CN106608936B - Catalytic component for olefinic polymerization and its preparation method and application and catalyst and its application for olefinic polymerization - Google Patents
Catalytic component for olefinic polymerization and its preparation method and application and catalyst and its application for olefinic polymerization Download PDFInfo
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- CN106608936B CN106608936B CN201510708423.3A CN201510708423A CN106608936B CN 106608936 B CN106608936 B CN 106608936B CN 201510708423 A CN201510708423 A CN 201510708423A CN 106608936 B CN106608936 B CN 106608936B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The present invention relates to field of olefin polymerisation, specifically provide a kind of catalytic component and its preparation method and application for olefinic polymerization, this method comprises: magnesium halide alcohol adduct carrier, titanium compound and internal electron donor are carried out haptoreaction, the internal electron donor contains diether compounds；The preparation step of the magnesium halide alcohol adduct carrier includes: under elevated pressure, magnesium halide alcohol adduct melt to be passed through structural unit with hole and is contacted with liquid cooling medium.The present invention provides a kind of catalyst for olefinic polymerization and its applications.The catalyst of the carrier synthesis of technology preparation of the invention has good hydrogen response and/or vertical structure directionality compared to the catalyst of existing production, this lays a good foundation for developing the acrylic resin of high added value.
Description
Technical field
The present invention relates to a kind of preparation methods of catalytic component for olefinic polymerization, and the use obtained by this method
In the catalytic component of olefinic polymerization and its application in olefin polymerization；With for olefinic polymerization catalyst and its
Application in olefin polymerization.
Technical background
Spheric polypropylene catalyst is widely used in loop technology polypropylene production apparatus, has polymer apparent density
The advantages that height, particle shape are regular, and high, the vertical structure directionality of polymerization catalyst activity is high.Carrier technique is the technology core of spheric catalyst
One of heart.
Chlorination magnesium alcoholate ball type carrier applying and be in polyolefin catalyst field in polyolefin catalyst synthesis
It is well known.Currently, the preparation method of chlorination magnesium alcoholate ball type carrier includes spray drying process, spray cooling, high pressure extrusion
Method, high-speed mixing method and high-gravity rotating bed method.
US4421674 and CN1765940A discloses a kind of spray drying the preparation method and prepares carrier for olefin polymerization catalyst
(for carrier alcohol content less than 14%, apparent density 0.32g/ml, the partial size of carrier is less than 20 microns), by the ethanol solution of magnesium chloride
(about 100-300g/L) is sprayed in the vaporizer of flow of warm nitrogen gas after being preheated to 90-100 DEG C, forms chlorine after removing most of alcohol
Change the ball type carrier of magnesium alcoholate.This method first prepares the ethanol solution of magnesium chloride, and ethanol consumption is big, and energy consumption is higher.
US6020279 discloses a kind of chlorination magnesium alcoholate misting cooling the preparation method.By the fusant of chlorination magnesium alcoholate
Chlorination magnesium alcoholate carrier is formed into cooling medium by nozzle spray.The partial size of the carrier of this method preparation is small, and equipment is negative
Lotus is low, and particle size adjusts difficult.
The height that CN1330086A and US6686307 discloses chlorination magnesium alcoholate stirs preparation process, first in inert media
The suspension for preparing chlorination magnesium alcoholate will be put into cooling medium after the dispersion of chlorination magnesium alcoholate melt liquid pearl by high-speed stirred
Middle formation chlorination magnesium alcoholate particle.The particle diameter distribution of the carrier of this method preparation is wider.
CN1463990A discloses a kind of cooling preparation process of emulsification of chlorination magnesium alcoholate.Chlorine is prepared in inert media
Change the suspension of magnesium alcoholate, suspended matter enters cooling medium formation chlorination magnesium alcoholate particle after passing through mulser.This method
The partial size of the carrier of preparation is small, and machine utilization is low, and particle size adjusts difficult.
CN1267508C discloses a kind of magnesium halide/alcohol adducts and its preparation method and application.It is made in inert media
The suspension of standby chlorination magnesium alcoholate, suspended matter form chlorination magnesium alcoholate by the high-gravity rotating bed rear cooling medium that enters
Grain.Compared with small carrier difficulty, the regularity of the big partial size carrier of preparation is poor (abnormity material easily occur) for this method preparation.
The carrier of above-mentioned preparation prepares spheric polypropylene and urges by reacting with titanium tetrachloride and internal electron donor compound
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, which prepares key,
The dispersion technology of pearl, it controls diameter of carrier size and distribution.
