon compound can be but be not limited to：
Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane,
Second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane,
Dicyclopentyl dimethoxyl silane, 2- ethyl piperidines base -2- t-butyldimethoxysilanes and (1,1,1- trifluoros
- 2- propyl group) -2- ethyl piperidine base dimethoxysilanes and (tri- fluoro- 2- propyl group of 1,1,1-)-methyl dimethoxy epoxide silicon
Alkane.
Present invention also offers a kind of method of olefinic polymerization, the method includes：Under olefin polymerization conditions,
At least one alkene is carried out into olefinic polyreaction with catalyst for olefines polymerizing of the present invention.
The method of olefinic polymerization according to the present invention, by using the olefin polymerization of the present invention
Catalyst, can prepare that particle shape is good, the polymer that heap density is high.The alkene of the present invention gathers
The method of conjunction is not particularly limited for olefin polymerization conditions and the alkene for being used.The alkene for example may be used
Think ethylene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2- methyl
One or more in -2-butylene, 1- amylenes, 2- amylenes, 1- hexenes and styrene, preferably ethylene,
One or more in propylene, 1-butylene, 2-butylene and styrene.
The method of olefinic polymerization of the invention, the olefinic polymerization can be according to the routine sides of this area
Method is carried out.For example, the olefinic polymerization can be polymerisation in bulk, gas-phase polymerization or slurry polymerization.According to
The olefine polymerizing process of the present invention, the olefin polymerization conditions can be the normal condition of this area, for example,
Polymerization temperature can be 0-150 DEG C, preferably 60-90 DEG C；Polymerization pressure can be normal pressure or pressurization.
In the case of particularly preferably, the method for the olefinic polymerization of the present invention includes：Under olefin polymerization conditions,
At least one alkene is carried out into olefinic polyreaction with the catalyst for olefinic polymerization of the present invention.
Hereinafter will be described the present invention by embodiment.
In following preparation example, embodiment and comparative example, 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 the following example.This area
Technical staff should not be construed as the restriction to technical scheme.
Preparation example 1
The preparation example is used to illustrate catalyst support used for olefinic polymerization of present invention offer and preparation method thereof.
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.7mol ethanol are added, is heated up under agitation
To 90 DEG C.After isothermal reaction 1 hour, 15 DEG C are cooled to, addition is cooled to the ring of 15 DEG C of 0.3mol in advance
Oxygen chloropropane is simultaneously persistently stirred, and after temperature is in 15 DEG C of stable 0.5h, is started to warm up, and heating rate is 2 DEG C
/ min, to after 50 DEG C, maintains 20min.Filter pressing, filter pressing product is washed with hexane 5 times, and vacuum is done
It is dry, obtain catalyst support used for olefinic polymerization Z1.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 70 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,
Surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and there is no abnormity
Particle is present.
The catalyst support used for olefinic polymerization Z1 is by XRF analysis of spectrum, the wherein material of chlorine
Amount and the material of Mg amount ratio be 3.8.
The catalyst support used for olefinic polymerization Z1 passes through infrared spectrum analysiss, in 605.4cm-1；
1154.2cm-1, 1284.4cm-1, 1058.7cm-1, 747.3cm-1, 894.6cm-1, 1211.4cm-1Occur
Characteristic peak.
Contrast preparation example 1
In the reactor of 0.6L, 0.08mol magnesium chlorides, 0.96mol ethanol are added, is risen under agitation
Temperature is to 90 DEG C.Isothermal reaction adds epoxychloropropane 0.48mol after 2 hours, press after reaction half an hour
Filter, filter pressing product is washed with hexane 5 times, is vacuum dried, is obtained catalyst support used for olefinic polymerization
D-Z1。
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization D-Z1 is 100 microns,
Particle diameter distribution ((D90-D10)/D50) is 1.6.Using the particle morphology of observation by light microscope as schemed
Shown in 3.It can be seen that there is substantial amounts of abnormity in catalyst support used for olefinic polymerization D-Z1
Particle, and surface is more coarse.
Catalyst support used for olefinic polymerization D-Z1 by XRF analysis of spectrum, the wherein material of chlorine
Amount is 2.4 with the amount ratio of the material of Mg.
The catalyst support used for olefinic polymerization D-Z1 passes through infrared spectrum analysiss, in 701.1cm-1；
758.4cm-1, 1658.3cm-1, 1054.8cm-1, 1077.6cm-1, 830.1cm-1, 1294.5cm-1Occur
Characteristic peak.
