CN106543311B - Catalyst support used for olefinic polymerization and its preparation method and application - Google Patents
Catalyst support used for olefinic polymerization and its preparation method and application Download PDFInfo
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- CN106543311B CN106543311B CN201510612682.6A CN201510612682A CN106543311B CN 106543311 B CN106543311 B CN 106543311B CN 201510612682 A CN201510612682 A CN 201510612682A CN 106543311 B CN106543311 B CN 106543311B
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Abstract
The present invention relates to field of olefin polymerisation, disclose catalyst support used for olefinic polymerization and its preparation method and application, the method comprise the steps that 1) by magnesium halide shown in formula M gXY, general formula R1OH compound represented, oxirane compound and optional inert liquid medium are mixed under conditions of being no more than 35 DEG C, obtain mixture solution；2) mixture solution that step 1) obtains is warming up under agitation not less than 40 DEG C.The pattern for the catalyst support used for olefinic polymerization that the above method of the invention is prepared is preferable, when the catalyst prepared with obtained carrier is used for alkene (especially propylene) polymerization, the heap density of polymerizate can also be improved, and the appearance substantially without opposite sex material.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular, to a kind of preparation method of catalyst support used for olefinic polymerization,
Catalyst support used for olefinic polymerization prepared by the above method and its application.
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.Therefore, it is mostly currently used for the catalyst of olefinic polymerization
It is prepared and halogenated titanium is carried on chlorination magnesium alcoholate.It, can be by being spray-dried, spraying in order to obtain ball type carrier
The methods of mist cooling, high pressure extrusion, high-speed stirred, mulser method and high-gravity rotating bed method preparation, such as WO1999044009A1
It discloses and can be quenched by under high temperature after high-speed stirred emulsified magnesium chloride alcohol adduct system with shape with US4399054 etc.
At spherical alcohol adduct.
But when the catalyst for preparing the chlorination magnesium alcoholate as disclosed in the above-mentioned prior art is used for olefinic polymerization,
It is easy to that the Fragmentation Phenomena of polymer particle occurs in the course of the polymerization process, to cause fine polymer powder more.In order to overcome this
One disadvantage, people attempt to introduce electron donor compound in advance in the carrier preparation of chlorination magnesium alcoholate again, such as:
Internal electron donor phthalate compound commonly understood in the industry is introduced into chlorination by CN1169840C and CN1286863C
In the synthesis of magnesium alcoholate carrier, to obtain " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier, then by the carrier with
Titanium tetrachloride reaction is to form catalyst.But the compound ball type carrier is easy tacky during the preparation process, it is difficult to be formed
The suitable spheric granules of particle size.
In addition, above-mentioned chlorination magnesium alcoholate is to use cryogenic quenching means to solidify the alcohol adduct melt of high temperature and be made,
It is not only larger to the consumption of the energy, preparation process is complicated, multiple reactors is needed to carry out joint preparation, but also obtained alcohol adduct
Particle diameter distribution it is wider.In order to solve this problem, CN102040683A discloses a kind of by magnesium halide alcohol adduct and epoxy second
The method that alkyl compound reacts to prepare carrier, and specifically disclose after magnesium halide alcohol adduct melting dispersion, epoxy is added
Ethane compound；Either the reaction containing oxirane compound will be added directly into after magnesium halide alcohol adduct melting dispersion
In device.The feature of this method is to react to obtain solid at high temperature with the alcohol adduct of melting using epoxychloropropane.However, using
This method prepares catalyst carrier, and that there are preparation process is unstable, is easy to happen carrier adhesion, and carrier molding effect is bad
Disadvantage, therefore, it is necessary to other surfactants, such as stearic acid, sapn, quaternary ammonium compound are added during the preparation process.These objects
The addition of matter not only increases cost, and has an adverse effect to the recovery processing of by-product, in addition, in by-product
In post-processing recycling, the recycling of ethyl alcohol and epoxy compounds is more difficult, and which increases operating costs.
Therefore, developing one kind can overcome the new catalyst support used for olefinic polymerization of the drawbacks described above of the prior art to have
Significance.
Summary of the invention
The purpose of the present invention is overcoming the drawbacks described above of the prior art, the alkene that a kind of pattern is preferable, production cost is low is provided
Polymerized hydrocarbon catalyst carrier.