Summary of the invention
It it is an object of the invention to overcome the deficiencies of existing technologies, provides a kind of easy to operate, can steadily control halogenation
The particle size and size distribution of magnesium alcoholate carrier, and obtain carrier preparation olefin polymerization catalysis have hydrogen tune it is quick
The preparation method of the magnesium halide alcohol adduct carriers of advantages 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 includes spray drying process, misting cooling
Method, high pressure extrusion methods, high-speed mixing method and high-gravity rotating bed method.
(1) method of the spray drying process preparation for the carrier of polyolefin catalyst: with nitrogen by MgCl2-ol mixture
System sprays into hothouse by specially designed nozzle, and spherical magnesium chloride support is dried in the inert gas of preheating；
However, the present inventor has found under study for action, using spray drying process in carrier preparation process, expend big
Ethyl alcohol, nitrogen, energy are measured, and finally obtained carrier granular form is bad, and alcohol content is insufficient in carrier；
Simultaneous spray drying preparation carrier have following influence to catalyst: due to spray-dried instrument outlet temperature compared with
Height, the ball type carrier alcohol content caused is lower, and especially spherical carrier particle surfactant alkanol is very few, in subsequent loading process
In, active component cannot with carrier useful effect and combine on the surface, make in catalyst active ingredient content low and influence most
Whole catalytic polymerization activity.
(2) method of the spray cooling for the carrier of polyolefin catalyst: magnesium chloride alcohol mixed system is led to nitrogen
It crosses specially designed nozzle and sprays into hothouse, and condensation forms spherical magnesium chloride support in cooling medium；
However, the process is complex, instrument and equipment is more demanding, is not easy that the small ball type carrier of partial size is made, and
Alcohol content is excessively high in the carrier of preparation；
The carrier of misting cooling preparation simultaneously has following influence to catalyst: in ball type carrier, since average grain diameter is larger,
N is greater than 3, and alcohol content is higher, excessively fierce due to reacting when carrier is reacted with titanium-containing compound, often makes carrier broken, causes
Final fine powder increases.
(3) high pressure squeezes out the method that cooling method is used to prepare the carrier of polyolefin catalyst: with the lesser oil refining of viscosity, stone
The reaction mediums such as wax, white oil are filled with height into reaction kettle after temperature of reaction system rises to 120-130 DEG C and maintains a period of time
Pure nitrogen gas makes reacting kettle inner pressure reach 10-15 atmospheric pressure；Later, the mixture of chlorination magnesium alcoholate melt and reaction medium
It is discharged into cooling medium by a discharge duct；The length of discharge duct is 3-10m, and bore 1-2mm, mixed liquor is in pipe
Flow rate is about 4-7m/s；
The technique has the drawback that the high requirements on the equipment, and the form of obtained chlorination magnesium alcoholate particle
Not good enough, so that the catalyst granules form finally prepared is not good enough, the particle shape of polymer is not ideal enough, the heap of polymer
Product density is not high.
(4) method that high-speed mixing method is used to prepare the carrier of polyolefin catalyst: by anhydrous magnesium chloride and alcohol by certain
Ratio is added in the inert liquid medium immiscible with it, is heated under stiring, and EtOH/MgCl is made2It is formed composite melting
Dispersion in the medium, is then emulsified in high speed agitator or mulser, and be transferred in the medium of low temperature, by MgCl2-
Alcohol compound wherein rapid condensation cured at spherical MgCl2Carrier；
The carrier granular that the technique has the drawback that is larger, broad particle distribution, the work of prepared catalyst
Property is also unsatisfactory.
(5) method that higee technology preparation is used to prepare the carrier of polyolefin catalyst: by anhydrous magnesium chloride
It is added in the inert liquid medium immiscible with it by a certain percentage with alcohol, heats under stiring, make EtOH/MgCl2It is formed
In the medium, entrance is high-gravity rotating bed for composite melting dispersion, uniform by the static distribution device at the setting in the rotor heart
Ground is sprayed on the inner edge for the filler that adjustment is rotating, and after material is adjusted the filler shearing of rotation, dispersion, magnesium chloride/alcohol adds
Polymer melt is scattered in inert media in the form of fine drop；
The shortcomings that technique: high-gravity rotating bed to carry producing smaller (<30 microns) partial size and greater particle size (>65 micron)
When body, diameter of carrier wider distribution；During steady production, it is necessary to just using blending agent (generally white oil and silicone oil mix)
It can normally produce, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, keep the ratio of the two
Example increases difficulty in this way for the repetition stability for maintaining carrier production.
With the gradually development of carrier technique, the technology of Beijing Chemical Research Institute has evolved to hypergravity machine technology polyene
Hydrocarbon carrier, but there are aforementioned drawbacks for this technology, need perspective study and exploitation:
And the present inventor be put forward for the first time it is a kind of it is easy to operate, repetition stability is strong, can steadily control halogenation
The particle size and size distribution of magnesium alcoholate carrier, and obtain carrier preparation olefin polymerization catalysis have hydrogen tune it is quick
The preparation method of the magnesium halide alcohol adduct carriers of advantages such as perceptual and/or vertical structure directionality height, this method are only needed through pressurization, will
Magnesium halide alcohol adduct melt, which is contacted across structural unit with hole with liquid cooling medium, can be realized foregoing purpose.
