CN106608925A - Catalyst component used for olefin polymerization, preparation method and applications thereof, catalyst used for olefin polymerization, and applications of catalyst - Google Patents
Catalyst component used for olefin polymerization, preparation method and applications thereof, catalyst used for olefin polymerization, and applications of catalyst Download PDFInfo
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- CN106608925A CN106608925A CN201510706714.9A CN201510706714A CN106608925A CN 106608925 A CN106608925 A CN 106608925A CN 201510706714 A CN201510706714 A CN 201510706714A CN 106608925 A CN106608925 A CN 106608925A
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Abstract
The invention belongs to the field of olefin polymerization, and more specifically provides a catalyst component used for olefin polymerization, and a preparation method and applications thereof. The preparation method comprises following steps: a magnesium halide alcohol adduct carrier, a titanium compound, and an internal electron donor are subjected contact reaction, wherein the internal electron donor contains a carboxylic acid diol ester and a phosphate, and the magnesium halide alcohol adduct carrier is prepared via following steps: a magnesium halide alcohol adduct melt is delivered through a structure unit provided with holes for contact with a liquid cooling medium under increased pressure. The invention also provides a catalyst used for olefin polymerization, and applications thereof. Compared with conventional catalysts, the catalyst synthesized from the carrier via the preparation method disclosed in the invention possesses following advantages: the catalyst possesses excellent steric directional catalytic performance, and foundation is provided for development of polypropylene resin with high additional value.
Description
Technical field
The present invention relates to a kind of preparation method of the catalytic component for olefinic polymerization, and by being used for that the method is obtained
The catalytic component of olefinic polymerization and its application in olefinic polyreaction；With for olefinic polymerization catalyst and its
Application in olefinic polyreaction.
Technical background
Spheric polypropylene catalyst is widely used in loop technology polypropylene production apparatus, with polymer apparent density
High, particle shape is regular, the advantages of high, the vertical structure directionality of polymerization catalyst activity are high.Carrier technique is the skill of spheric catalyst
One of art core.
Chlorination magnesium alcoholate ball type carrier applying in polyolefin catalyst field in polyolefin catalyst synthesis is public
Know.At present, the preparation method of chlorination magnesium alcoholate ball type carrier includes spray drying method, spray cooling, high extrusion
Go out method, high-speed mixing method and high-gravity rotating bed method.
US4421674 and CN1765940A disclose a kind of preparation method that is spray-dried and prepare carrier for olefin polymerization catalyst
(carrier alcohol content is less than 14%, and apparent density 0.32g/ml, the particle diameter of carrier is less than 20 microns), by the second of magnesium chloride
Alcoholic solution (about 100-300g/L) is preheated to after 90-100 DEG C and is sprayed in the vaporizer of flow of warm nitrogen gas, after the most of alcohol of removing
Form the ball type carrier of chlorination magnesium alcoholate.The method first prepares the ethanol solution of magnesium chloride, and ethanol consumption is big, energy consumption compared with
It is high.
US6020279 discloses a kind of chlorination magnesium alcoholate spray cooling and prepares method.By the fused mass Jing of chlorination magnesium alcoholate
Cross nozzle spray and chlorination magnesium alcoholate carrier is formed into cooling medium.The particle diameter of carrier prepared by the method is little, and equipment is born
Lotus is low, and size adjusts difficult.
CN1330086A and US6686307 disclose the height of chlorination magnesium alcoholate and stir preparation technology, first in inert media
The suspension of chlorination magnesium alcoholate is prepared, cooling is put into after high-speed stirred is by the dispersion of chlorination magnesium alcoholate melt liquid pearl and is situated between
Chlorination magnesium alcoholate granule is formed in matter.The particle diameter distribution of carrier prepared by the method is wider.
CN1463990A discloses a kind of emulsifying cooling preparation technology of chlorination magnesium alcoholate.Chlorine is prepared in inert media
Change the suspension of magnesium alcoholate, float is entered cooling medium after mulser and forms chlorination magnesium alcoholate granule.The party
The particle diameter of carrier prepared by method is little, and machine utilization is low, and size adjusts difficult.
CN1267508C discloses a kind of magnesium halide/alcohol adducts and its preparation method and application.Prepare in inert media
The suspension of chlorination magnesium alcoholate, float forms chlorination magnesium alcoholate by the high-gravity rotating bed rear cooling medium that enters
Grain.The method prepares, the regularity poor (abnormity material easily occur) of the big particle diameter carrier of preparation difficult compared with small carrier.
The carrier of above-mentioned preparation with titanium tetrachloride and internal electron donor compound reaction by preparing spheric polypropylene catalysis
Agent.The particle shape of chlorination magnesium alcoholate carrier determines the particle shape of catalyst, and it is chlorination magnesium alcoholate melt liquid that it prepares key
The dispersion technology of pearl, it controls diameter of carrier size and distribution.
The content of the invention
It is an object of the invention to overcome the defect of prior art, there is provided a kind of simple to operate, magnesium halide can be stably controlled
The size and size distribution of alcohol adduct carrier, and the olefin polymerization catalysis that prepare of the carrier that obtains that there is hydrogen to adjust is quick
The preparation method of the magnesium halide alcohol adduct carriers of advantage such as perceptual and/or vertical structure directionality height.
As stated in the Background Art, the preparation method of magnesium halide alcohol adduct ball type carrier include spray drying method, spray cooling,
High pressure extrusion methods, high-speed mixing method and high-gravity rotating bed method.
(1) method that spray drying method prepares the carrier for polyolefin catalyst：With nitrogen by MgCl2-ol mixture
System sprays into hothouse by specially designed nozzle, and is dried to spherical magnesium chloride support in the noble gases of preheating；
However, the present inventor has found under study for action, using spray drying method in carrier preparation process, expend big
Amount ethanol, nitrogen, energy, and the carrier granular form for finally giving is not good, and alcohol content is not enough in carrier；
Carrier prepared by simultaneous spray drying has following impact on catalyst：Due to the outlet temperature of spray-dried instrument it is higher,
Cause that the ball type carrier alcohol content for obtaining is relatively low, especially spherical carrier particle surfactant alkanol is very few, in follow-up loading process,
Active component can not affect final with carrier useful effect and with reference on the surface, making active ingredient content in catalyst low
Catalytic polymerization activity.
(2) method that spray cooling is used for the carrier of polyolefin catalyst：Magnesium chloride alcohol mixed system is led to nitrogen
Cross specially designed nozzle and spray into hothouse, and condensation forms spherical magnesium chloride support in cooling medium；
However, the process is complex, instrument and equipment requirement is higher, is difficult that the little ball type carrier of particle diameter is obtained, and
Alcohol content is too high in the carrier of preparation；
The carrier that simultaneously prepared by spray cooling has following impact on catalyst：In ball type carrier, due to mean diameter it is larger,
N is more than 3, and alcohol content is higher, when carrier and titanium-containing compound react, because reaction is excessively fierce, often crushes carrier,
Final fine powder is caused to increase.
(3) method that high pressure extrusion cooling method is used for the carrier for preparing polyolefin catalyst：With the less oil refining of viscosity,
The reaction mediums such as paraffin, white oil, temperature of reaction system rise to 120-130 DEG C and maintain a period of time after, fill into reactor
Enter high pure nitrogen, make reacting kettle inner pressure reach 10-15 atmospheric pressure；Afterwards, chlorination magnesium alcoholate melt and reaction medium
Mixture be discharged in cooling medium by a discharge duct；The length of discharge duct is 3-10m, and bore is 1-2mm,
Flow rate of the mixed liquor in pipe is about 4-7m/s；
The technique has as a drawback that：The form of higher to equipment requirements and resulting chlorination magnesium alcoholate granule is owed
Good, so that the final catalyst granules form for preparing is not good enough, the particle shape of polymer is not ideal enough, polymer
Bulk density is not high.