To achieve the goals above, in a first aspect, the present invention provides a kind of preparation side of catalyst support used for olefinic polymerization
Method, this method comprises:
1) by magnesium halide shown in formula M gXY and general formula R1OH compound represented and oxirane compound and
Optional inert liquid medium is mixed under conditions of being no more than 35 DEG C, obtains mixture solution；
2) mixture solution that step 1) obtains is warming up under agitation not less than 40 DEG C；
Wherein, in formula M gXY, X is halogen element, and Y is selected from by halogen element, C1-C14Alkyl, C1-C14Alkoxy,
C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C8Alkyl or C3-C8Naphthenic base；
The oxirane compound has structure shown in formula (I):
Formula (I),
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or halogenated alkyl.
Second aspect, the present invention provide catalyst support used for olefinic polymerization prepared by the above method.
The third aspect, the present invention provide above-mentioned carrier and are preparing the application in catalyst for olefines polymerizing.
The pattern for the catalyst support used for olefinic polymerization that the above method of the invention is prepared is preferable, will be with obtained
When the catalyst of carrier preparation polymerize for alkene (especially propylene), additionally it is possible to improve the heap density of polymerizate, and base
This appearance without opposite sex material.
Preparation method of the invention uses and mixes magnesium halide, alcohol compound and oxirane compound at low temperature
It closes, after forming uniform solution, is obtained with the good carrier of pattern by simply heating up, has not only saved cost of material,
And need not separating alcohol compound and oxirane compound, operating cost is greatly saved, and surface need not be used
The additives such as activating agent.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the catalyst support used for olefinic polymerization pattern optical microscope that preparation example 1 of the invention is prepared.
Fig. 2 is the catalyst support used for olefinic polymerization pattern optical microscope that preparation example 2 of the invention is prepared.
Fig. 3 is the catalyst support used for olefinic polymerization pattern optical microscope that preparation example 3 of the invention is prepared.
Fig. 4 is the catalyst support used for olefinic polymerization pattern optical microscope that preparation example 4 of the invention is prepared.
Fig. 5 is the catalyst support used for olefinic polymerization pattern optical microscopy that comparison preparation example 1 of the invention is prepared
Figure.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In a first aspect, the present invention provides a kind of preparation methods of catalyst support used for olefinic polymerization, this method comprises:
1) by magnesium halide shown in formula M gXY and general formula R1OH compound represented and oxirane compound and
Optional inert liquid medium is mixed under conditions of being no more than 35 DEG C, obtains mixture solution；
2) mixture solution that step 1) obtains is warming up under agitation not less than 40 DEG C；
Wherein, in formula M gXY, X is halogen element, and Y is selected from by halogen element, C1-C14Alkyl, C1-C14Alkoxy,
C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C8Alkyl or C3-C8Naphthenic base；
The oxirane compound has structure shown in formula (I):
Formula (I),
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or halogenated alkyl.
In the present invention, described " and optional inert liquid medium " refers to that the inert liquid medium can participate in mixing
Close or be not involved in mixing.That is, inert liquid medium can be needed or not needed in method of the invention.
In the present invention, the halogen element includes fluorine, chlorine, bromine and iodine.
In the present invention, the C1-C14Alkyl refer to that carbon number is the alkyl of 1-14, including branched alkyl and branch
Alkyl, including unsubstituted alkyl and the hydrogen atom selectively substitution alkyl substituted by halogen element etc..
In the present invention, the C1-C14Alkoxy refer to that carbon number is the alkoxy of 1-14, including branched alkoxy
And branched alkoxy, including unsubstituting alkoxy and the hydrogen atom selectively substituted alkoxy substituted by halogen element etc..
In the present invention, the C6-C14Aryl refer to carbon atom number be 6-14 aryl, the aryl includes phenyl,
The C6-C14Aryl may include the hydrogen atom aryl substituted by halogen element etc..
In the present invention, the C6-C14Aryloxy group refer to that carbon atom number is the aryloxy group of 6-14, the aryloxy group includes
Phenoxy group, the C6-C14Aryloxy group may include the hydrogen atom aryloxy group substituted by halogen element etc..
In the present invention, the C1-C5Alkyl include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, just
Amyl, isopentyl.