As a result, according to the first aspect of the invention, the present invention provides a kind of catalytic components for olefinic polymerization
Preparation method, this method comprises: magnesium halide alcohol adduct carrier, titanium compound and internal electron donor are carried out haptoreaction, institute
It states internal electron donor and contains diether compounds；The preparation step of the magnesium halide alcohol adduct carrier includes: under elevated pressure, by halogenation
Magnesium alcoholate melt passes through structural unit with hole and contacts with liquid cooling medium.
According to the second aspect of the invention, the present invention provides what preparation method of the present invention was prepared to be used for alkene
The catalytic component of polymerized hydrocarbon.
According to the third aspect of the invention we, the present invention provides a kind of catalyst for olefinic polymerization, which contains
Have: (i) catalytic component, the catalytic component are the catalytic component of the present invention for olefinic polymerization；
(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 present invention provides the catalytic components of the present invention for olefinic polymerization
Or the application for the catalyst of olefinic polymerization in olefin polymerization.
Method of the invention has the advantage that
First, compared to currently advanced technology hypergravity machine technology, in the consistent production process of hypergravity machine, it is necessary to
It could normally be produced using blending agent (the usually blending agent of white oil and silicone oil), but constantly disappearing with production process
Consumption, needs to be continuously replenished fresh inert media, the ratio of the two is kept, in this way for maintaining the repetition of carrier production to stablize
Property, increase difficulty；And technology of the invention can be produced normally in addition to the inert media of mixing can be used, and can also be used
For example individual white oil of single medium or silicone oil produce carrier, better effect, it is therefore apparent that using Single Medium for carrier
Production undoubtedly improves the repetition stability of its production.
Second, compared to the preparation method of the various carriers in front, the equipment of technology of the invention is simple, and energy consumption and material consumption are low.
Third, by adjusting elements such as the mesh number in hole, the number of plies of structural unit and pressure, be easier to realize to partial size,
The control of particle shape, that is to say, that can be according to market needs, the production for the formula that cut the garment according to the figure is changed the line of production convenient and easy.
4th, the catalyst of the carrier synthesis of technology preparation of the invention has good compared to the catalyst of existing production
Hydrogen response and/or vertical structure directionality, this for develop high added value acrylic resin lay a good foundation.
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 schematic diagram according to the mounting means with pore structure unit of one embodiment of the present invention；
Fig. 2 is the schematic diagram according to the mounting means with pore structure unit of one embodiment of the present invention.
Description of symbols
1: magnesium halide alcohol adduct melt material feed-line；
2: the unit with pore structure.
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.
As previously mentioned, the present invention provides a kind of preparation method of catalytic component for olefinic polymerization, this method packet
It includes: magnesium halide alcohol adduct carrier, titanium compound and internal electron donor being subjected to haptoreaction, the internal electron donor contains two
Ether compound；The preparation step of the magnesium halide alcohol adduct carrier includes: under elevated pressure, magnesium halide alcohol adduct melt to be passed through tool
Porose structural unit is contacted with liquid cooling medium.
With the method for the invention it is preferred to which it is 0.05-1MPa, more preferably 0.1- that the condition of the pressurization, which includes: pressure,
0.5MPa, further preferably 0.2-0.5MPa.Using the preferred pressure, particle size and size point can be advanced optimized
Cloth, while the olefin polymerization catalysis of obtained carrier preparation has the advantages such as hydrogen response and/or vertical structure directionality height.
According to the method for the present invention, the pressure be by atmospheric pressure be 0MPa in terms of relative pressure, that is, with existing atmospheric pressure
On the basis of relative pressure.
Method of the invention, only need to be by pressurization, without setting under the conditions of hypergravity and without using spray nozzle etc.
It is standby that the purpose of the present invention can be realized, it can be seen that, method of the invention, compared to the preparation method of the various carriers in front, equipment
Simply, 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 be 10-1800 μm, more preferably 20-800 μm, further
Preferably 30-150 μm.
According to the method for the present invention, the structural unit with hole can be various forms, plate for example, with hole,
Net with hole etc..For the present invention, it is however preferred to have the net in hole is examined according to the needs of actual production and the ready availability of material
Consider, most preferred diameters are the twine of 0.025-4mm.
According to the method for the present invention, the material of the structural unit with hole is without particular/special requirement, for example, metal material,
One of fabric material, plastic material and ceramic material are a variety of.It is excellent according to the ready availability of the needs of actual production and material
It is selected as metal material.