(4) method that high-speed mixing method is used for the carrier for preparing polyolefin catalyst：By anhydrous magnesium chloride and alcohol by certain
Ratio is added in the inert liquid medium immiscible with it, is heated under agitation, makes EtOH/MgCl2Form complex to melt
Change dispersion in media as well, emulsifying is then carried out in high speed agitator or mulser, and be transferred in the medium of low temperature, will
MgCl2-ol complex rapid condensation cured globulate MgCl wherein2Carrier；
The technique has as a drawback that：The carrier granular for obtaining is larger, broad particle distribution, the work of prepared catalyst
Property is also unsatisfactory.
(5) higee technology prepares the method for preparing the carrier of polyolefin catalyst：By anhydrous magnesium chloride
It is added to by a certain percentage in the inert liquid medium immiscible with it with alcohol, heats under agitation, makes EtOH/MgCl2
Composite melting dispersion is formed in media as well, into high-gravity rotating bed, through the static distribution being arranged at rotor center
Device is equably sprayed on the inner edge of the filler that adjustment is rotating, and material is adjusted after filler shearing, the dispersion for rotating, chlorine
Change magnesium/alcohol adducts melt to be scattered in inert media in the form of fine drop；
The shortcoming of the technique：It is high-gravity rotating bed produce it is less (<30 microns) particle diameter and greater particle size (>65 microns)
During carrier, diameter of carrier wider distribution；During steady production, it is necessary to using blending agent (generally white oil and silicone oil
Mixing) could normally produce, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, protect
The ratio of the two is held, so for the repetition stability for maintaining carrier production, difficulty is increased.
With the progressively development of carrier technique, the technology of Beijing Chemical Research Institute has evolved to hypergravity machine technology polyolefin
Carrier, but this technology is the drawbacks of have aforementioned, needs perspective study and exploitation：
And the present inventor proposes first a kind of simple to operate, repetition stability by force, magnesium halide can be stably controlled
The size and size distribution of alcohol adduct carrier, and the olefin polymerization catalysis that prepare of the carrier that obtains that there is hydrogen to adjust is quick
The preparation method of the magnesium halide alcohol adduct carriers of advantage such as perceptual and/or vertical structure directionality height, the method is only needed by pressurization,
Magnesium halide alcohol adduct melt is contacted through the construction unit with hole with liquid cooling medium and be capable of achieving object defined above.
Thus, according to the first aspect of the invention, the invention provides a kind of system of the catalytic component for olefinic polymerization
Preparation Method, the method includes：Magnesium halide alcohol adduct carrier, titanium compound and internal electron donor are carried out into haptoreaction,
The internal electron donor contains carboxylic acid diol ester and phosphate ester；The preparation process of the magnesium halide alcohol adduct carrier includes：
Plus pressure, magnesium halide alcohol adduct melt is contacted through the construction unit with hole with liquid cooling medium.
According to the second aspect of the invention, the invention provides preparation method of the present invention prepare for alkene
The catalytic component of polymerization.
According to the third aspect of the invention we, the invention provides a kind of catalyst for olefinic polymerization, the catalyst contains：
I () catalytic component, the catalytic component is the catalytic component for olefinic polymerization of the present invention；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
According to the fourth aspect of the invention, the invention provides catalytic component for olefinic polymerization of the present invention or
The described application for the catalyst of olefinic polymerization in olefinic polyreaction.
The method of the present invention has following advantage：
First, compared to currently advanced technology hypergravity machine technology, in the consistent production process of hypergravity machine, it is necessary to
Could normally be produced using blending agent (the usually blending agent of white oil and silicone oil), but it is continuous with production process
Consume, need to be continuously replenished fresh inert media, the ratio of the two is kept, so for the repetition for maintaining carrier production
Stability, increased difficulty；And the technology of the present invention is gone back except the inert media of mixing can be used normally to produce
Can be better, it is therefore apparent that using single using for example single white oil of single medium or silicone oil production carrier
Medium undoubtedly improves the repetition stability of its production for carrier production.
Second, the preparation method of above various carriers is compared, the equipment of the technology of the present invention is simple, and energy consumption and material consumption are low.
3rd, by key elements such as the mesh number of adjusting hole, the number of plies of construction unit and pressure, be easier realize to particle diameter,
The control of particle shape, that is to say, that can be according to market demand, the production of the formula that carries out cutting the garment according to the figure is changed the line of production convenient and easy.
4th, the catalyst of the carrier synthesis of the technology preparation of the present invention compares the catalyst of existing production, possesses good
Vertical structure directionality, this for exploitation high added value acrylic resin lay a good foundation.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, concrete with following
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 schematic diagram of the mounting means with pore structure unit according to one embodiment of the present invention；
Fig. 2 is the schematic diagram of the mounting means with pore structure unit according to one embodiment of the present invention.
Description of reference numerals
1：Magnesium halide alcohol adduct melt material feed-line；
2：Unit with pore structure.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that concrete reality described herein
The mode of applying is merely to illustrate and explains the present invention, is not limited to the present invention.
As it was previously stated, the invention provides a kind of preparation method of the catalytic component for olefinic polymerization, the method includes：
Magnesium halide alcohol adduct carrier, titanium compound and internal electron donor are carried out into haptoreaction, the internal electron donor contains carboxylic
Sour diol ester and phosphate ester；The preparation process of the magnesium halide alcohol adduct carrier includes：Under elevated pressure, magnesium halide alcohol is closed
Thing melt is contacted through the construction unit with hole with liquid cooling medium.
With the method for the invention it is preferred to the condition of the pressurization includes：Pressure is 0.05-1MPa, more preferably
0.1-0.5MPa, more preferably 0.2-0.5MPa.Using the preferred pressure, can further optimize size and
Size distribution, while olefin polymerization catalysis prepared by the carrier for obtaining have hydrogen response and/or vertical structure directionality height etc.
Advantage.
The method according to the invention, the pressure is the relative pressure counted as 0MPa with atmospheric pressure, i.e. with existing air
Relative pressure on the basis of pressure.
The method of the present invention, only need to be by pressurization, without the need under the conditions of hypergravity and without using equipment such as spray nozzles
It is capable of achieving the purpose of the present invention, it can be seen that, the method for the present invention compares the preparation method of above various carriers, if
Standby simple, operation is simple, energy consumption and material consumption are low.
With the method for the invention it is preferred to the aperture in the hole is 10-1800 μm, more preferably 20-800 μm, further
Preferably 30-150 μm.
The method according to the invention, the construction unit with hole can be various forms, for example, the plate with hole,
Net with hole etc..For the present invention, it is however preferred to have the net in hole, according to the needs of actual production and being easy to get for material
Property consider, most preferred diameters for 0.025-4mm twine.
The method according to the invention, the material of the construction unit with hole without particular/special requirement, for example, metal material,
One or more in cloth material, plastic material and ceramic material.According to the ready availability of the needs of actual production and material,
Preferably metal material.
A preferred embodiment of the invention, the construction unit with hole is stratum reticulare.
The method according to the invention, the wire netting using multilamellar macropore gauge structure is tied with the small-bore using the relatively little of number of plies
Structure wire netting, it is possible to obtain the suitable adduct solid particle of particle morphology.Prepare small particle (such as less than 30 μm) adduction
The metal mesh structure of 1-20 layer aperture gauge structures (if aperture is for 30-50 μm) is preferably adopted during thing carrier, big grain is being prepared
1-20 layers are preferably adopted to tie with respect to large aperture (if aperture is for 65-200 μm) during footpath (such as larger than 65 μm) adduct carrier
The metal mesh structure of structure.
A preferred embodiment of the invention, the stratum reticulare includes 1-20 layers, preferably includes 2-8 layers；Per thickness
Degree is respectively 0.01-0.35mm, more preferably preferably 0.05-0.25mm, 0.1-0.15mm.
A preferred embodiment of the invention, the stratum reticulare is metal net layer.
The method of the present invention, by key elements such as the mesh number of adjusting hole, the number of plies of construction unit and pressure, easily realizes to grain
Footpath, the control of particle shape, that is to say, that the method for the present invention can be according to market demand, the production of the formula that carries out cutting the garment according to the figure,
Change the line of production convenient and easy.
