CN106543309B - Catalyst support used for olefinic polymerization and catalyst for olefines polymerizing and their preparation method and application - Google Patents
Catalyst support used for olefinic polymerization and catalyst for olefines polymerizing and their preparation method and application Download PDFInfo
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Abstract
The present invention relates to field of olefin polymerisation, it discloses a kind of catalyst support used for olefinic polymerization and catalyst for olefines polymerizing and their preparation method and application, the preparation method of catalyst support used for olefinic polymerization of the invention includes: 1) by magnesium halide shown in formula M gXY and general formula R1Alcohol compound shown in OH and optional inert liquid medium are contacted to form lotion；2) lotion for obtaining step 1) carries out haptoreaction with oxirane compound shown in logical formula (I) with the flow-rate ratio that ratio is 1.5-6:1.Method of the invention can obtain the catalyst support used for olefinic polymerization that pattern is preferable, high income and production cost are low under conditions of not needing using surfactant.
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
And the catalyst support used for olefinic polymerization being prepared by this method, a kind of preparation method of catalyst for olefines polymerizing and
The catalyst for olefines polymerizing be prepared by this 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.
Above-mentioned chlorination magnesium alcoholate is to use cryogenic quenching means to solidify the alcohol adduct melt of high temperature and be made, not only right
The consumption of the energy is larger, preparation process is complicated, multiple reactors is needed to carry out joint preparation, and the partial size of obtained alcohol adduct
Wider distribution.In order to solve this problem, CN102040683A discloses a kind of by magnesium halide alcohol adduct and ethylene oxide
The method for closing object reaction to prepare carrier, and specifically disclose after magnesium halide alcohol adduct melting dispersion, ethylene oxide is added
Compound；It will be either added directly into the reactor containing oxirane compound after magnesium halide alcohol adduct melting dispersion.
The feature of this method is to react to obtain solid at high temperature with the alcohol adduct of melting using epoxychloropropane.However, using the party
Method prepares catalyst carrier, and that there are preparation process is unstable, is easy to happen carrier adhesion, and the disadvantage that carrier molding effect is bad,
Therefore, it is necessary to other surfactants, such as stearic acid, sapn, quaternary ammonium compound are added during the preparation process.These substances add
Enter, cost is not only increased, and have an adverse effect to the recovery processing of by-product, in addition, in the post-processing of by-product
In recycling, the recycling of ethyl alcohol and epoxy compounds is more difficult, and which increases operating costs.
The method of the prior art is to be directly added into oxirane compound for after magnesium halide alcohol adduct melting dispersion
In the system, or the reactor containing oxirane compound will be added directly into after magnesium halide alcohol adduct melting dispersion
It is interior.Due to the property of high-viscous liquid, experiment condition is not easy to control, and this method prepares unstable result, is easy to happen carrier adhesion
Phenomenon, the disadvantage for causing carrier molding effect bad.
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, a kind of do not needing using surfactant is provided
Under the conditions of obtain pattern preferably, the method for high income and the low catalyst support used for olefinic polymerization of production cost.
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 R1Alcohol compound shown in OH and optional inert fluid
Medium is contacted to form lotion；
2) oxirane compound shown in the lotion for obtaining step 1) and logical formula (I) is with ratio for 1.5-6:1's
Flow-rate ratio carries out haptoreaction；
Wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from by chlorine, bromine, C1-C14Alkyl, C1-C14Alkoxy,
C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl；
The oxirane compound has structure shown in 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 preferably load
Particle diameter distribution < 1.2 of body.
The third aspect, the present invention provide a kind of preparation method of catalyst for olefines polymerizing, this method comprises:
1) it prepares carrier: carrier is prepared using present invention method above-mentioned；
2) prepare catalyst: the carrier and titanium source and internal electron donor compound that step 1) is obtained carry out haptoreaction.
Fourth aspect, the present invention provide catalyst for olefines polymerizing prepared by the above method.
5th aspect, the present invention provide application of the catalyst for olefines polymerizing in olefin polymerization.
The preparation method of above-mentioned catalyst support used for olefinic polymerization of the invention can increase the stability of preparation, improve and produce
The yield of product, formed product effect are good.