A preferred embodiment of the invention, the structural unit with hole are stratum reticulare.
According to the method for the present invention, using the metal mesh of multilayer macropore gauge structure and using the small-bore of the relatively little of number of plies
Structural metal net can obtain the comparable adduct solid particle of particle morphology.Prepare small particle (such as less than 30 μm) adduct
The metal mesh structure that 1-20 layers of aperture gauge structure (such as aperture is 30-50 μm) is preferably used when carrier is preparing big partial size (as greatly
In 65 μm) adduct carrier when preferably use the metal mesh knots of 1-20 layers of opposite large aperture (such as aperture is 65-200 μm) structure
Structure.
A preferred embodiment of the invention, the stratum reticulare include 1-20 layers, preferably include 2-8 layers；Every thickness
Degree is respectively 0.01-0.35mm, preferably 0.05-0.25mm, more preferably 0.1-0.15mm.
A preferred embodiment of the invention, the stratum reticulare are metal net layer.
Method of the invention, it is easy to accomplish to grain by adjusting elements such as the mesh number in hole, the number of plies of structural unit and pressure
The control of diameter, particle shape, that is to say, that method of the invention can be according to market needs, and the production for the formula that cut the garment according to the figure is changed the line of production
It is 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 preferably described carrier
General formula is shown below:
MgXY–mROH–nE–pH2O；
Wherein, m 1-5, preferably 2.4-3.5；
Wherein, n 0-0.3, preferably 0.005-0.2；
Wherein, p 0-0.08；
Wherein, X is halogen, preferably chlorine or bromine, more preferably chlorine；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxy, C6-C14Aryl or C6-C14Aryloxy group；
Wherein, R C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl, preferably C1-C4Alkyl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
According to a preferred embodiment of the present invention, the MgXY is magnesium dichloride, magnesium dibromide, chlorination phenoxy group
One of magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium are a variety of, preferably magnesium dichloride.
A kind of preferred embodiment according to the present invention, the ROH is methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, different
One of butanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol and propylene glycol are a variety of.
, according to the invention it is preferred to which the E is ether, ester and ketone compound.
According to the present invention, the H in above formula2O for institute's band in reaction raw materials and reaction medium water.
According to the present invention, the present invention to the preparation method of the magnesium halide alcohol adduct melt without particular/special requirement, can be according to
Prepared by routine techniques, for the present invention, the preparation step of the preferably described magnesium halide alcohol adduct melt includes:
In confined conditions, magnesium halide MgXY, alcohol roh, optionally electron donor compound E and inert liquid medium are mixed
It closes, mixture is heated to 100-160 DEG C under stiring；
Wherein, X is halogen, preferably chlorine or bromine, more preferably chlorine；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxy, C6-C14Aryl or C6-C14Aryloxy group；
Wherein, R C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl, preferably C1-C4Alkyl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
According to a preferred embodiment of the present invention, the MgXY is magnesium dichloride, magnesium dibromide, chlorination phenoxy group
One of magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium are a variety of, preferably magnesium dichloride.
According to a preferred embodiment of the present invention, the ROH be methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol,
One of isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol and propylene glycol are a variety of.
, according to the invention it is preferred to which the E is ether, ester and ketone compound.
According to the present invention, the inert liquid medium is the change that do not react with magnesium halide, alcohol, electron donor compound E
Object is closed, the preferably described inert liquid medium is silicone oil and/or inert fluid hydrocarbon solvent；Preferably, the inert liquid medium is
C4-C10Alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil
With one of methyl phenyl silicone oil or a variety of；Preferably, the inert liquid medium is silicone oil.
Method of the invention, compared to currently advanced technology hypergravity machine technology, hypergravity machine is consistent to be produced
Cheng Zhong, it is necessary to could normally be produced using blending agent (the usually blending agent of white oil and silicone oil), but with production process
Continuous consumption, need to be continuously replenished fresh inert media, the ratio both kept, the in this way weight for maintaining carrier production
Multiple stability, increases difficulty；And technology of the invention can also make in addition to using the inert media of mixing that can normally produce
Carrier, better effect are produced with for example individual white oil of single medium or silicone oil.It is clear that using Single Medium for carrying
Body production undoubtedly increases the repetition stability of its 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 dosage of alcohol roh is 1-
5.5mol, preferably 2-3.7mol, more preferably 2.4-3.7mol；The dosage of E is 0.001-0.32mol, preferably 0.005-
0.17mol, more preferably 0.015-0.12mol.