According to the present invention, the present invention is to the composition of the carrier without particular/special requirement, for the present invention, the preferred carrier
Shown in formula such as formula (I)：
MgXY–mROH–nE–pH2O (I)；
Wherein, m is 1-5, preferably 2.4-3.5；
Wherein, n is 0-0.3, preferably 0.005-0.2；
Wherein, p is 0-0.08；
Wherein, X is halogen, preferably chlorine or bromine, more preferably chlorine；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Fragrant oxygen
Base；
Wherein, R is C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl, preferably C1-C4Alkyl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
Preferred embodiment, the MgXY is magnesium dichloride, dibrominated magnesium, Benzene Chloride oxygen to one kind of the invention
One or more in base magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium, preferably magnesium dichloride.
According to one kind of the invention preferred embodiment, the ROH is methanol, ethanol, propanol, isopropanol, positive fourth
One kind in alcohol, isobutanol, amylalcohol, isoamyl alcohol, hexanol n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol and Propylene Glycol or
It is various.
, according to the invention it is preferred to the E is ether, ester and assimilation compound.
According to the present invention, the H in formula (I)2O for institute's band in reaction raw materials and reaction medium water.
According to the present invention, the preparation method to the magnesium halide alcohol adduct melt of the invention, can be according to normal without particular/special requirement
Rule technology is prepared, and for the present invention, the preparation process of the preferably magnesium halide alcohol adduct melt includes：
In confined conditions, by magnesium halide MgXY, optionally alcohol roh, electron donor compound E and inert fluid
Medium mixes, and under agitation mixture is heated to into 100-160 DEG C；
Wherein, X is halogen, preferably chlorine or bromine, more preferably chlorine；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Fragrant oxygen
Base；
Wherein, R is C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl, preferably C1-C4Alkyl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
Preferred embodiment, the MgXY is magnesium dichloride, dibrominated magnesium, Benzene Chloride oxygen to one kind of the invention
One or more in base magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium, preferably magnesium dichloride.
It is of the invention it is a kind of preferred embodiment, the ROH is methanol, ethanol, propanol, isopropanol, just
One kind in butanol, isobutanol, amylalcohol, isoamyl alcohol, hexanol n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol and Propylene Glycol
Or it is various.
, according to the invention it is preferred to the E is ether, ester and assimilation compound.
According to the present invention, described inert liquid medium is the change do not reacted with magnesium halide, alcohol, electron donor compound E
Compound, the preferably inert liquid medium are silicone oil and/or inert fluid hydrocarbon solvent；Preferably, the inert liquid medium
For C4-C10Alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicon
One or more in oil, phenyl silicone oil and methyl phenyl silicone oil；Preferably, the inert liquid medium is silicone oil.
The method of the present invention, compared to currently advanced technology hypergravity machine technology, the consistent production process of hypergravity machine
In, it is necessary to could normally be produced using blending agent (the usually blending agent of white oil and silicone oil), but with producing
The continuous consumption of journey, needs to be continuously replenished fresh inert media, keeps the ratio of the two, so for maintenance carrier life
The repetition stability of product, increased difficulty；And the technology of the present invention except using mixing inert media can normally produce,
Can also be better using for example single white oil of single medium or silicone oil production carrier.It is clear that using list
One medium undoubtedly increased the repetition stability of its production for carrier production.
According to the present invention, in the preparation of magnesium halide alcohol adduct melt, charging sequence is in no particular order.
A preferred embodiment of the invention, by 1mol on the basis of the MgXY that magnesium is counted, the use of alcohol roh
Measure as 1-5.5mol, more preferably preferably 2-3.7mol, 2.4-3.7mol；The consumption of E is 0.001-0.32mol, preferably
For 0.005-0.17mol, more preferably 0.015-0.12mol.
In the present invention, the consumption of the inert liquid medium can be selected according to the concrete consumption of MgXY.Usually,
Relative to 1 mole of MgXY in terms of magnesium, the consumption of inert liquid medium is 0.2-13L；Preferably, relative to 1 mole
MgXY in terms of magnesium, the consumption of inert liquid medium is 0.6-6.5L.
According to the present invention, the liquid cooling medium be unreactive hydrocarbons solvent, preferably pentane, hexane, heptane, gasoline and
One or more in petroleum ether；It is preferred that the temperature of the liquid cooling medium is (- 10 DEG C)-(- 40 DEG C).
The method for preparing carrier of the present invention is simple, for example, the unit with pore structure can be arranged on into halogenation
It is situated between in magnesium alcoholate melt material feed-line or installed in magnesium halide alcohol adduct melt material feed-line and liquid cooling
Between matter storage tank, specifically for example as shown in figure 1, the unit 2 with pore structure is arranged on into magnesium halide alcohol adduct
In melt material feed-line 1, magnesium halide alcohol adduct melt passes through the list with pore structure before contacting with cooling medium
Unit.
And for example as shown in Fig. 2 the unit 2 with pore structure is arranged on into magnesium halide alcohol adduct melt material delivery pipe
Between line 1 and liquid cooling medium storage tank (not shown), magnesium halide alcohol adduct melt is worn before contacting with cooling medium
Cross the unit with pore structure.
With the method for the invention it is preferred to the preparation process of the magnesium halide alcohol adduct carrier of the present invention also includes：Will
The spherical magnesium halide alcohol polymer granule Jing inert hydrocarbon solvents washing arrived, the step being dried.This is techniques known,
It is not described here in detail.
Diameter of carrier size and particle diameter distribution prepared by the technology of the present invention is easily controlled, and the catalysis synthesized using carrier
Agent, compares the catalyst of existing production, possesses good vertical structure directionality, and this is for the polypropylene tree of exploitation high added value
Fat is laid a good foundation.
The catalyst of carrier synthesis prepared by the method for the present invention, the catalyst for producing compared to existing technology possesses good
Vertical structure directionality, this lays a good foundation for the acrylic resin of exploitation high added value.
According to the present invention, certain collaboration just can be produced when the internal electron donor contains carboxylic acid diol ester and phosphate ester
Effect, on the basis of the consumption of the internal electron donor, total consumption of carboxylic acid diol ester and phosphate ester can be 80-100 weights
Amount %.And, it was found by the inventors of the present invention that when the mol ratio of the phosphate ester and carboxylic acid diol ester is (0.001-0.4)：
1, preferably (0.02-0.3)：1, more preferably (0.05-0.15)：When 1, both can cooperate with and allocate more preferably, from
And obtain the higher catalyst of vertical structure capacity of orientation.
According to the present invention, the carboxylic acid diol ester can be it is various can be used as electron in the catalyst of olefinic polymerization
The carboxylic acid diol ester of body, it is preferable that the structure of the carboxylic acid diol ester is shown below：
Wherein, R1And R2It is identical or different, and it is each independently C1-C10Straight or branched alkyl, C3-C20's
Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl or C7-C20Aralkyl, the aryl, alkaryl and aralkyl
Hydrogen atom on middle phenyl ring is optionally replaced by halogen atom；In formula, the content representation of bracket [] has n carbon atom to be bonded successively,
And each carbon atom is also bonded with two substituent groups, i.e., n carbon atom and R are had in bracket1、R2、R3…R2nDeng
2n substituent group；R3-R6And R1-R2nIt is identical or differ, and it is each independently hydrogen, halogen, C1-C20Straight chain or
Branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20Aralkyl, C2-C10
Alkylene or C10-C20Fused ring aryl, R3-R6And R1-R2nOn carbon atom and/or hydrogen atom optionally taken by hetero atom
Generation, the hetero atom is selected from nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atom, or R3-R6And R1-R2nIn two or many
It is individual to bond together to form saturation or undersaturated ring structure；N for 0-10 integer, as n=0, then the carboxylic acid two shown in above formula
Substituent group is R in alcohol ester3、R4Carbon atom directly with substituent group be R5、R6Carbon atom be bonded.