Specifically, the preparation method of above-mentioned catalyst support used for olefinic polymerization of the invention is to be initially formed the conjunction of magnesium halide alcohol
Object, and it is subjected to haptoreaction with certain flow and the oxirane compound with certain flow after emulsification.
Method of the invention reduces the collision probability of unformed particle, reduces carrier particle adhesion phenomenon, substantially increases carrier
The stability and dispersibility of preparation.Product yield is improved, economic benefit is considerably increased.It is urged using what the carrier was prepared
Agent heap density is higher, and polymer particle shape is good.
Method of the invention is not needed using surfactant, to reduce production cost, and avoids impurity pollution.
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 process unit schematic diagram for preparing catalyst support used for olefinic polymerization according to the method for the present invention.
Description of symbols
1, lotion 2, oxirane compound
3, blender
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 R1Alcohol compound shown in OH and optional inert fluid
Medium is contacted to form lotion；
2) oxirane compound shown in the lotion for obtaining step 1) and logical formula (I) is with ratio for 1.5-6:1's
Flow-rate ratio carries out haptoreaction；
Wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from by chlorine, bromine, C1-C14Alkyl, C1-C14Alkoxy,
C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl；
The oxirane compound has structure shown in 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 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 chlorine element or bromo element, and Y is selected from by chlorine element, bromine
Element, C1-C5Alkyl, C1-C5Alkoxy, C6-C10Aryl or C6-C10Aryloxy group composition group.The C1-C5Alkane
Base for example can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isoamyl
Base, tertiary pentyl or neopentyl, the C1-C5Alkoxy such as can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, fourth
Oxygroup or isobutoxy, the C6-C10Aryl can be for example phenyl, o-tolyl, tolyl, p-methylphenyl, adjacent second
Phenyl, ethylbenzene, to ethylbenzene or naphthalene, the C6-C10Aryloxy group for example can be phenoxy group or naphthoxy.General formula is
The magnesium halide of MgXY can be a kind of magnesium halide or the mixture of a variety of magnesium halides.General formula is the tool of the magnesium halide of MgXY
Body example can be but be not limited to: magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy
One of 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.
Under preferable case, in the present invention, in step 2), shown in the lotion that preferably obtains step 1) and logical formula (I)
Oxirane compound with ratio be 2-4:1 flow-rate ratio carry out haptoreaction.
In the present invention, it should be strongly noted that being not particularly limited to the method for the flow for controlling the raw material,
Those skilled in the art can control according to ordinary skill in the art means.
Other than being limited by operating pressure and equipment region, above-mentioned pipe range can change in a wide range.The pipe
The length of the long tubular area for referring to conveying lotion or the tubular area length or mixing for conveying oxirane compound
Length for the tubular area of the two reaction afterwards.
Signified " tubular area " term of the invention refers to the region with tube shape, and this preferred example in region is
Pipeline or tubular reactor.
A kind of preferred embodiment according to the present invention, the lotion of the invention and the ethylene oxide
Pipeline transportation can be passed through by closing object.Also there is no particular limitation for the internal diameter of method of the invention to the pipeline.
According to the present invention, in step 2), before haptoreaction generation, the flow direction of the preferably described lotion and described
The angle of the flow direction of oxirane compound is less than 90 °.
In more preferred situation, in step 2), before haptoreaction generation, the flow direction of the lotion and described
The angle of the flow direction of oxirane compound is less than or equal to 15 °.It was found by the inventors of the present invention that by the stream of the lotion
The angle of dynamic direction and the flow direction of the oxirane compound be limited to less than or equal to 15 ° in the range of when, can
So that the carrier granular form being prepared is good, and when catalyst reaction of the use containing the carrier being prepared, make
The heap density for obtaining polymeric articles is high.
In the present invention, in step 2), the preferably described lotion contact instead with the oxirane compound
It should be transported respectively by different pipelines before, and the lotion from different pipelines and the ethylene oxide
It closes object and merges into one to carry out the haptoreaction.In the present invention, it should be strongly noted that the lotion and the ring
Oxidative ethane class compound is just reacted in merging into the pipeline after one.In the present invention, described " to pass through difference respectively
Pipeline transported " refer to that the lotion is not transported with the oxirane compound in same root pipeline, but
It is that the transport lotion and the shape material in two root canal roads of the oxirane compound etc. can be identical.