In the case of in the present invention, it is preferred to, in formula M gXY, X is fluorine, chlorine or bromine element, and Y is selected from by fluorine element, chlorine
Element, bromo element, C1-C5Alkyl, C1-C5Alkoxy, C6-C10Aryl or C6-C10Aryloxy group composition group.It is described
C1-C5Alkyl for example can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, positive penta
Base, isopentyl, tertiary pentyl or neopentyl, the C1-C5Alkoxy such as can be methoxyl group, ethyoxyl, propoxyl group, isopropyl
Oxygroup, butoxy or isobutoxy, the C6-C10Aryl for example can for phenyl, o-tolyl, tolyl, to toluene
Base, adjacent ethylbenzene, ethylbenzene, to ethylbenzene or naphthalene, the C6-C10Aryloxy group for example can be phenoxy group or naphthalene oxygen
Base.The magnesium halide that general formula is MgXY can be the mixture of a kind of magnesium halide or a variety of magnesium halides.General formula is the halogen of MgXY
The specific example for changing magnesium can be but be not limited to: magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination
One of n-butoxy magnesium is a variety of.The angle ready availability from raw material, preferably magnesium chloride.
In the case of in the present invention, it is preferred to, in general formula R1In OH, R1For C1-C6Alkyl or C3-C8Naphthenic base.More
Under preferable case, in general formula R1In OH, R1For C1-C5Alkyl or C3-C6Naphthenic base.In particularly preferred situation, in general formula
R1In OH, R1For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, cyclopropyl, cyclopenta,
Methylcyclopropyl groups, Dimethvlcvclopropvl, cyclohexyl, methylcyclopentyl.
Another kind preferred embodiment according to the present invention, in the present invention, the general formula R1Alcohol shown in OH
Class compound is selected from by ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2- second
The group of base hexanol composition.
In the present invention, in formula (I), R2And R3It is each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, bromopropyl.
Another kind preferred embodiment according to the present invention, in the present invention, epoxy second shown in the formula (I)
Alkyl compound be selected from by ethylene oxide, propylene oxide, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and
The group of epoxy bromobutane composition.
In the present invention, it is preferred to by magnesium halide shown in formula M gXY and general formula R1OH compound represented and ethylene oxide
Class compound and optional inert liquid medium are mixed under conditions of 0-35 DEG C；The temperature more preferably mixed is 5-
30℃。
It should be strongly noted that above-mentioned by magnesium halide shown in formula M gXY and general formula R1OH compound represented and ring
The method that oxidative ethane class compound and optional inert liquid medium are mixed under conditions of being no more than 35 DEG C includes two
Kind specific embodiment.The first are as follows: is first by magnesium halide shown in formula M gXY and general formula R1OH compound represented and
Optional inert liquid medium carries out the first haptoreaction, then by obtained product and ethylene oxide after the first contact
It closes object and carries out the second haptoreaction, as long as the temperature of second contact is no more than 35 DEG C, method of the invention is to described
There is no particular limitation for the temperature of first contact, and the temperature of first contact can fluctuate in the larger context, for example, described
The temperature of first contact can be 0-120 DEG C.The time of method of the invention to first contact, there is no particular limitation, only
Want magnesium halide and general formula R shown in the formula M gXY1OH compound represented is capable of forming molten condition.Of the invention
Illustratively given in embodiment it is described first contact temperature and time, and give it is described second contact temperature and
Time, those skilled in the art should not be construed as the restriction to method of the invention.In fact, as previously mentioned, side of the invention
Method only needs in oxirane compound addition system the mixture until in the oxirane compound and system
It forms limiting temperature in the time between uniform solution and is no more than 35 DEG C.Second of specific embodiment are as follows: general formula
Magnesium halide, general formula R shown in MgXY1OH compound represented, oxirane compound and optional inert liquid medium
It is mixed to obtain the temperature during the entire process of mixture and be no more than 35 DEG C.
According to the present invention, in step 2), the mixture is preferably warming up to 40-120 DEG C under agitation.By institute
Stating mixture and being warming up to condition not less than 40 DEG C to be the existing various catalyst support used for olefinic polymerization that are capable of forming
Condition, for example, heating rate can be controlled, preferably heating rate is 0.0001-15 DEG C/min, from economic angle and institute
From the aspect of the final particle shape control of obtained carrier, heating rate is particularly preferably 1-6 DEG C/min.