Wherein, C1-C10The example of straight or branched alkyl can including but not limited to：Methyl, ethyl, n-pro-pyl,
Isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, just oneself
Base, n-heptyl and n-octyl.C3-C20The example of cycloalkyl can including but not limited to：Cyclopropyl, cyclopenta, ring
Hexyl, 4- methylcyclohexyls, 4- ethylcyclohexyls, 4- n-pro-pyls cyclohexyl and 4- normal-butyl cyclohexyl.C6-C20Aryl
Example can including but not limited to：Phenyl, naphthyl, 4- aminomethyl phenyls and 4- ethylphenyls.C7-C20Alkaryl reality
Example can be including but not limited to：Aminomethyl phenyl, ethylphenyl, n-pro-pyl phenyl, n-butylphenyl, tert-butyl-phenyl,
Isopropyl phenyl and n-pentyl phenyl.C7-C20The example of aralkyl can including but not limited to：Phenyl methyl, phenyl
Ethyl, phenyl n-pro-pyl, phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base and phenyl n-pentyl.C1-C20It is straight
The example of chain or branched alkyl can be including but not limited to：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl,
Positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, positive 17
Alkyl, n-octadecane base, AI3-36122 base and AI3-28404 base.C2-C10Alkylene example can include but do not limit
In：Vinyl, pi-allyl, cyclobutenyl, hexenyl, phenyl vinyl, phenyl n-butene base.C10-C20Condensed ring virtue
The example of base can be including but not limited to：Naphthyl, methyl naphthyl, ethyl naphthyl, anthryl, methylanthryl, ethyl anthryl,
Phenanthryl, methyl phenanthryl and ethyl phenanthryl.
, according to the invention it is preferred in the case of, the structure of the carboxylic acid diol ester is shown below：
Wherein, R7-R12It is identical or differ, and it is each independently selected from hydrogen, C1-C20Straight or branched alkyl.Such as
It is upper described, C1-C20The example of straight or branched alkyl can including but not limited to：It is methyl, ethyl, n-pro-pyl, different
Propyl group, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl,
N-heptyl, n-octyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, just
Cetyl, n-heptadecane base, n-octadecane base, AI3-36122 base and AI3-28404 base.
Specifically, the carboxylic acid diol ester can for example be selected from 1,3-PD dibenzoate, 2- methyl isophthalic acids, ammediol
Dibenzoate, 2- ethyl -1,3- propylene glycol dibenzoates, 2- propyl group -1,3- propylene glycol dibenzoates, 2- butyl -1,3-
Propylene glycol dibenzoate, 2，2-dimethyl-1，3-propanediol dibenzoate, 2- ethyls -2- butyl -1,3-PD hexichol
Formic acid esters, 2,2- diethyl -1,3- propylene glycol dibenzoates, 2- methyl-2-propyl -1,3- propylene glycol dibenzoates, 2- are different
Propyl group -2- isopentyl -1,3- propylene glycol dibenzoates, 2,4-PD dibenzoate, 3- methyl -2,4-PD hexichol first
Acid esters, 3- ethyls -2,4-PD dibenzoate, 3- propyl group -2,4-PD dibenzoate, 3- butyl -2,4-PD
Dibenzoate, 3,3- dimethyl -2,4-PD dibenzoate, 2- methyl isophthalic acids, 3- glycol dibenzoates, 2,2- bis-
Methyl isophthalic acid, 3- glycol dibenzoates, 2- ethyl -1,3- glycol dibenzoates, 2- butyl -1,3- pentanediol dibenzoic acids
Ester, 2- methyl isophthalic acids, 3- glycol dibenzoates, 2- ethyl -1,3- glycol dibenzoates, 2- propyl group -1,3- pentanediols two
Benzoate, 2- butyl -1,3- glycol dibenzoates, 2,2- dimethyl -1,3- glycol dibenzoates, 2- methyl isophthalic acids, 3-
Glycol dibenzoate, 2,2- dimethyl -1,3- glycol dibenzoates, 2- ethyl -1,3- glycol dibenzoates,
2- butyl -1,3- glycol dibenzoates, 2,2,4- trimethyl -1,3- glycol dibenzoates, 3- methyl -3- butyl -2,4-
Glycol dibenzoate, 2,2- dimethyl -1,5- glycol dibenzoates, 1,6-HD dibenzoate, 6- heptene
- 2,4- heptandiol dibenzoates, 2- methyl -6- heptene -2,4- heptandiol dibenzoates, 3- methyl -6- heptene -2,4- heptandiols
Dibenzoate, 4- methyl -6- heptene -2,4- heptandiol dibenzoates, 5- methyl -6- heptene -2,4- heptandiol dibenzoic acids
Ester, 6- methyl -6- heptene -2,4- heptandiol dibenzoates, 3- ethyl -6- heptene -2,4- heptandiol dibenzoates, 4- ethyls
- 6- heptene -2,4- heptandiol dibenzoates, 5- ethyl -6- heptene -2,4- heptandiol dibenzoates, 6- ethyl -6- heptene -2,4-
Heptandiol dibenzoate, 3- propyl group -6- heptene -2,4- heptandiol dibenzoates, 4- propyl group -6- heptene -2,4- heptandiols two
Benzoate, 5- propyl group -6- heptene -2,4- heptandiol dibenzoates, 6- propyl group -6- heptene -2,4- heptandiol dibenzoates,
3- butyl -6- heptene -2,4- heptandiol dibenzoates, 4- butyl -6- heptene -2,4- heptandiol dibenzoates, 5- butyl -6-
Heptene -2,4- heptandiol dibenzoates, 6- butyl -6- heptene -2,4- heptandiol dibenzoates, 3,5- dimethyl -6- heptene
- 2,4- heptandiol dibenzoates, 3,5- diethyl -6- heptene -2,4- heptandiol dibenzoates, 3,5- dipropyl -6- heptene -2,4-
Heptandiol dibenzoate, 3,5- dibutyl -6- heptene -2,4- heptandiol dibenzoates, 3,3- dimethyl -6- heptene -2,4- heptan
Bisbenzoate, 3,3- diethyl -6- heptene -2,4- heptandiol dibenzoates, 3,3- dipropyl -6- heptene -2,4- heptan two
Alcohol dibenzoate, 3,3- dibutyl -6- heptene -2,4- heptandiol dibenzoates, 3,5- heptandiol dibenzoates, 2- first
Base -3,5- heptandiol dibenzoates, 3- methyl -3,5- heptandiol dibenzoates, 4- methyl -3,5- heptandiol dibenzoates,
5- methyl -3,5- heptandiol dibenzoates, 6- methyl -3,5- heptandiol dibenzoates, 3- ethyl -3,5- heptandiol hexichol first
Acid esters, 4- ethyl -3,5- heptandiol dibenzoates, 5- ethyl -3,5- heptandiol dibenzoates, 3- propyl group -3,5- heptandiols
Dibenzoate, 4- propyl group -3,5- heptandiol dibenzoates, 3- butyl -3,5- heptandiol dibenzoates, 2,3- dimethyl
- 3,5- heptandiol dibenzoates, 2,4- dimethyl -3,5- heptandiol dibenzoates, 2,5- dimethyl -3,5- heptandiol hexichol
Formic acid esters, 2,6- dimethyl -3,5- heptandiol dibenzoates, 3,3- dimethyl -3,5- heptandiol dibenzoates, 4,4- diformazans
Base -3,5- heptandiol dibenzoates, 6,6- dimethyl -3,5- heptandiol dibenzoates, 2,6- dimethyl -3,5- heptandiols two
Benzoate, 3,4- dimethyl -3,5- heptandiol dibenzoates, 3,5- dimethyl -3,5- heptandiol dibenzoates, 3,6-
Dimethyl -3,5- heptandiol dibenzoates, 4,5- dimethyl -3,5- heptandiol dibenzoates, 4,6- dimethyl -3,5- heptan two
Alcohol dibenzoate, 4,4- dimethyl -3,5- heptandiol dibenzoates, 6,6- dimethyl -3,5- heptandiol dibenzoates,
2- methyl -3- ethyl -3,5- heptandiol dibenzoates, 2- methyl -4- ethyl -3,5- heptandiol dibenzoates, 2- methyl -5-
Ethyl -3,5- heptandiol dibenzoates, 3- methyl -3- ethyl -3,5- heptandiol dibenzoates, 3- methyl -4- ethyl -3,5-
Heptandiol dibenzoate, 3- methyl -5- ethyl -3,5- heptandiol dibenzoates, 4- methyl -3- ethyl -3,5- heptandiols two
Benzoate, 4- methyl -4- ethyl -3,5- heptandiol dibenzoates, 4- methyl -5- ethyl -3,5- heptandiol dibenzoates,
2- methyl -3- propyl group -3,5- heptandiol dibenzoates, 2- methyl -4- propyl group -3,5- heptandiol dibenzoates, 2- methyl -5-
Propyl group -3,5- heptandiol dibenzoates, 3- methyl -3- propyl group -3,5- heptandiol dibenzoates, 3- methyl -4- propyl group -3,5-
Heptandiol dibenzoate, 3- methyl -5- propyl group -3,5- heptandiol dibenzoates, 4- methyl -3- propyl group -3,5- heptandiols two
Benzoate, 4- methyl -4- propyl group -3,5- heptandiols dibenzoate and 4- methyl -5- propyl group -3,5- heptandiol dibenzoates
In one or more.