Preparation example 2
The preparation example is used to illustrate catalyst support used for olefinic polymerization of present invention offer and preparation method thereof.
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.2mol ethanol are added, is heated up under agitation
To 80 DEG C.After isothermal reaction 1.5 hours, 20 DEG C are cooled to, addition is cooled to 20 DEG C of 0.35mol in advance
Epoxychloropropane, after temperature is in 20 DEG C of stable 20min, start to warm up, heating rate is 3 DEG C/min,
To after 60 DEG C, 20min is maintained.Filter pressing, filter pressing product is washed with hexane 5 times, vacuum drying, is obtained
To catalyst support used for olefinic polymerization Z2.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z2 is 72 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.Using particle morphology such as Fig. 2 of observation by light microscope
It is shown.It can be seen that the particle shape of catalyst support used for olefinic polymerization Z2 is more regular,
Surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and there is no abnormity
Particle is present.
Catalyst support used for olefinic polymerization Z2 is by XRF analysis of spectrum, the wherein amount of the material of chlorine
Amount ratio with the material of Mg is 3.4.
The catalyst support used for olefinic polymerization Z2 passes through infrared spectrum analysiss, in 606.3cm-1；
1152.9cm-1, 1285.4cm-1, 1057.9cm-1, 746.6cm-1, 894.9cm-1, 1210.6cm-1Occur
Characteristic peak.
Preparation example 3
The preparation example is used to illustrate catalyst support used for olefinic polymerization of present invention offer and preparation method thereof.
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.44mol ethanol are added, is risen under agitation
Temperature is to 100 DEG C.After isothermal reaction 1 hour, 5 DEG C are cooled to, addition is cooled to 5 DEG C of 0.35mol's in advance
Epoxychloropropane, after temperature is in 5 DEG C of stable 40min, starts to warm up, and heating rate is 3 DEG C/min,
To after 70 DEG C, 30min is maintained.Filter pressing, filter pressing product is washed with hexane 5 times, vacuum drying, is obtained
To catalyst support used for olefinic polymerization Z3.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 75 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.Can be seen using the particle morphology of observation by light microscope
Go out, the particle shape of catalyst support used for olefinic polymerization Z3 is more regular, and surface is smooth, is substantially all
It is spherical, particle size distribution compares concentration, and there is no that irregular particle is present.
Catalyst support used for olefinic polymerization Z3 is by XRF analysis of spectrum, the wherein amount of the material of chlorine
Amount ratio with the material of Mg is 3.5.
The catalyst support used for olefinic polymerization Z3 passes through infrared spectrum analysiss, in 605.9cm-1；
1155.4cm-1, 1283.2cm-1, 1056.9cm-1, 748.4cm-1, 892.7cm-1, 1211.5cm-1Occur
Characteristic peak.
Preparation example 4
The preparation example is used to illustrate catalyst support used for olefinic polymerization of present invention offer and preparation method thereof.
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.7mol ethanol, the ring of 0.3mol are added
Oxygen chloropropane is simultaneously persistently stirred at 15 DEG C, after temperature is in 15 DEG C of stable 1.5h, is started to warm up, is risen
Warm speed is 2 DEG C/min, to after 50 DEG C, maintains 20min.Filter pressing, filter pressing product is washed with hexane
5 times, vacuum drying obtains catalyst support used for olefinic polymerization Z4.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z4 is 72 microns, grain
Footpath distribution ((D90-D10)/D50) is 1.1.The particle shape of catalyst support used for olefinic polymerization Z4
Comparison is regular, and surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and substantially
Upper no irregular particle is present.
The catalyst support used for olefinic polymerization Z4 is by XRF analysis of spectrum, the wherein material of chlorine
Amount and the material of Mg amount ratio be 3.0.
The catalyst support used for olefinic polymerization Z4 passes through infrared spectrum analysiss, in 606.2cm-1；
1153.8cm-1, 1284.4cm-1, 1057.5cm-1, 747.9cm-1, 893.5cm-1, 1211.2cm-1Occur
Characteristic peak.
Embodiment 1
The embodiment be used for illustrate the present invention offer catalyst support used for olefinic polymerization prepare alkene gather
Application in catalysts and prepare alkene.