In the present invention, the dosage of the inert liquid medium can be selected according to the specific dosage of MgXY.Generally, phase
For 1 mole of MgXY in terms of magnesium, the dosage of inert liquid medium is 0.2-13L；Preferably, relative to 1 mole in terms of magnesium
MgXY, the dosage of inert liquid medium are 0.6-6.5L.
According to the present invention, the liquid cooling medium is unreactive hydrocarbons solvent, preferably pentane, hexane, heptane, gasoline and stone
One of oily ether is a variety of；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 invention is simple and easy, such as the unit with pore structure can be mounted on halogen
Change in magnesium alcoholate melt material feed-line or be mounted on magnesium halide alcohol adduct melt material feed-line and liquid is cooling
Between medium reservoirs, specifically for example melted as shown in Figure 1, the unit 2 with pore structure is mounted on magnesium halide alcohol adduct
In body Location Detection of Medium Transportation Pipeline 1, magnesium halide alcohol adduct melt passes through the unit with pore structure before contacting with cooling medium.
For another example as shown in Fig. 2, the unit 2 with pore structure is mounted on magnesium halide alcohol adduct melt material delivery pipe
Between line 1 and liquid cooling medium storage tank (not shown), magnesium halide alcohol adduct melt passes through institute before contacting with cooling medium
State the unit with pore structure.
With the method for the invention it is preferred to the preparation step of the magnesium halide alcohol adduct carrier of the invention further include: will
Obtained spherical magnesium halide alcohol polymer particle is through inert hydrocarbon solvent washing, dry step.This is techniques known,
This is not described in detail here.
The diameter of carrier size and particle diameter distribution of technology preparation of the invention are easy to control, and using the catalysis of carrier synthesis
Agent has good hydrogen response and/or vertical structure directionality compared to the catalyst of existing production, this is high for exploitation additional
The acrylic resin of value is laid a good foundation.
The catalyst of the carrier synthesis of method preparation of the invention, the catalyst produced compared with prior art have good
Hydrogen response and/or vertical structure directionality, this for develop high added value acrylic resin lay a good foundation.
According to the present invention, the purpose of the present invention can be realized when the internal electron donor contains diether compounds, preferably institute
The total dosage for stating diether compounds can be 80-100 weight %.
According to the present invention, the diether compounds are I compound represented of formula,
Formula I,
In formula I, R '1、R’2、R’3、R’4、R’5And R '6It is identical or different, it is each independently hydrogen, halogen, C1-C20It is straight
Chain or branched alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Take
Generation or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl；
R’7And R '8Can be identical or different, and it is each independently C1-C20Linear or branched alkyl group, C3-C20Substitution
Or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20
One of substituted or unsubstituted alkaryl；
Alternatively, R '1、R’2、R’3、R’4、R’5And R '6In two or more be mutually bonded, with formed saturation or not
The ring of saturation.
In preferred situation, the internal electron donor compound b is 1,3- diether compounds shown in formula II,
Formula II,
In formula II, R '9And R '10Can be identical or different, it is each independently hydrogen, halogen, C1-C18Linear chain or branched chain alkane
Base, C3-C18Substituted or unsubstituted naphthenic base, C6-C18Substituted or unsubstituted aryl and C7-C18It is substituted or unsubstituted
One of aralkyl, alternatively, R '9And R '10It is mutually bonded, to form ring；R'11And R '12Can be identical or different, respectively
It independently is C1-C10Linear or branched alkyl group.
According to the present invention, the example of the diether compounds can include but is not limited to: 2- (2- ethylhexyl) -1,3- bis-
Methoxy propane, 2- isopropyl -1,3- dimethoxy propane, 2- butyl -1,3- dimethoxy propane, 2- sec-butyl -1,3- two
Methoxy propane, 2- cyclohexyl -1,3- dimethoxy propane, 2- phenyl -1,3- dimethoxy propane, 2- (2- phenylethyl) -
1,3- dimethoxy propane, 2- (2- cyclohexyl-ethyl) -1,3- dimethoxy propane, 2- (p- chlorphenyl) -1,3- dimethoxy
Propane, 2- (diphenyl methyl) -1,3- dimethoxy propane, 2,2- dicyclohexyl -1,3- dimethoxy propane, bis- ring penta of 2,2-
Base -1,3- dimethoxy propane, 2,2- diethyl -1,3- dimethoxy propane, 2,2- dipropyl -1,3- dimethoxy propane,
2,2- diisopropyl -1,3- dimethoxy propane, 2,2- dibutyl -1,3- dimethoxy propane, 2- methyl-2-propyl -1,3-
Dimethoxy propane, 2- methyl -2- benzyl -1,3- dimethoxy propane, 2- methyl -2- ethyl -1,3- dimethoxy propane, 2-
Methyl -2- isopropyl -1,3- dimethoxy propane, 2- methyl -2- phenyl -1,3- dimethoxy propane, 2- methyl -2- hexamethylene
Bis- (2- the cyclohexyl-ethyl) -1,3- dimethoxy propanes of base -1,3- dimethoxy propane, 2,2-, isobutyl group -1 2- methyl -2-,
3- dimethoxy propane, 2- methyl -2- (2- ethylhexyl) -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy
Base propane, 2,2- diphenyl -1,3- dimethoxy propane, 2,2- dibenzyl -1,3- dimethoxy propane, the bis- (cyclohexyl of 2,2-
Methyl) -1,3- dimethoxy propane, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propane, 2- (1- methyl butyl) -2- be different
Propyl -1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2- phenyl -2- isopropyl -1,3-
Dimethoxy propane, 2- phenyl -2- sec-butyl -1,3- dimethoxy propane, 2- benzyl -2- isopropyl -1,3- dimethoxy third
Alkane, 2- cyclopenta -2- isopropyl -1,3- dimethoxy propane, 2- cyclopenta -2- sec-butyl 1,3- dimethoxy propane, 2- ring
Hexyl -2- isopropyl -1,3- dimethoxy propane, 2- cyclohexyl -2- sec-butyl -1,3- dimethoxy propane, 2- isopropyl -2-
Sec-butyl -1,3- dimethoxy propane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propane, 9,9- dimethoxy first
Base fluorenes.