A kind of preferred embodiment according to the present invention, method of the invention is by using technique shown in FIG. 1
Device carries out, and specifically, the lotion 1 is transported by different pipelines respectively from the oxirane compound 2, and
And one is converged into the pipeline for preferably comprising blender 3 to carry out haptoreaction, and the product generated passes through containing stirring
The pipeline of device 3 is into subsequent collecting zone.
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.
According to the present invention, in step 1), the preferably described contact includes: temperature for 0-100 DEG C with the condition for forming lotion,
Time is 0.1-6h.
In the present invention, in step 1), the step of formation lotion may include: by halogenation shown in formula M gXY
Magnesium and general formula R1Alcohol compound shown in OH and optional inert liquid medium are mixed, and by gained mixture into
Row stirring, the condition of the stirring include: that revolving speed is 50-1000rpm, more preferably 200-600rpm.
In the present invention, in step 2), the lotion and the oxirane compound carry out catalytic item
Part may include: that temperature is 60-120 DEG C, time 0.1-2h.
Method of the invention preferably the lotion and the oxirane compound are preheated in advance with reach into
Required temperature when row contact.
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.
Under preferable case, in the present invention, the average grain diameter of the carrier is 10-100 microns, and 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 a kind of preparation method of catalyst for olefines polymerizing, this method comprises:
1) it prepares carrier: carrier is prepared using present invention method above-mentioned；
2) prepare catalyst: the carrier and titanium source and internal electron donor compound that step 1) is obtained carry out haptoreaction.
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 titanium source is selected from general formula Ti (OR4)4-aX’aCompound represented, wherein R4For C1-C14Fat
Alkyl, X ' are halogen, and a is the integer of 0-4.In more preferred situation, the titanium source is titanium tetrachloride, titanium tetrabromide, tetrafluoride
Titanium, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy dichloro
Change 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.
Fourth aspect, the present invention provide catalyst for olefines polymerizing prepared by the above method.
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, In 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.
5th aspect, the present invention provide application of the 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 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
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
After reaction 1 hour, high-speed stirred (1800rpm) 0.5h, pressurize input channel, so that flow of the lotion in the pipeline
For 15mL/min, at the same from the inlet feed stream amount of another pipeline be 5mL/min, epoxychloropropane at a temperature of 90 °C (two pipes
Angle between road is 12 °), the two is in the reaction kettle that tubular area is mixed into equipped with hexane, filters pressing after conveying, will
Filters pressing product is washed 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 70 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.The particle shape of catalyst support used for olefinic polymerization Z1 is more regular, and surface is smooth, is essentially all ball
Shape, particle size distribution compares concentration, 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 90 DEG C under stiring.Constant temperature
After reaction 1 hour, then the epoxychloropropane constant temperature of 90 DEG C of 0.3mol is added in high-speed stirred (1800rpm) 0.5h thereto
0.5h is reacted, filters pressing is then carried out, filters pressing product is washed 5 times with hexane, is dried in vacuo, obtains carrier D-Z1.
The average grain diameter (D50) of the D-Z1 is 98 microns, and particle diameter distribution ((D90-D10)/D50) is 1.7.Carrier
There are a large amount of irregular particles in D-Z1, and surface is more coarse.
Preparation example 2
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.2mol ethyl alcohol is added, is warming up to 65 DEG C under stiring.Constant temperature
After reaction 1 hour, 85 DEG C are warming up to after high-speed stirred (1800rpm) 0.5h, pressurize input channel, so that the lotion is described
Flow in pipeline is 20mL/min, while from the epoxy that the inlet feed stream amount of another pipeline is 5mL/min, temperature is 85 DEG C
Chloropropane (angle between two pipelines is 12 °), the two has conveyed in the reaction kettle that tubular area is mixed into equipped with hexane
Filters pressing after finishing, filters pressing product is washed 5 times with hexane, is dried in vacuo, is obtained catalyst support used for olefinic polymerization Z2.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z2 is 72 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.The particle shape of catalyst support used for olefinic polymerization Z2 is more regular, and surface is smooth, is essentially all ball
Shape, particle size distribution compares concentration, and there is no that irregular particle exists.