In a particular embodiment of the present invention, use for 4- ethyl -3,5- heptandiol dibenzoates, 2,4- pentanediols two
Benzoate property explanation as an example.
The present invention is also not particularly limited to the species of the phosphate ester, can for it is various can be used as olefinic polymerization
Catalyst internal electron donor phosphate ester, under preferable case, the structure of the phosphate ester is shown below：
Wherein, R13、R14And R15It is each independently selected from C1-C4Straight or branched alkyl, C3-C20Cycloalkyl,
C6-C20Aryl, C7-C20Alkaryl, C7-C20Aralkyl, in the aryl, alkaryl and aralkyl on phenyl ring
Hydrogen atom optionally replaced by halogen atom.C1-C4The example of straight or branched alkyl can including but not limited to：Methyl,
Ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.C3-C20Cycloalkyl, C6-C20
Aryl, C7-C20Alkaryl and C7-C20Aralkyl can be according to being selected above, here will not be described in great detail.
Specifically, the phosphate ester can for example be selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate
Phenyl ester, tricresyl phosphate, IPPP, tripotassium phosphate epoxide phenyl ester, phosphoric acid phenyl dimethyl ester, phosphoric acid
Tolyl dibutyl ester, p isopropylbenzoic acid phenyl dimethyl ester, p isopropylbenzoic acid diethylamino phenyl ester, p isopropylbenzoic acid phenyl dibutyl ester, phosphorus
Tolyl dibutyl ester between sour phenyl diformazan phenyl ester, phosphoric acid phenyl 6-diisopropyl benzene ester, phosphoric acid p-methylphenyl dibutyl ester, phosphoric acid,
Phosphoric acid is to cumenyl dimethyl ester, phosphoric acid to cumenyl diethylester, phosphoric acid to tert-butyl-phenyl dimethyl ester and phosphoric acid neighbour's first
Phenyl is to one or more in two 2-methyl-2-phenylpropane base esters.
In a particular embodiment of the present invention, use for tributyl phosphate property explanation as an example.
According to the present invention, in the preparation process for the catalytic component of olefinic polymerization, titanium compound can be this area
Conventional selection, for example, the titanium compound can be Ti (OR ') for formula3-aZaAnd/or Ti (OR ')4-bZbMaterial,
Wherein, R ' is C1-C20Alkyl, Z be F, Cl, Br or I, a for 1-3 integer, b for 1-4 integer.It is preferred that
In the case of, the titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy
Titanium chloride, butoxy titanous chloride., triethoxy titanium chloride, diethoxy titanium chloride, ethyoxyl titanous chloride. and
One or more in titanous chloride..
According to the present invention, in the catalytic component for olefinic polymerization, titanium elements, magnesium elements and internal electron donor
Weight ratio can be 1：(3-15)：(2-10), preferably 1：(3-12)：(2-7), more preferably 1：(3-5)：(2-4).
Preferred embodiment, the method includes one kind of the invention：By magnesium halide alcohol adduct carrier and titanium compound
Reaction, and one or more times before and after, during the magnesium halide alcohol adduct carrier and titanium compound reaction
The internal electron donor is added to carry out the haptoreaction in section.
Specifically, the magnesium halide alcohol adduct carrier can be according to mode same as the prior art with the reaction of titanium compound
Carry out, for example, titanium compound can be cooled to less than 0 DEG C (preferably -5 to -25 DEG C), be subsequently adding the conjunction of magnesium halide alcohol
Thing carrier, and stirring mixing 10-60 minutes at such a temperature, are warming up to afterwards reaction temperature (i.e. about 60-130 DEG C), and
0.5-10 hours are maintained under the reaction temperature.In the preparation method for the catalytic component of olefinic polymerization, institute
During internal electron donor compound is stated before and after, during the reaction of the magnesium halide alcohol adduct carrier and titanium compound
Add in one or more time periods.The magnesium halide alcohol adduct carrier is referred to the time period before the reaction of titanium compound
Time period after the magnesium halide alcohol adduct carrier is added in reactor and before reaction temperature is warming up to.
According to the present invention, in the preparation process for the catalytic component of olefinic polymerization, the halogenation in terms of magnesium elements
The mol ratio of the consumption of magnesium alcoholate carrier, the titanium compound counted with titanium elements and internal electron donor can be 1：(20-140)：
(0.1-0.8), preferably 1：(40-90)：(0.15-0.6).
As it was previously stated, a kind of the invention provides urging for olefinic polymerization for preparing according to the method described in the present invention
Agent component.
As it was previously stated, the invention provides a kind of catalyst for olefinic polymerization, the catalyst contains：
I () catalytic component, the catalytic component is the catalytic component for olefinic polymerization of the present invention；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
According to the present invention, the alkyl aluminum can be the conventional selection of this area, and for example, the formula of the alkyl aluminum can be with
For AlR16R16′R16", wherein, R16、R16′、R16" it is each independently C1-8Alkyl, and wherein one or two base
Group can be halogen；The C1-8The instantiation of alkyl can including but not limited to：Methyl, ethyl, propyl group, just
Butyl, isobutyl group, amyl group, hexyl, n-heptyl, n-octyl, the halogen can be fluorine, chlorine, bromine, iodine.Specifically
Ground, the alkyl aluminum can for example be selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, a chlorine
Diethyl aluminum, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminum, a chlorine di-n-hexyl aluminum, the aluminium ethide of dichloro one, dichloro
One or more in one aluminium isobutyl, the n-butylaluminum of dichloro one and the n-hexyl aluminum of dichloro one.
According to the present invention, the external electron donor can be various external electron donors commonly used in the art, for example, described outer
Electron donor can be the one kind in carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound
Or it is various；Preferably, the external electron donor is containing at least one Si-OR keys and formula is (R17)a(R18)bSi(OR19)c
Silicon compound, wherein, R17、R18And R19For C1-C18Alkyl, optionally contain hetero atom, a and b are each only
Found the integer for 0-2, c for 1-3 integer, and a, b and c and for 4.Preferably, R17、R18For C3-C10's
Alkyl, cycloalkyl, optionally contain hetero atom；R19For C1-C10Alkyl, optionally contain hetero atom.Specifically,
The external electron donor for example can be selected from Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, two just
Butyldimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl tertbutyl dimethoxy
Base silane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- t-butyldimethoxysilanes, (the fluoro- 2- of 1,1,1- tri-
Propyl group) one kind in -2- ethyl piperidine base dimethoxysilanes and (1,1,1-, three fluoro- 2- propyl group)-methyl dimethoxysilane
Or it is various.