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the glass reaction bottle of 300mL, is added, subzero 20 DEG C are cooled to,
40 grams of the catalyst support used for olefinic polymerization Z1 obtained by preparation example 1 is added thereto, and
30min is stirred at subzero 20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C, add in temperature-rise period
The diisobutyl phthalate of 1.5mL, filters off liquid after maintaining 30min at 110 DEG C.Then,
Add titanium tetrachloride to wash 2 times, finally washed with hexane 3 times, after being dried, obtain olefin polymerization catalysis
Agent C1.
(2) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The alkene of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg gathers
The liquid propene of the hydrogen and 2.5L of catalysts C1,1.5L (normal volume).70 DEG C are warming up to,
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 gained polypropylene powder is 0.44g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Comparative example 1
This comparative example is carried out using method similar to Example 1, in particular：
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the glass reaction bottle of 300mL, is added, subzero 20 DEG C are cooled to,
40 grams of the catalyst support used for olefinic polymerization D-Z1 obtained by contrast preparation example 1 is added into which
In, and 30min is stirred at subzero 20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C, heating up
The diisobutyl phthalate of 1.5mL is added in journey, filters off liquid after 30min being maintained at 110 DEG C.
Then, add titanium tetrachloride to wash 2 times, finally washed with hexane 3 times, after being dried, obtain olefinic polymerization
Use catalyst D-C1.
(2) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The alkene of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg gathers
The liquid propene of the hydrogen and 2.5L of catalysts D-C1,1.5L (normal volume).70 DEG C are warming up to,
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 is 0.38g/cm3, additionally, the polypropylene powder granule
In be all special-shaped material, mobility is bad.
Embodiment 2
The embodiment be used for illustrate the present invention offer catalyst support used for olefinic polymerization prepare alkene gather
Application in catalysts and prepare alkene.
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the glass reaction bottle of 300mL, is added, subzero 20 DEG C are cooled to,
40 grams of the catalyst support used for olefinic polymerization Z2 obtained by preparation example 2 is added thereto, and
30min is stirred at subzero 20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C, add in temperature-rise period
The diisobutyl phthalate of 1.5mL, filters off liquid after maintaining 30min at 110 DEG C.Then,
Add titanium tetrachloride to wash 2 times, finally washed with hexane 3 times, after being dried, obtain olefin polymerization catalysis
Agent C2.
(2) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The alkene of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg gathers
The liquid propene of the hydrogen and 2.5L of catalysts C2,1.5L (normal volume).70 DEG C are warming up to,
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 gained polypropylene powder is 0.45g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Embodiment 3
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the glass reaction bottle of 300mL, is added, subzero 20 DEG C are cooled to,
40 grams of the catalyst support used for olefinic polymerization Z3 obtained by preparation example 3 is added thereto, and
30min is stirred at subzero 20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C, add in temperature-rise period
The diisobutyl phthalate of 1.5mL, filters off liquid after maintaining 30min at 110 DEG C.Then,
Add titanium tetrachloride to wash 2 times, finally washed with hexane 3 times, after being dried, obtain olefin polymerization catalysis
Agent C3.
(2) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The alkene of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg gathers
The liquid propene of the hydrogen and 2.5L of catalysts C3,1.5L (normal volume).70 DEG C are warming up to,
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 gained polypropylene powder is 0.44g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Embodiment 4
The embodiment be used for illustrate the present invention offer catalyst support used for olefinic polymerization prepare alkene gather
Application in catalysts and prepare alkene.
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the glass reaction bottle of 300mL, is added, subzero 20 DEG C are cooled to,
40 grams of the catalyst support used for olefinic polymerization Z4 obtained by preparation example 4 is added thereto, and
30min is stirred at subzero 20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C, add in temperature-rise period
The diisobutyl phthalate of 1.5mL, filters off liquid after maintaining 30min at 110 DEG C.Then,
Add titanium tetrachloride to wash 2 times, finally washed with hexane 3 times, after being dried, obtain olefin polymerization catalysis
Agent C4.