Preparation example 3
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.0mol ethyl alcohol, the high-speed stirred at 25 DEG C is added
(1800rpm) is warming up to 100 DEG C after 1 hour, pressurize input channel, so that flow of the lotion in the pipeline is
10mL/min, while from epoxychloropropane (two pipelines that the inlet feed stream amount of another pipeline is 5mL/min, temperature is 100 DEG C
Between angle be 12 °), in the reaction kettle that tubular area is mixed into equipped with hexane, filters pressing after conveying will press the two
Filter product is washed 5 times with hexane, is dried in vacuo, is obtained catalyst support used for olefinic polymerization Z3.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 75 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.9.The particle shape of catalyst support used for olefinic polymerization Z3 is more regular, and surface is smooth, is essentially all ball
Shape, particle size distribution compares concentration, and there is no that irregular particle exists.
Preparation example 4
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.2mol ethyl alcohol, the high-speed stirred at 10 DEG C is added
(1800rpm) is warming up to 90 DEG C after 1 hour, pressurize input channel, so that flow of the lotion in the pipeline is 8mL/
Min, at the same from the inlet feed stream amount of another pipeline be 2mL/min, epoxychloropropane at a temperature of 90 °C is (between two pipelines
Angle is 12 °), the two is in the reaction kettle that tubular area is mixed into equipped with hexane, filters pressing after conveying, by filters pressing product
It is washed 5 times with hexane, is dried in vacuo, obtains catalyst support used for olefinic polymerization Z4.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z4 is 73 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.The particle shape of catalyst support used for olefinic polymerization Z4 is more regular, and surface is smooth, is essentially all ball
Shape, particle size distribution compares concentration, and there is no that irregular particle exists.
Preparation example 5
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
After reaction 1 hour, high-speed stirred (1800rpm) 0.5h, pressurize input channel, so that flow of the lotion in the pipeline
For 30mL/min, at the same from the inlet feed stream amount of another pipeline be 5mL/min, epoxychloropropane at a temperature of 90 °C (two pipes
Angle between road is 12 °), the two is in the reaction kettle that tubular area is mixed into equipped with hexane, filters pressing after conveying, will
Filters pressing product is washed 5 times with hexane, and vacuum drying obtains catalyst support used for olefinic polymerization Z5.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z5 is 77 microns, particle diameter distribution ((D90-
D10)/D50) it is 1.0.The particle shape of catalyst support used for olefinic polymerization Z5 is more regular, and surface is smooth, is essentially all ball
Shape, particle size distribution compares concentration, 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 heap density for measuring polypropylene powder is 0.44g/cm3, in addition, the polypropylene powder particle shape is good,
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 heap density for measuring polypropylene powder is 0.37g/cm3, in addition, being all different in the polypropylene powder particle
Shape material, mobility are 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 heap density for measuring polypropylene powder is 0.43g/cm3, in addition, the polypropylene powder particle shape is good,
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 heap density for measuring polypropylene powder is 0.45g/cm3, in addition, the polypropylene powder particle shape is good,
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
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
Catalyst for olefines polymerizing C4,1.5L'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 heap density for measuring polypropylene powder is 0.44g/cm3, in addition, the polypropylene powder particle shape is good,
Special-shaped material is substantially not present.
Embodiment 5
(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 5
To the catalyst support used for olefinic polymerization Z5 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 C5 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 C5,1.5L'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 heap density for measuring polypropylene powder is 0.40g/cm3, in addition, the polypropylene powder particle shape is good,
Special-shaped material is substantially not present.
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.
Moreover, present method avoids use surfactant.
In addition, the result of comparative example 1 and embodiment 5 can also be seen that lotion and oxirane compound
The particle diameter distribution of the carrier enabled to when flow ratio control system is in preferred scope of the invention is more excellent, moreover, using
Enable to the heap density for the polymeric articles being prepared higher when catalyst polymerization reaction containing the carrier.