Under most preferred case, the diether compounds be 2- isopropyl -2- isopentyl -1,3- dimethoxy propane and/or
9,9- dimethoxy-methyl fluorenes.
In the present invention, 1, the 3- diether compound be referred to CN1020448C, CN100348624C and
The synthesis of method disclosed in CN1141285A.Repeats no more herein.
According to the present invention, in the preparation process for the catalytic component of olefinic polymerization, titanium compound can be ability
The conventional selection in domain, for example, it is Ti (OR ') that the titanium compound, which can be general formula,3-aZaAnd/or Ti (OR ')4-bZbSubstance,
In, R ' is C1-C20Alkyl, Z F, Cl, Br or I, a be 1-3 integer, b be 1-4 integer.Under preferable case, the titanium
Compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy trichlorine
Change one of titanium, triethoxy titanium chloride, diethoxy titanium chloride, ethyoxyl titanium trichloride and titanium trichloride or a variety of,
Preferably titanium tetrachloride.
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).
According to a preferred embodiment of the present invention, this method comprises: magnesium halide alcohol adduct carrier and titanizing are closed
Object reaction, and one or more times before and after, during the magnesium halide alcohol adduct carrier is reacted with titanium compound
The internal electron donor is added in section and carries out the haptoreaction.
Specifically, the magnesium halide alcohol adduct carrier can be according to side same as the prior art with reacting for titanium compound
Formula carries out, for example, titanium compound can be cooled to 0 DEG C or less (preferably -30 DEG C to 10 DEG C, preferably -30 DEG C to -10
DEG C), magnesium halide alcohol adduct carrier is then added, and be stirred at such a temperature 0.2-3 hours, preferably 0.5-2 hours；Later
It is warming up to reaction temperature (i.e. about 60-130 DEG C), and is maintained 0.5-10 hours under the reaction temperature.Described poly- for alkene
In the preparation method of the catalytic component of conjunction, the internal electron donor compound is closed in the magnesium halide alcohol adduct carrier and titanizing
It is added in one or more periods in front of and after, during the reaction of object.The magnesium halide alcohol adduct carrier and titanizing
Period before closing the reaction of object refers to after the magnesium halide alcohol adduct carrier is added in reactor and is being warming up to instead
Answer the period before temperature.
According to the present invention, the halogen in the preparation process of the catalytic component for olefinic polymerization, in terms of magnesium elements
The molar ratio for changing the dosage of magnesium alcoholate carrier, the titanium compound in terms of titanium elements and internal electron donor can be 1:(2-200):
(0.05-0.6), preferably 1:(5-180): (0.1-0.4), preferably 1:(10-150): (0.12-0.3).
As previously mentioned, the present invention provides one kind be prepared according to the method described in the present invention for olefinic polymerization
Catalytic component.
As previously mentioned, the catalyst contains the present invention provides a kind of catalyst for olefinic polymerization:
(i) catalytic component, the catalytic component are the catalytic component of the present invention for olefinic polymerization；
(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 field, for example, the general 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 group can be with
For halogen；The C1-8The specific example of alkyl can include but is not limited to: methyl, ethyl, propyl, normal-butyl, isobutyl group,
Amyl, hexyl, n-heptyl, n-octyl, the halogen can be fluorine, chlorine, bromine, iodine.Specifically, the alkyl aluminum can for example select
From triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, tri-n-octylaluminium, a hydrogen diethyl aluminum,
One hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, dichloro
One aluminium ethide, one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro, one n-hexyl aluminium of dichloro, Al (n-C6H13)3With Al (n-C8H17)3
One of or a variety of, preferably triethyl aluminum and/or triisobutyl aluminium.