Typically also, in the catalyst for olefinic polymerization, olefinic polymerization to be used for described in terms of titanium elements
Catalytic component and the mol ratio of the alkyl aluminum consumption counted with aluminium element can be 1：(1-2000), preferably 1：
(10-500)；The mol ratio of the external electron donor and the alkyl aluminum consumption counted with aluminium element can be 1：(2-200),
Preferably 1：(2.5-100).
According to the present invention, in the preparation process for the catalyst of olefinic polymerization, alkyl aluminum and optional external electron donor
Compound reacts after can mix with the catalytic component for olefinic polymerization respectively, or can also be by alkyl aluminum and optional
External electron donor in advance mixing after mix and react with the catalytic component for olefinic polymerization again.
According to the present invention, when by olefinic polymerization is used for for the catalyst of olefinic polymerization, the urging for olefinic polymerization
Agent component, alkyl aluminum and optional external electron donor can be separately added in polymer reactor, added after also can mixing
In polymer reactor, prepolymerization method commonly understood in the industry may also be employed will be added in polymer reactor after alkene pre-polymerization.
As it was previously stated, the invention provides the catalytic component or of the present invention for olefinic polymerization of the present invention
For the application of the catalyst in olefinic polyreaction of olefinic polymerization.
Theing improvement is that for the present invention employs a kind of new catalyst for olefinic polymerization, urging for olefinic polymerization
Agent component, and the concrete species of alkene, the polymerisation process of alkene and condition can be with same as the prior art.
According to the present invention, above-mentioned catalyst is particularly well-suited to formula for CH2(wherein, R is hydrogen, C to=CHR1-C6Alkane
Base or C6-C12Aryl) alkene homopolymerization and copolyreaction.
According to the present invention, the polyreaction of the alkene can be carried out according to existing method, specifically, in noble gases
Protection under, in liquid monomer or the atent solvent containing polymerized monomer, or in the gas phase, or by liquid phase
Polymerization mix technique carries out polyreaction.The temperature of the polyreaction can be typically 0-150 DEG C, preferably 60-90 DEG C.
The pressure of the polyreaction can be normal pressure or higher；For example can be 0.01-10MPa, preferably 0.01-2MPa,
More preferably 0.1-2MPa.The pressure of the present invention refers both to gauge pressure.In the course of the polymerization process, hydrogen can be used as polymer molecular weight
Regulator is added in reaction system to adjust the molecular weight and melt index of polymer.Additionally, in the polyreaction of alkene
During, the noble gases, the species of solvent and consumption are known to the skilled person, and here will not be described in great detail.
The examples below is used for illustrating the present invention, is not for limiting the scope of the present invention.
Method of testing：
1st, melt index：At 230 DEG C of temperature and the pressure of 2.16kg, surveyed according to ASTM D1238-99
It is fixed.
2nd, polymer isotacticity：Determined (heptane boiling extracting 6 hours) using heptane extraction process：Two grams of dry polymerizations
Thing sample, is placed in extractor after being extracted 6 hours with boiling heptane, by residue drying to the polymer weight obtained by constant weight
Ratio of the amount (g) with 2 is isotacticity.
3rd, particle diameter distribution test：The mean diameter and particle size distribution Masters Sizer 2000 of magnesium halide alcohol adduct granule
(being manufactured by Malvern Instruments Ltd) particle size analyzer determination.
4th, the molecular weight distribution of polymer is determined using Shimadzu LC-10AT type chromatograph of gel permeation (GPC), wherein,
THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.
Prepare embodiment 1
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 125 DEG C are warmed up under agitation,
Stir at 125 DEG C 3 hours, it is at 0.2 mpa, mixture is (every through the wire netting of 2 layer of 200 mesh by blanking pipeline
Thickness degree 0.1mm) after be directly placed into and pre-cool into -30 DEG C of 3L hexanes, filter off liquid, wash solid with hexane
Three times, vacuum drying obtains 50 grams of spherical chlorination magnesium alcoholate solid particle S1, and alcohol/magnesium mol ratio is 2.6, is characterized
As a result such as table 1.
Prepare embodiment 2
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 125 DEG C are warmed up under agitation,
Stir 3 hours at 125 DEG C, it is under 0.5MPa, mixture is (every through the wire netting of 4 layer of 200 mesh by blanking pipeline
Thickness degree 0.1mm) after be directly placed into and pre-cool into -30 DEG C of 3L hexanes, filter off liquid, wash solid with hexane
Three times, vacuum drying obtains 54 grams of spherical chlorination magnesium alcoholate solid particle S2, characterization result such as table 1.
Prepare embodiment 3
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 125 DEG C are warmed up under agitation,
Stir 3 hours at 125 DEG C, it is under 0.3MPa, mixture is (every through the wire netting of 3 layer of 200 mesh by blanking pipeline
Thickness degree 0.1mm) after be directly placed into and pre-cool into -30 DEG C of 3L hexanes, filter off liquid, wash solid with hexane
Three times, vacuum drying obtains 60 grams of spherical chlorination magnesium alcoholate solid particle S3, characterization result such as table 1.
Prepare embodiment 4
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol and 3ml O-methoxy benzene first are added
Acyl chlorides, is warmed up under agitation 125 DEG C, stirs 3 hours at 125 DEG C, at 0.2 mpa, by mixture by blanking
Pipeline be directly placed into after the wire netting (per thickness degree 0.1mm) of 4 layer of 200 mesh pre-cool to -30 DEG C 3L
In alkane, liquid is filtered off, solid three times wash with hexane, be vacuum dried, obtain 56 grams of spherical chlorination magnesium alcoholate solid
Granule S4, characterization result such as table 1.
Prepare embodiment 5
In the autoclave of 1L, silicone oil 300ml and white oil 200ml, 30 grams of magnesium chlorides, 50ml ethanol are added, stirred
Mix down and be warmed up to 125 DEG C, stir 3 hours at 125 DEG C, under 0.5MPa, by mixture by blanking pipeline through 6
It is directly placed into after the wire netting (per thickness degree 0.1mm) of 200 mesh of layer and pre-cools into -30 DEG C of 3L hexanes, filters off
Liquid, solid three times is washed with hexane, and vacuum drying obtains 51 grams of spherical chlorination magnesium alcoholate solid particle S5,
Characterization result such as table 1.
Prepare embodiment 6
In the autoclave of 1L, white oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 125 DEG C are warmed up under agitation,
Stir at 125 DEG C 3 hours, it is at 0.2 mpa, mixture is (every through the wire netting of 4 layer of 200 mesh by blanking pipeline
Thickness degree 0.1mm) after be directly placed into and pre-cool into -30 DEG C of 3L hexanes, filter off liquid, wash solid with hexane
Three times, vacuum drying obtains 49 grams of spherical chlorination magnesium alcoholate solid particle S6, characterization result such as table 1.
Prepare embodiment 7
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 125 DEG C are warmed up under agitation,
Stir 3 hours at 125 DEG C, it is under 0.6MPa, mixture is (every through the wire netting of 8 layer of 150 mesh by blanking pipeline
Thickness degree 0.15mm) after be directly placed into and pre-cool into -30 DEG C of 3L hexanes, filter off liquid, wash solid with hexane
Three times, vacuum drying obtains 55 grams of spherical chlorination magnesium alcoholate solid particle S7, characterization result such as table 1.
Prepare embodiment 8
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 120 DEG C are warmed up under agitation,
Stir 3 hours at 120 DEG C, it is under 0.6MPa, mixture is (every through the wire netting of 4 layer of 300 mesh by blanking pipeline
Thickness degree 0.09mm) after be directly placed into and pre-cool into -30 DEG C of 3L hexanes, filter off liquid, wash solid with hexane
Three times, vacuum drying obtains 58 grams of spherical chlorination magnesium alcoholate solid particle S8, characterization result such as table 1.