As previously mentioned, the mixture is preferably warming up to 40-120 DEG C in step 2), more preferably by the mixing
Object is warming up to 50-90 DEG C.In particular it is preferred to be 1-60 minutes in the residence time of the outlet temperature of the heating, more preferably stop
Staying the time is 15-50 minutes.The residence time of the outlet temperature of heating of the present invention is namely in the heat preservation of outlet temperature
Time.
According to the present invention, in step 2), the mixture is warming up to 40-120 DEG C under agitation, it is preferably described
The condition of stirring includes: that revolving speed is 50-1000rpm, more preferably 200-600rpm.
According to the present invention, general formula is MgXY magnesium halide, general formula R1The use of the compound of OH, oxirane compound
Amount can make appropriate choice according to the composition of expected catalyst support used for olefinic polymerization.In the present invention, relative to
Magnesium halide shown in 1mol formula M gXY, the preferably described general formula R1The dosage of OH compound represented is 4-30mol, the epoxy
The dosage of ethane compound is 1-10mol.
In more preferred situation, in the present invention, relative to magnesium halide shown in 1mol formula M gXY, the general formula R1OH
The dosage of compound represented is 10-25mol, and the dosage of the oxirane compound is 3-6mol.
According to the present invention, the minor amount of water in above-mentioned each reactant can also participate in forming catalyst support used for olefinic polymerization
Reaction.
According to the present invention, the dosage of the optional inert liquid medium can the magnesium halide according to shown in formula M gXY
Dosage selects.Generally, shown in the 1mol formula M gXY on the basis of magnesium halide, the dosage of the inert liquid medium can be with
For 0.8-10L, preferably 2-8L.The inert liquid medium can for it is commonly used in the art it is various not with reactant and react production
Chemically interactive liquid medium occurs for object.Such as: the inert liquid medium can be silicone oil and/or inert fluid hydro carbons
Solvent.Specifically, the inert liquid medium is preferably kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon
At least one of oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil are a variety of.Inert fluid of the present invention is situated between
Matter is particularly preferably white oil.
Preferred embodiment of the invention is without using inert liquid medium.
According to the present invention, this method can also include being separated by solid-liquid separation the product obtained by step 2), by solid phase
Product is washed and is dried.The separation of solid and liquid can be the existing various methods that can be realized solid phase and liquid phase separation,
Such as filter, filters pressing or centrifuge separation, under preferable case, the method for the separation of solid and liquid is filter press technique.The present invention is to filters pressing
Condition is not particularly limited, be subject to as far as possible fully realize solid phase and liquid phase separation.The washing can be using this
Method well known to the technical staff of field washs obtained solid product, for example, can using inert hydrocarbon solvent (such as:
Pentane, hexane, heptane, petroleum ether and gasoline) obtained solid product is washed.Condition of the present invention for the drying
It is not particularly limited, such as: the temperature of the drying can be 20-70 DEG C, and the time of the drying can be 0.5-10 hours.
According to the present invention, the drying can carry out under normal pressure or reduced pressure.
Second aspect, the present invention provide catalyst support used for olefinic polymerization prepared by the above method.
In the present invention, it is preferred to which the average grain diameter of the carrier is 10-100 microns, particle diameter distribution is less than 1.2.
In more preferred situation, the average grain diameter of carrier of the present invention is 30-70 microns, particle diameter distribution 0.7-
0.9.In the preferred embodiment, the catalyst for olefines polymerizing prepared by the catalyst support used for olefinic polymerization can be obtained
Olefin polymer with more high-bulk-density.In the present invention, the average grain of the catalyst support used for olefinic polymerization is straight
Diameter and particle diameter distribution (can be produced using 2000 laser particle analyzer of Master Sizer by Malvern Instruments Ltd
Manufacture) it measures.
The third aspect, the present invention provide above-mentioned carrier and are preparing the application in catalyst for olefines polymerizing.
In an application of the invention, including by carrier of the present invention with titanium source and internal electron donor compound it connects
Touching reaction, obtains 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 internal electron donor
The weight ratio of 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 conventional during preparing catalyst for olefines polymerizing
The various internal electron donor compounds used, the preferably described internal electron donor compound are carboxylate, alcohol ester, ether, ketone, nitrile, amine
At least one of with silane；The more preferred internal electron donor compound is unitary or polyhydric aliphatic race carboxylate, unitary
Or at least one of polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.In the present invention, the unitary or polyhydric aliphatic race
The specific kind of selection of carboxylate, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether can refer to existing skill
Art is selected, and the present invention is no longer described in detail herein.