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 one of carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound or a variety of；
Preferably, the external electron donor is containing at least one Si-OR key and general formula is (R17)a(R18)bSi(OR19)cSilication close
Object, wherein R17、R18And R19For C1-C18Alkyl, optionally contain hetero atom, a and b respectively stand alone as the integer of 0-2, and c is
The integer of 1-3, and a, b and c and be 4.Preferably, R17、R18For C3-C10Alkyl, naphthenic base, optionally contain hetero atom；
R19For C1-C10Alkyl, optionally contain hetero atom.Specifically, the external electron donor can for example be selected from cyclohexyl methyl
Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane,
Dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclohexyl trimethoxy
Silane, tert-butyl trimethoxy silane, tertiary hexyl trimethoxysilane, 2- ethyl piperidine base -2- t-butyldimethoxysilane,
(the fluoro- 2- propyl of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilane and (1,1,1-, three fluoro- 2- propyl)-methyl dimethoxy oxygen
One of base silane is a variety of.
Typically also, in the catalyst for olefinic polymerization, in terms of titanium elements described in be used for olefinic polymerization
Catalytic component and the molar ratio of the alkyl aluminum dosage in terms of aluminium element can be 1:(1-1000), preferably 1:(10-
300), more preferably 1:(20-200)；The molar ratio of the external electron donor and the alkyl aluminum dosage in terms of aluminium element can
Think 1:(2-500), preferably 1:(5-200).
According to the present invention, in the preparation process for the catalyst of olefinic polymerization, alkyl aluminum and optional outer electron
Body compound can respectively with for olefinic polymerization catalytic component mixing after react, or can also by alkyl aluminum and optionally
External electron donor mix in advance after mix and react with the catalytic component for olefinic polymerization again.
According to the present invention, described for olefinic polymerization when the catalyst for being used for olefinic polymerization is used for olefinic polymerization
Catalytic component, alkyl aluminum and optional external electron donor can be separately added into polymer reactor, be added after can also mixing poly-
It closes in reactor, prepolymerization method commonly understood in the industry, which can also be used, to be added in polymer reactor after alkene pre-polymerization.
As previously mentioned, the present invention provides the catalytic components of the present invention for olefinic polymerization or of the present invention
The application for the catalyst of olefinic polymerization in olefin polymerization.
It is of the invention the improvement is that use it is a kind of it is new for the catalyst of olefinic polymerization, for olefinic polymerization
Catalytic component, and the polymerisation process of the specific type of alkene, alkene and condition can be same as the prior art.
According to the present invention, above-mentioned catalyst is CH especially suitable for general formula2(wherein, R is hydrogen, C to=CHR1-C6Alkyl or
C6-C12Aryl) alkene homopolymerization and copolyreaction, specifically for example, ethylene, propylene, 1- n-butene, 1- n-pentene, 1- be just
The positive octene of hexene, 1- and 4-methyl-1-pentene.It is described by formula CH under preferable case2The alkene that=CHR is indicated is ethylene, third
One of alkene, 1- n-butene, 1- n-hexylene and 4-methyl-1-pentene are a variety of.It is highly preferred that described by formula CH2=CHR table
The alkene shown is propylene.
According to the present invention, the polymerization reaction of the alkene can be carried out according to existing method, specifically, in inert gas
Protection under, in liquid monomer or atent solvent containing polymerized monomer, or in the gas phase, or pass through the combination in liquid phase
Polymerization technique carries out polymerization reaction.The temperature of the polymerization reaction can be generally 0-150 DEG C, preferably 60-100 DEG C.It is described
The pressure of polymerization reaction can be normal pressure or higher；It such as can be 0.01-10MPa, preferably 0.5-5MPa.The time of polymerization
It is 0.1-5 hours, preferably 0.5-3 hours.Pressure of the invention refers both to gauge pressure.In the course of the polymerization process, hydrogen can be used as polymerizeing
Object molecular weight regulator is added to the molecular weight and melt index that polymer is adjusted in reaction system.In addition, in the poly- of alkene
It closes in reaction process, the inert gas, the type of solvent and dosage are known to the skilled person, and will no longer be gone to live in the household of one's in-laws on getting married herein
It states.
Following example is used to illustrate the present invention, is not for limiting the scope of the invention.
Test method:
1, it melt index: at 230 DEG C of temperature and the pressure of 2.16kg, is measured according to ASTM D1238-99.