Prepare comparative example 1
In the autoclave of 1L, silicone oil 300ml, white oil 150ml, 30 grams of magnesium chlorides, 50ml ethanol are added, stirred
Mix down and be warmed up to 125 DEG C, stir 3 hours at 125 DEG C, material is put in the hypergravity machine of unlatching, by hypergravity
Machine is entered and pre-cooled into -30 DEG C of 3L hexanes, filters off liquid, and solid three times wash with hexane, is vacuum dried, and is obtained
To 58 grams of spherical chlorination magnesium alcoholate solid particle DS1, characterization result such as table 1.
Prepare comparative example 2
In the autoclave of 1L, white oil 500ml, 30 grams of magnesium chlorides, 50ml ethanol are added, 125 are warmed up under agitation
DEG C, stir 3 hours at 125 DEG C, material is put in the hypergravity machine of unlatching, entered by hypergravity machine and pre-cooled
To in -30 DEG C of hexanes, liquid is filtered off, solid three times wash with hexane, be vacuum dried, obtain 56 grams of spherical magnesium chloride
Alcohol adduct solid particle DS2, characterization result such as table 1.
Table 1
| Embodiment | D10(μm) | D50(μm) | D90(μm) | Span |
| 1 | 16.9 | 45.3 | 62.5 | 1.0 |
| 2 | 17.1 | 44.3 | 56.9 | 0.9 |
| 3 | 18.3 | 42.1 | 60.5 | 1.0 |
| 4 | 17.5 | 44.9 | 62.4 | 1.0 |
| 5 | 22.5 | 43.4 | 65.9 | 1.0 |
| 6 | 24.1 | 50.2 | 78.2 | 1.1 |
| 7 | 39.8 | 70.6 | 108.3 | 0.98 |
| 8 | 18.7 | 22.3 | 39.8 | 0.95 |
| Comparative example 1 | 21.4 | 43.2 | 63.3 | 0.97 |
| Comparative example 2 | 26.1 | 53.4 | 105.9 | 1.5 |
Note：Span=(D90-D10)/D50
Can be seen that by the result of table 1 and compare higee technology, the present invention can prepare the adduction of different-grain diameter
Thing carrier, and narrower particle size distribution, the big particle diameter (D50 for particularly preparing>60 μm) adduct carrier, still with narrower
Particle size distribution.
Embodiment 1
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
(1) it is used for the preparation of the catalytic component of olefinic polymerization using the carrier S 1 for preparing the preparation of embodiment 1：
In the glass reaction bottle of 300ml, add the titanium tetrachloride of 90ml and be cooled to -20 DEG C, by 8 grams of magnesium chloride
Alcohol adduct S1 is added thereto, and then heats to 110 DEG C, and the tributyl phosphate of 0.0002mol is added in temperature-rise period
With 4- ethyl -3 of 0.015mol, 5- heptandiol dibenzoates, liquid is filtered off after maintaining 30min at 110 DEG C, afterwards
Add titanium tetrachloride to wash 2 times, finally washed with hexane 5 times, after vacuum drying, obtain urging for olefinic polymerization
Agent component C1.
(2) propylene polymerization：
In the autoclave of a 5L, purged using stream of nitrogen gas, 5ml is then introduced in stream of nitrogen gas
Triethyl aluminum hexane solution (concentration of triethyl aluminum be 0.5mmol/ml), the cyclohexyl methyl dimethoxy silicon of 1ml
The hexane solution (concentration of CHMMS be 0.1mmol/ml) of alkane (CHMMS), the anhydrous hexane of 10ml and 8mg
The catalytic component C1 for olefinic polymerization.Autoclave is closed, the hydrogen and 2.3L of 1.5L (normal volume) is added
Liquid propene, be warming up to 70 DEG C, and react 1 hour at such a temperature.Acquired results are as shown in table 2.
Embodiment 2
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of hydrogen is 6.5L during propylene polymerization.Acquired results are as shown in table 2.
Embodiment 3
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
(1) it is used for the preparation of the catalytic component of olefinic polymerization using the carrier S 1 for preparing the preparation of embodiment 1：
In the glass reaction bottle of 300ml, add the titanium tetrachloride of 90ml and be cooled to -20 DEG C, by 8 grams of magnesium halide
Carrier S 1 is added thereto, and then heats to 110 DEG C, and add in temperature-rise period 0.0015mol tributyl phosphate and
2, the 4- glycol dibenzoates of 0.005mol, after maintaining 30min at 110 DEG C liquid is filtered off, and tetrachloro is added afterwards
Change titanium to wash 2 times, finally washed with hexane 5 times, after vacuum drying, obtain the catalytic component C2 for olefinic polymerization.
(2) propylene polymerization：
It is same as Example 1.Acquired results are as shown in table 2.
Embodiment 4
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
Method according to embodiment 3 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of hydrogen is 6.5L during propylene polymerization.Acquired results are as shown in table 2.
Embodiment 5
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
(1) it is used for the preparation of the catalytic component of olefinic polymerization using the carrier S 2 for preparing the preparation of embodiment 2：
In the glass reaction bottle of 300ml, add the titanium tetrachloride of 90ml and be cooled to -20 DEG C, by 8 grams of magnesium halide
Carrier S 2 is added thereto, and then heats to 110 DEG C, and add in temperature-rise period 0.001mol tributyl phosphate and
2, the 4- glycol dibenzoates of 0.01mol, after maintaining 30min at 110 DEG C liquid is filtered off, and tetrachloro is added afterwards
Change titanium to wash 2 times, finally washed with hexane 5 times, after vacuum drying, obtain the catalytic component C3 for olefinic polymerization.
(2) propylene polymerization：
It is same as Example 1.Acquired results are as shown in table 2.
Embodiment 6
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
Method according to embodiment 5 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of hydrogen is 6.5L during propylene polymerization.Acquired results are as shown in table 2.
Embodiment 7
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of the tributyl phosphate is 0.001mol, 4- ethyl -3, the addition of 5- heptandiol dibenzoates
Measure as 0.008mol, obtain the catalytic component C4 for olefinic polymerization.Acquired results are as shown in table 2.
Embodiment 8
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization
Agent and its application.
Method according to embodiment 7 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of hydrogen is 6.5L during propylene polymerization.Acquired results are as shown in table 2.
Comparative example 1
The comparative example is used for catalytic component of olefinic polymerization and preparation method thereof and for olefinic polymerization for illustrating reference
Catalyst and its application.
Magnesium halide carrier (as disclosed in preparing comparative example 1 prepared by method)
Method according to embodiment 5 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, in the preparation process for the catalytic component of olefinic polymerization, the tributyl phosphate is with the 2,4- of identical weight part
Glycol dibenzoate is substituted, and obtains the catalytic component DC1 for olefinic polymerization.Acquired results are as shown in table 2.
Comparative example 2
The comparative example is used for catalytic component of olefinic polymerization and preparation method thereof and for olefinic polymerization for illustrating reference
Catalyst and its application.
Method according to comparative example 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of hydrogen is 6.5L during propylene polymerization.Acquired results are as shown in table 2.
Comparative example 3
The comparative example is used for catalytic component of olefinic polymerization and preparation method thereof and for olefinic polymerization for illustrating reference
Catalyst and its application.
Magnesium halide carrier (as disclosed in preparing comparative example 1 prepared by method)
Method according to embodiment 7 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, in the preparation process for the catalytic component of olefinic polymerization, the tributyl phosphate 4- of identical weight part
Ethyl -3,5- heptandiols dibenzoate is substituted, and obtains the catalytic component DC2 for olefinic polymerization.Acquired results such as table
Shown in 2.
Comparative example 4
The comparative example is used for catalytic component of olefinic polymerization and preparation method thereof and for olefinic polymerization for illustrating reference
Catalyst and its application.
Method according to comparative example 3 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different
, the addition of hydrogen is 6.5L during propylene polymerization.Acquired results are as shown in table 2.
Comparative example 5
The comparative example is used for catalytic component of olefinic polymerization and preparation method thereof and for olefinic polymerization for illustrating reference
Catalyst and its application.