According to the present invention, the titanium source can be conventional use of during preparing catalyst for olefines polymerizing various contains
Titanium compound.It is preferred that the titanium source has general formula Ti (ORn)4-mXmShown in structure, wherein RnFor C1-C14Aliphatic group, X
It is the integer of 1-4 for F, Cl or Br, m；In more preferred situation, the titanium source be titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride,
Three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy dichloride
At least one of titanium and ethyoxyl titanium trichloride.
In the present invention, carrier and titanium source and internal electron donor compound are subjected to catalytic condition without spy to described
Other restriction, under preferable case, which may include: that reaction temperature is 80-130 DEG C, and the reaction time is
0.5-10 hours.
In the present invention, it is preferred to which it is mixed that titanium source and the catalyst support used for olefinic polymerization are first carried out contact at low temperature
It closes, then slowly heats up again to reach above-mentioned reaction temperature.Those skilled in the art understood technical solution of the present invention it
It can be operated afterwards according to Conventional wisdom in the art, details are not described herein by the present invention.
Under preferable case, the present invention also provides a kind of catalyst for olefinic polymerization, which contains: institute of the present invention
Catalyst for olefines polymerizing, alkyl aluminum compound and the optional external donor compound stated.It is described that " optional is outer to electricity
Donor compound " refers to that external donor compound can have or be not present in the catalyst for olefinic polymerization of the invention
In, that is to say, that the catalyst of the present invention for olefinic polymerization can contain or without containing external electron donor chemical combination
Object.
In the present invention, detailed description has been carried out in the composition of the catalyst for olefines polymerizing above,
This is repeated no more.
In the present invention, it is catalyzed in the catalyst for olefinic polymerization containing olefin polymerization of the present invention
Agent, therefore, the catalyst according to the present invention for olefinic polymerization is when being used as the catalyst of olefin polymerization, polymerization
The heap density of obtained polymer greatly improves.
Moreover, the catalyst according to the present invention for olefinic polymerization is for alkyl aluminum compound and external electron donor
The type and dosage for closing object are not particularly limited.
Generally, in the catalyst for olefinic polymerization, alkyl aluminum compound in terms of aluminium element and with titanium member
The molar ratio of the catalyst for olefines polymerizing of element meter can be 1-2000:1, preferably 20-500:1；The external electron donor
The molar ratio for closing object and alkyl aluminum compound can be 0.005-0.5:1, preferably 0.01-0.4:1.
Catalyst according to the present invention for olefinic polymerization, the alkyl aluminum compound can be commonly used in the art each
Kind alkyl aluminum compound.For example, the alkyl aluminum compound can be for triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, three just
Hexyl aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, one ethyl of dichloro
One of aluminium, one n-hexyl aluminium of one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro and dichloro are a variety of.
Catalyst according to the present invention for olefinic polymerization, the external donor compound can be commonly used in the art
Various external donor compounds, for example, the external donor compound can for carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol,
One of organic phosphorus compound and organo-silicon compound are a variety of；Preferably, the external electron donor is with general formula
R8 aR9 bSi(OR10)cSilicon compound, wherein a and b is respectively 0, an integer of 1 or 2, and c is the integer of 1-3, and the sum of a+b+c
It is 4, R8、R9、R10It is each independently C1-C18Substituted or unsubstituted alkyl；It is highly preferred that a and b are respectively 1, c 2,
R8、R9It is each independently C3-C10Substituted or unsubstituted alkyl, R10For C1-C10Substituted or unsubstituted alkyl.Specifically
The example on ground, the organo-silicon compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy
Base silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl- tert fourth
Base dimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- t-butyldimethoxysilane and (1,1,
The fluoro- 2- propyl of 1- tri-) -2- ethyl piperidine base dimethoxysilane and (the fluoro- 2- propyl of 1,1,1- tri-)-methyl dimethoxy oxygroup silicon
Alkane.
The present invention also provides application of the above-mentioned catalyst for olefines polymerizing in olefin polymerization.
Application of the invention includes: to gather at least one alkene and alkene of the present invention under olefin polymerization conditions
Catalysts carry out olefin polymerization.