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 (20)
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 R1Alcohol compound shown in OH and optional inert liquid medium into
Row contact is to form lotion；
2) lotion for obtaining step 1) is the flow of 1.5-6:1 with ratio with oxirane compound shown in logical formula (I)
Than carrying out haptoreaction；
Wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from by chlorine, bromine, C1-C14Alkyl, C1-C14Alkoxy, C6-C14
Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl；
The oxirane compound has structure shown in formula (I):
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or halogenated alkyl；
In step 2), the lotion passes through different pipes from the oxirane compound respectively before carrying out haptoreaction
Road is transported, and the lotion from different pipelines and the oxirane compound merge into one to carry out institute
State haptoreaction.
2. according to the method described in claim 1, wherein, in step 2), shown in lotion and logical formula (I) that step 1) is obtained
Oxirane compound with ratio be 2-4:1 flow-rate ratio carry out haptoreaction.
3. according to the method described in claim 1, wherein, in step 2), before haptoreaction generation, the stream of the lotion
The angle of dynamic direction and the flow direction of the oxirane compound is less than 90 °.
4. according to the method described in claim 3, wherein, in step 2), before haptoreaction generation, the stream of the lotion
The angle of dynamic direction and the flow direction of the oxirane compound is less than or equal to 15 °.
5. method described in any one of -3 according to claim 1, wherein relative to 1mol magnesium halide, general formula R1Shown in OH
The dosage of compound is 4-30mol, and the dosage of oxirane compound is 1-10mol.
6. method described in any one of -3 according to claim 1, wherein relative to 1mol magnesium halide, general formula R1Shown in OH
The dosage of compound is 10-25mol, and the dosage of oxirane compound is 1-10mol.
7. method described in any one of -3 according to claim 1, wherein relative to 1mol magnesium halide, general formula R1Shown in OH
The dosage of compound is 4-30mol, and the dosage of oxirane compound is 3-6mol.
8. method described in any one of -3 according to claim 1, wherein relative to 1mol magnesium halide, general formula R1Shown in OH
The dosage of compound is 10-25mol, and the dosage of oxirane compound is 3-6mol.
9. method described in any one of -3 according to claim 1, wherein in step 1), the contact is to form lotion
Condition include: temperature be 0-100 DEG C, time 0.1-6h.
10. method described in any one of -3 according to claim 1, wherein in step 1), the step of the formation lotion
It include: by magnesium halide shown in formula M gXY and general formula R1Alcohol compound shown in OH and optional inert liquid medium into
Row mixing, and gained mixture is stirred, the condition of the stirring includes: that revolving speed is 50-1000rpm.
11. according to the method described in claim 10, wherein, in step 1), the step of formation lotion includes: by general formula
Magnesium halide and general formula R shown in MgXY1Alcohol compound shown in OH and optional inert liquid medium are mixed, and
Gained mixture is stirred, the condition of the stirring includes: that revolving speed is 200-600rpm.
12. method described in any one of -3 according to claim 1, wherein in step 2), the lotion and the epoxy
The catalytic condition of ethane compound progress includes: that temperature is 60-120 DEG C, time 0.1-2h.
13. the catalyst support used for olefinic polymerization that method described in any one of claim 1-12 is prepared.
14. catalyst carrier according to claim 13, wherein particle diameter distribution < 1.2 of the carrier.
15. a kind of preparation method of catalyst for olefines polymerizing, which is characterized in that this method comprises:
1) it prepares carrier: carrier is prepared using method described in any one of claim 1-12；
2) prepare catalyst: the carrier and titanium source and internal electron donor compound that step 1) is obtained carry out haptoreaction.
16. according to the method for claim 15, wherein the titanium source is selected from general formula Ti (OR4)4-aX’aCompound represented,
Wherein, R4For C1-C14Aliphatic group, X ' be halogen, a be 0-4 integer.
17. according to the method for claim 15, wherein the internal electron donor compound is ester, ether, ketone, nitrile, amine, acyl
At least one of amine and alkoxy silane.
18. according to the method for claim 15, wherein in step 2), the catalytic condition includes: that temperature is
80-130 DEG C, time 0.5-10h.
19. the catalyst for olefines polymerizing that method described in any one of claim 15-18 is prepared.
20. application of the catalyst for olefines polymerizing described in claim 19 in olefin polymerization.
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