Method according to embodiment 7 carries out propylene polymerization, except that, the catalyst for olefinic polymerization
The DQ catalyst that component is produced with identical weight part purchased from Sinopec Ao Da catalyst branch company is (referred to as：DC3,
Internal electron donor is diisobutyl phthalate) substitute.Acquired results are as shown in table 2.
Comparative example 6
The comparative example is used for catalytic component of olefinic polymerization and preparation method thereof and for olefinic polymerization for illustrating reference
Catalyst and its application.
Method according to comparative example 5 carries out propylene polymerization, except that, hydrogen during propylene polymerization
Addition is 6.5L.Acquired results are as shown in table 2.
Table 2
Can be seen that when using the chlorination magnesium alcoholate prepared by the present invention from the result of embodiment 1-8 and comparative example 1-4
When containing carboxylic acid diol ester and phosphate ester simultaneously for carrier, and internal electron donor, the vertical of catalyst can be effectively improved
Structure capacity of orientation, the isotactic index (or claiming polymer isotacticity) of the polymer for obtaining is significantly improved.From embodiment 7-8
Can be seen that using present invention offer without electron in phthalate with the comparing result of comparative example 5-6
Catalyst has and the suitable performance of the existing industrial catalyst with phthalic acid ester as internal electron donor.
Embodiment 9-14
Method according to embodiment 1-2 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is not
With, catalytic component C5-C10 is prepared using carrier S 3-S8, the results are shown in Table 3.
Comparative example 7
Method according to embodiment 1-2 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is not
With, catalytic component DC4 is prepared using carrier DS2, the results are shown in Table 3.
Table 3
In table, triethyl aluminum and the mol ratio of Cyclohexyl Methyl Dimethoxysilane that Al/ED is added when being polymerization.
Can be seen that the catalyst prepared using the preparation method of the carrier of the present invention has higher vertical structure by the result of table 3
Directionality.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, can carry out various simple variants to technical scheme,
These simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not contradiction
In the case of, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention is to various
Possible compound mode is no longer separately illustrated.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as it is without prejudice to this
Bright thought, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of preparation method of the catalytic component for olefinic polymerization, the method includes：Magnesium halide alcohol adduct is carried
Body, titanium compound and internal electron donor carry out haptoreaction, it is characterised in that the internal electron donor contains carboxylic acid two
Alcohol ester and phosphate ester；The preparation process of the magnesium halide alcohol adduct carrier includes：Under elevated pressure, magnesium halide alcohol adduct is melted
Body is contacted through the construction unit with hole with liquid cooling medium.
2. preparation method according to claim 1, wherein, the condition of the pressurization includes：Pressure is 0.05-1MPa,
Preferably 0.1-0.5MPa.
3. preparation method according to claim 1 and 2, wherein, the aperture in the hole is 10-1800 μm, preferably
For 20-800 μm, more preferably 30-150 μm.
4. the preparation method according to any one in claim 1-3, wherein, the construction unit with hole is
Stratum reticulare.
5. preparation method according to claim 4, wherein, the stratum reticulare includes 1-20 layers, preferably includes 2-8
Layer；0.01-0.35mm, preferably 0.05-0.25mm are respectively per thickness degree.
6. preparation method according to claim 4, wherein, the stratum reticulare is metal net layer.
7. preparation method according to claim 1, wherein, shown in the formula such as formula (I) of the carrier：
MgXY–mROH–nE–pH2O (I)；
Wherein, m is 1-5, preferably 2.4-3.5；
Wherein, n is 0-0.3, preferably 0.005-0.2；
Wherein, p is 0-0.08；
Wherein, X is halogen；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Fragrant oxygen
Base；
Wherein, R is C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl, preferably C1-C4Alkyl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
8. the preparation method according to claim 1 or 7, wherein, the preparation step of the magnesium halide alcohol adduct melt
Suddenly include：
In confined conditions, by magnesium halide MgXY, optionally alcohol roh, electron donor compound E and inert fluid
Medium mixes, and under agitation mixture is heated to into 100-160 DEG C；
Wherein, X is halogen；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Fragrant oxygen
Base；
Wherein, R is C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl, preferably C1-C4Alkyl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
9. preparation method according to claim 8, wherein, the inert liquid medium is silicone oil and/or inert liquid
Body hydrocarbon solvent；Preferably, the inert liquid medium is C4-C10Alkane, kerosene, paraffin oil, vaseline oil, white
One or more in oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil；
Preferably, the inert liquid medium is silicone oil.
10. preparation method according to claim 8, wherein, by 1mol on the basis of the MgXY that magnesium is counted, alcohol
The consumption of ROH is 1-5.5mol, and the consumption of E is 0.001-0.32mol.
11. preparation methoies according to claim 1 and 2, wherein, the liquid cooling medium is unreactive hydrocarbons solvent,
One or more preferably in pentane, hexane, heptane, gasoline or petrol ether；The temperature of the liquid cooling medium is
(-10℃)-(-40℃)。
12. preparation methoies according to claim 1 and 2, wherein, on the basis of the consumption of the internal electron donor,
Total consumption of carboxylic acid diol ester and phosphate ester is 80-100 weight %；The mol ratio of the phosphate ester and carboxylic acid diol ester consumption
For (0.001-0.4)：1, preferably (0.02-0.3)：1, more preferably (0.05-0.15)：1.
13. preparation methoies according to claim 1 and 2,
Wherein, the structure of the carboxylic acid diol ester is shown below：
Wherein, R1And R2It is identical or different, and it is each independently C1-C10Straight or branched alkyl, C3-C20's
Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl or C7-C20Aralkyl, the aryl, alkaryl and aralkyl
Hydrogen atom on middle phenyl ring is optionally replaced by halogen atom；R3-R6And R1-R2nIt is identical or differ, and be each independently hydrogen,
Halogen, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20
Aralkyl, C2-C10Alkylene or C10-C20Fused ring aryl, R3-R6And R1-R2nOn carbon atom and/or hydrogen it is former
Son is optionally exchanged for heteroatoms, and the hetero atom is selected from nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atom, or R3-R6And R1-R2n
In two or more bond together to form saturation or undersaturated ring structure；N is the integer of 0-10；
Wherein, the structure of the phosphate ester is shown below：
Wherein, R13、R14And R15It is each independently selected from C1-C4Straight or branched alkyl, C3-C20Cycloalkyl,
C6-C20Aryl, C7-C20Alkaryl, C7-C20Aralkyl, in the aryl, alkaryl and aralkyl on phenyl ring
Hydrogen atom optionally replaced by halogen atom.
14. preparation methoies according to claim 1 and 2, wherein, the method includes：Magnesium halide alcohol adduct is carried
Body reacts with titanium compound, and before and after, during the magnesium halide alcohol adduct carrier and titanium compound reaction
The internal electron donor is added to carry out the haptoreaction in individual or multiple time periods.
The catalytic component for olefinic polymerization that method in 15. claim 1-14 described in any one is prepared.
A kind of 16. catalyst for olefinic polymerization, the catalyst contains：
I () catalytic component, the catalytic component is the catalytic component for olefinic polymerization described in claim 15；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
Described in catalytic component or claim 16 for olefinic polymerization described in 17. claim 15 for alkene
Application of the catalyst of polymerization in olefinic polyreaction.
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| US4069169A (en) * | 1975-11-24 | 1978-01-17 | Mitsui Petrochemical Industries Ltd. | Process for preparation of catalyst component supported on high performance carrier |
| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
| CN101486776A (en) * | 2008-01-17 | 2009-07-22 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization , and catalyst thereof |
| CN103665205A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst component applied to olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application of catalyst |
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Patent Citations (4)
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| US4069169A (en) * | 1975-11-24 | 1978-01-17 | Mitsui Petrochemical Industries Ltd. | Process for preparation of catalyst component supported on high performance carrier |
| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
| CN101486776A (en) * | 2008-01-17 | 2009-07-22 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization , and catalyst thereof |
| CN103665205A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst component applied to olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application of catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109694425A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst and its application |
| CN109694425B (en) * | 2017-10-24 | 2021-10-19 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof |
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