The method of olefinic polymerization according to the present invention, by using the catalyst for olefines polymerizing of the invention,
The polymer that particle shape is good, heap density is high can be prepared.The method of the olefinic polymerization of the invention is for olefinic polymerization
Condition and used alkene are not particularly limited.The alkene for example can be ethylene, propylene, 1- butylene, 2- butylene, 2- first
One of base -1- butylene, 3-methyl-1-butene, 2- methyl-2-butene, 1- amylene, 2- amylene, 1- hexene and styrene or
It is a variety of, preferably one of ethylene, propylene, 1- butylene, 2- butylene and styrene or a variety of.
The method of olefinic polymerization according to the present invention, the olefinic polymerization can carry out according to conventional methods in the art.
For example, the olefinic polymerization can be bulk polymerization, gas-phase polymerization or slurry polymerization.Olefine polymerizing process according to the present invention,
The olefin polymerization conditions can be the normal condition of this field, for example, polymerization temperature can be 0-150 DEG C, preferably 60-90
℃；Polymerization pressure can be normal pressure or pressurization.
Application according to the present invention, preferably under olefin polymerization conditions, by least one alkene and present invention use above-mentioned
Olefin polymerization is carried out in the catalyst of olefinic polymerization.
In following preparation example, embodiment and comparative example, in case of no particular description, used various raw materials
It is all from commercially available.
1, the average grain diameter and particle diameter distribution of catalyst support used for olefinic polymerization use Masters Sizer 2000
Particle size analyzer (being manufactured by Malvern Instruments Ltd) is measured；
2, the apparent form of catalyst support used for olefinic polymerization is by being commercially available from the model Eclipse of Nikon company
The optical microscopy of E200 is observed；
3, the heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
In order to verify the catalyst that the carrier that method of the invention obtains is prepared have better catalytic performance and
So that the heap density of obtained polymerizate is higher, in following embodiment illustratively using one of conventional techniques come
Explanation.Specific experimental method is as shown in the following example.Those skilled in the art should not be construed as to technology of the invention
The limitation of scheme.
Preparation example 1
The preparation example is used to prepare catalyst support used for olefinic polymerization of the invention.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.7mol ethyl alcohol, 0.3mol epoxychloropropane is added, is stirring
It after lower temperature control is 25 DEG C, isothermal reaction 1 hour, starts to warm up, heating rate is 2 DEG C/min, until maintaining after 60 DEG C
20min.Filters pressing washs filters pressing product 5 times with hexane, and vacuum drying obtains catalyst support used for olefinic polymerization Z1.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 60 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.9.Particle morphology using optical microphotograph sem observation is as shown in Figure 1.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z1 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
Compare preparation example 1
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.7mol ethyl alcohol is added, is warming up to 80 DEG C under stiring, constant temperature
Epoxychloropropane 0.3mol is added after reaction 2 hours, filters pressing product is washed 5 times with hexane, very by filters pressing after reaction 0.5 hour
Sky is dry, obtains catalyst support used for olefinic polymerization D-Z1.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization D-Z1 is 100 microns, particle diameter distribution
((D90-D10)/D50) is 1.6.Particle morphology using optical microphotograph sem observation is as shown in Figure 5.It can be seen from the figure that alkene
There are a large amount of irregular particles in polymerized hydrocarbon catalyst carrier D-Z1, and surface is more coarse.
Preparation example 2
The preparation example is used to prepare catalyst support used for olefinic polymerization of the invention.