(2) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The alkene of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg gathers
The liquid propene of the hydrogen and 2.5L of catalysts C4,1.5L (normal volume).70 DEG C are warming up to,
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 gained polypropylene powder is 0.40g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Can be seen that what is prepared using the method for the present invention from the result of above example and comparative example
The particle shape of catalyst support used for olefinic polymerization is good, surface is smooth, be not in irregular particle substantially,
And when being used for alkene (particularly propylene) polymerization with the catalyst of the carrier preparation of gained, additionally it is possible to carry
The heap density of high polymerizating product, the appearance substantially without opposite sex material, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
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 (11)
1. a kind of catalyst support used for olefinic polymerization, the carrier have the structure shown in formula (I),
Wherein,
R1For C1-C12Alkyl or C3-C12Cycloalkyl；X and Y are each independently selected from by halogen unit
Element, C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n
For 2-m；
In the carrier, the amount sum of the material of X and Y is not less than 3 with the amount ratio of the material of Mg.
2. carrier according to claim 1, wherein, the amount of the material of X and Y in the carrier
Sum is 3-4 with the amount ratio of the material of Mg elements：1.
3. carrier according to claim 1, wherein, the infrared spectrogram of the carrier includes
Following characteristics peak：605±10cm-1；1154±10cm-1, 1284 ± 10cm-1, 1058 ± 10cm-1,
747±10cm-1, 894 ± 10cm-1, 1211 ± 10cm-1。
4. carrier according to claim 1, wherein, the average particulate diameter of the carrier is 10-100
Micron, particle diameter distribution are less than 1.2；It is preferred that
The average particulate diameter of the carrier is 30-90 microns, and particle diameter distribution is less than or equal to 0.9.
5. the preparation method of the catalyst support used for olefinic polymerization in claim 1-4 described in any one,
The method includes：
1) by formula M gX2Shown magnesium halide, general formula R1Compound shown in OH and optional
Inert liquid medium carries out the first contact, then by the mixture obtained after the first contact and ethylene oxide
Compound carries out the second contact at not higher than 30 DEG C, obtains liquefied mixture；
2) by step 1) liquefied mixture that obtains is warming up to and is not less than 40 DEG C；
Wherein, in formula M gX2In, two X are identical or different, be each independently selected from by halogen element,
C1-C14Alkyl or alkoxyl, C6-C14The group of aryl or aryloxy group composition；In general formula R1In OH, R1
For C1-C12Alkyl or C3-C12Cycloalkyl；The oxirane compound has formula (II) institute
The structure shown,
Wherein, Y is selected from halogen element, C1-C14Alkyl or alkoxyl, C6-C14Aryl or aryloxy group group
Into group.
6. method according to claim 5, wherein, relative to 1mol formula Ms gX2Shown
Magnesium halide, the general formula R1The consumption of the compound shown in OH be 4-30mol, the ethylene oxide
The consumption of compound is 1-10mol；It is preferred that
Relative to 1mol formula Ms gX2Shown magnesium halide, the general formula R1Compound shown in OH
Consumption be 10-25mol, the consumption of the oxirane compound is 3-6mol.
7. method according to claim 5, wherein, the condition of first contact includes：Temperature
Spend for 80-120 DEG C, the time is 0.5-5h；It is preferred that
The condition of second contact includes：Temperature is 0-28 DEG C, and the time is 0.1-2h.
8. method according to claim 5, wherein, in step 2) in, by step 1) obtain
Liquefied mixture be warming up to 40-120 DEG C.
9. method according to claim 5, wherein, in step 2) in, the speed of the intensification
For 0.0001-15 DEG C/min；Preferably 1-6 DEG C/min.
10. method according to claim 5, wherein, in step 1) in, the inert fluid
Medium is silicone oil and/or inert fluid varsol；
It is preferred that the inert liquid medium be kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil,
At least one in ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
Catalyst support used for olefinic polymerization in 11. claim 1-4 described in any one is preparing alkene
Application in catalyst for polymerization.
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| CN102040681A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Carrier for preparing olefin polymerization catalyst and preparation method thereof |
| CN102453127A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Spherical carrier for olefin polymerization catalyst and preparation method thereof |
| CN104558283A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Solid composition as well as preparation method and application thereof |
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| CN102040681A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Carrier for preparing olefin polymerization catalyst and preparation method thereof |
| CN102453127A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Spherical carrier for olefin polymerization catalyst and preparation method thereof |
| CN104558283A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Solid composition as well as preparation method and application thereof |
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| CN111072811A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application thereof |
| CN111072811B (en) * | 2018-10-19 | 2023-05-02 | 中国石油化工股份有限公司 | Spherical carrier of olefin polymerization catalyst, preparation method thereof, catalyst component, catalyst and application of spherical carrier |
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