In the reaction kettle of 0.6L, 0.16mol magnesium chloride, 3.4mol ethyl alcohol is added, 0.6mol epoxychloropropane is stirring
It after lower temperature control is 30 DEG C, isothermal reaction 1 hour, starts to warm up, heating rate is 1 DEG C/min, until maintaining after 60 DEG C
20min.Filters pressing washs filters pressing product 5 times with hexane, and vacuum drying obtains catalyst support used for olefinic polymerization Z2.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z2 is 55 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 2.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z2 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
Preparation example 3
The preparation example is used to prepare catalyst support used for olefinic polymerization of the invention.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.7mol ethyl alcohol is added, is warming up to 90 DEG C under stiring, constant temperature
Reaction is cooled to 15 DEG C after 1 hour, the pre- 0.3mol epoxychloropropane for being cooled to 15 DEG C is added, to temperature in 15 DEG C of stable 0.5h
Afterwards, it starts to warm up, heating rate is 2 DEG C/min, until maintaining 20min after 50 DEG C.Filters pressing product is washed 5 with hexane by filters pressing
Secondary, vacuum drying obtains catalyst support used for olefinic polymerization Z3.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 70 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 3.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z3 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
Preparation example 4
The preparation example is used to prepare catalyst support used for olefinic polymerization of the invention.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.7mol ethyl alcohol is added, is warming up to 90 DEG C under stiring, constant temperature
Reaction is cooled to 5 DEG C after 1 hour, the pre- 0.3mol epoxychloropropane for being cooled to 5 DEG C is added, after temperature after 5 DEG C of stable 40min,
It starts to warm up, heating rate is 1.5 DEG C/min, until maintaining 20min after 85 DEG C.Filters pressing washs filters pressing product 5 times with hexane,
Vacuum drying, obtains catalyst support used for olefinic polymerization Z4.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z4 is 70 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 4.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z4 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
Embodiment 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, by 40 grams obtained by preparation example 1
To the catalyst support used for olefinic polymerization Z1 be added thereto, and stir 30min at -20 DEG C.Later, start slowly heating
To 110 DEG C, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, filters off liquid after maintaining 30min at 110 DEG C
Body.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain catalyst for olefines polymerizing C1 after dry.
(3) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
Catalyst for olefines polymerizing C1,1.5L's (normal volume) for being obtained by step (1) of silane, the anhydrous hexane of 10mL and 10mg
The liquid propene of hydrogen and 2.5L.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, discharging is dried to obtain
Polypropylene powder.
As a result: the melt index and heap density of the activity and polypropylene powder that measure catalyst are as shown in table 1, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Comparative example 1
In the reaction flask of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -20 DEG C, by 40 grams prepared by comparison
The catalyst support used for olefinic polymerization D-Z1 that example 1 obtains is added thereto, and stirs 30min at -20 DEG C.Later, start
110 DEG C are to slowly warm up to, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, maintains 30min at 110 DEG C
After filter off liquid.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, olefin polymerization catalysis is obtained after dry
Agent D-C1.
(3) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
Catalyst for olefines polymerizing D-C1,1.5L (normal volume) for being obtained by step (1) of silane, the anhydrous hexane of 10mL and 10mg
Hydrogen and 2.5L liquid propene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and is discharged dry
To polypropylene powder.
As a result: the melt index and heap density of the activity and polypropylene powder that measure catalyst are as shown in table 1, this
It outside, is all special-shaped material in the polypropylene powder particle, mobility is bad.
Embodiment 2
(1) preparation of catalyst for olefines polymerizing
In the reaction flask of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -10 DEG C, by 40 grams obtained by preparation example 2
To the catalyst support used for olefinic polymerization Z2 be added thereto, and stir 45min at -10 DEG C.Later, start slowly heating
To 100 DEG C, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, filters off liquid after maintaining 30min at 100 DEG C
Body.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain catalyst for olefines polymerizing C2 after dry.
(3) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
Catalyst for olefines polymerizing C2,1.5L's (normal volume) for being obtained by step (1) of silane, the anhydrous hexane of 10mL and 10mg
The liquid propene of hydrogen and 2.5L.85 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, discharging is dried to obtain
Polypropylene powder.
As a result: the melt index and heap density of the activity and polypropylene powder that measure catalyst are as shown in table 1, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Embodiment 3
(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, by 40 grams obtained by preparation example 3
To the catalyst support used for olefinic polymerization Z3 be added thereto, and stir 30min at -20 DEG C.Later, start slowly heating
To 110 DEG C, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, filters off liquid after maintaining 30min at 110 DEG C
Body.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain catalyst for olefines polymerizing C3 after dry.
(3) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
Catalyst for olefines polymerizing C3,1.5L's (normal volume) for being obtained by step (1) of silane, the anhydrous hexane of 10mL and 10mg
The liquid propene of hydrogen and 2.5L.85 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, discharging is dried to obtain
Polypropylene powder.
As a result: the melt index and heap density of the activity and polypropylene powder that measure catalyst are as shown in table 1, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Embodiment 4
(1) preparation of catalyst for olefines polymerizing
In the reaction flask of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -10 DEG C, by 40 grams obtained by preparation example 4
To the catalyst support used for olefinic polymerization Z4 be added thereto, and stir 45min at -10 DEG C.Later, start slowly heating
To 100 DEG C, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, filters off liquid after maintaining 30min at 100 DEG C
Body.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain catalyst for olefines polymerizing C4 after dry.
(3) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
Triethyl aluminum hexane solution (concentration of triethyl aluminum be 0.5mmol/mL),
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg are obtained by step (1)
Catalyst for olefines polymerizing C4,1.5L (normal volume) hydrogen and 2.5L liquid propene.85 DEG C are warming up to, and in the temperature
Degree lower reaction 1 hour, cooling was bled off pressure, and discharging is dried to obtain polypropylene powder.
As a result: the melt index and heap density of the activity and polypropylene powder that measure catalyst are as shown in table 1, this
Outside, the polypropylene powder particle shape is good, and special-shaped material is substantially not present.
Table 1
As can be seen from the above results, for the catalyst support used for olefinic polymerization being prepared using method of the invention
Grain form is good, surface is smooth, is substantially not in irregular particle, and is used for alkene with the catalyst of resulting carrier preparation
When (especially propylene) polymerize, additionally it is possible to improve the heap density of polymerizate, the appearance substantially without opposite sex material, great industrial application
Prospect.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of preparation method of catalyst support used for olefinic polymerization, which is characterized in that this method comprises:
1) by magnesium halide shown in formula M gXY and general formula R1OH compound represented and oxirane compound and optional
Inert liquid medium is mixed under conditions of being no more than 35 DEG C, obtains mixture solution；
2) mixture solution that step 1) obtains is warming up under agitation not less than 40 DEG C, the rate of the heating is
0.0001-15℃/min；
Wherein, in formula M gXY, X is halogen element, and Y is selected from by halogen element, C1-C14Alkyl, C1-C14Alkoxy, C6-C14
Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C8Alkyl or C3-C8Naphthenic base；
The oxirane compound has structure shown in formula (I):
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or halogenated alkyl.
2. according to the method described in claim 1, wherein, in step 2), the mixture solution is risen under agitation
Temperature is to 40-120 DEG C.
3. method according to claim 1 or 2, wherein in step 2), the rate of the heating is 1-6 DEG C/min.
4. method according to claim 1 or 2, wherein in step 2), the condition of the stirring includes: that revolving speed is 50-
1000rpm。
5. method according to claim 1 or 2, wherein in step 2), the condition of the stirring includes: that revolving speed is
200-600rpm。
6. method according to claim 1 or 2, wherein relative to 1mol magnesium halide, general formula R1OH compound represented
Dosage is 4-30mol；
The dosage of oxirane compound is 1-10mol.
7. method according to claim 1 or 2, wherein relative to 1mol magnesium halide, general formula R1OH compound represented
Dosage is 10-25mol；
The dosage of oxirane compound is 3-6mol.
8. according to the method described in claim 1, wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from by chlorine, bromine, C1-C5's
Alkyl, C1-C5Alkoxy, C6-C10Aryl and C6-C10Aryloxy group composition group.
9. according to the method described in claim 8, wherein, the magnesium halide be selected from magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium,
At least one of chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.
10. according to the method described in claim 1, wherein, in general formula R1In OH, R1For C1-C8Alkyl.
11. according to the method described in claim 10, wherein, general formula R1OH compound represented be selected from ethyl alcohol, propyl alcohol, isopropanol,
At least one of n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
12. according to the method described in claim 1, wherein, in the structure shown in formula (I), R2And R3Respectively stand alone as hydrogen, C1-C3
Alkyl or halogenated alkyl.
13. according to the method for claim 12, wherein the oxirane compound is selected from ethylene oxide, epoxy third
At least one of alkane, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane.
14. the catalyst support used for olefinic polymerization that method described in any one of claim 1-12 is prepared.
15. carrier according to claim 14, wherein the average grain diameter of the carrier is 10-100 microns, partial size
Distribution is less than 1.2.
16. carrier according to claim 15, wherein the average grain diameter of the carrier is 30-90 microns, partial size point
Cloth is less than or equal to 0.9.
17. carrier described in any one of claim 14-16 is preparing the application in catalyst for olefines polymerizing.
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| 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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| 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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