2, polymer isotacticity: using the measurement of heptane extraction process (heptane boiling extracting 6 hours): two grams of dry polymer
Sample is placed in extractor after being extracted 6 hours with boiling heptane, and residue is dry to the resulting polymer weight (g) of constant weight
Ratio with 2 is isotacticity.
3, particle diameter distribution is tested: average grain diameter and size distribution the Masters Sizer of magnesium halide alcohol adduct particle
2000 (being manufactured by Malvern Instruments Ltd) particle size analyzer determinations.
4, the molecular weight distribution of polymer is measured using Shimadzu LC-10AT type gel permeation chromatograph (GPC), wherein THF
For mobile phase, 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 ethyl alcohol is added, is warming up to 125 DEG C under stiring,
It is stirred at 125 DEG C 3 hours, at 0.2 mpa, mixture is passed through to metal mesh (every thickness degree of 2 layer of 200 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after 0.1mm), filter off liquid, wash solid three times with hexane, vacuum is dry
It is dry, 50 grams of spherical chlorination magnesium alcoholate solid particle S1 is obtained, alcohol/magnesium molar ratio is 2.6, characterization result such as table 1.
Prepare embodiment 2
In the autoclave of 1L, silicone oil 500ml, 30 grams of magnesium chlorides, 50ml ethyl alcohol is added, is warming up to 125 DEG C under stiring,
It is stirred 3 hours at 125 DEG C, at 0.5MPa, mixture is passed through to metal mesh (every thickness degree of 4 layer of 200 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after 0.1mm), filter off liquid, wash solid three times with hexane, vacuum is dry
It is dry, obtain 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 ethyl alcohol is added, is warming up to 125 DEG C under stiring,
It is stirred 3 hours at 125 DEG C, at 0.3MPa, mixture is passed through to metal mesh (every thickness degree of 3 layer of 200 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after 0.1mm), filter off liquid, wash solid three times with hexane, vacuum is dry
It is dry, obtain 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 ethyl alcohol and 3ml O-methoxy benzoyl is added
Chlorine is warming up to 125 DEG C under stiring, stirs 3 hours at 125 DEG C, at 0.2 mpa, mixture is passed through 4 by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after the metal mesh (every thickness degree 0.1mm) of 200 mesh of layer, filter off liquid, use
Hexane washs solid three times, and vacuum drying obtains 56 grams of spherical chlorination magnesium alcoholate solid particle 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 ethyl alcohol is added, under stiring
125 DEG C are warming up to, is stirred 3 hours at 125 DEG C, at 0.5MPa, mixture is passed through to the gold of 6 layer of 200 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after category net (every thickness degree 0.1mm), filter off liquid, washed with hexane solid
Three times, vacuum drying obtains 51 grams of spherical chlorination magnesium alcoholate solid particle S5, characterization result such as table 1 to body.
Prepare embodiment 6
In the autoclave of 1L, white oil 500ml, 30 grams of magnesium chlorides, 50ml ethyl alcohol is added, is warming up to 125 DEG C under stiring,
It is stirred at 125 DEG C 3 hours, at 0.2 mpa, mixture is passed through to metal mesh (every thickness degree of 4 layer of 200 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after 0.1mm), filter off liquid, wash solid three times with hexane, vacuum is dry
It is dry, obtain 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 ethyl alcohol is added, is warming up to 125 DEG C under stiring,
It is stirred 3 hours at 125 DEG C, at 0.6MPa, mixture is passed through to metal mesh (every thickness degree of 8 layer of 150 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after 0.15mm), filter off liquid, wash solid three times with hexane, vacuum is dry
It is dry, obtain 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 ethyl alcohol is added, is warming up to 120 DEG C under stiring,
It is stirred 3 hours at 120 DEG C, at 0.6MPa, mixture is passed through to metal mesh (every thickness degree of 4 layer of 300 mesh by blanking pipeline
It is directly placed into and is pre-cooled into -30 DEG C of 3L hexane after 0.09mm), filter off liquid, wash solid three times with hexane, vacuum is dry
It is dry, obtain 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 ethyl alcohol is added, rises under stiring
Temperature stirs 3 hours at 125 DEG C to 125 DEG C, material is put into the hypergravity machine of unlatching, is entered by hypergravity machine preparatory
It is cooled in -30 DEG C of 3L hexane, filters off liquid, wash solid three times with hexane, be dried in vacuo, obtain 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 ethyl alcohol is added, is warming up to 125 DEG C under stiring,
It is stirred 3 hours at 125 DEG C, material is put into the hypergravity machine of unlatching, entered by hypergravity machine and pre-cooled to -30 DEG C
In hexane, liquid is filtered off, washs solid three times with hexane, is dried in vacuo, obtain 56 grams of spherical chlorination magnesium alcoholate solid
Grain 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
Compared to higee technology it can be seen from the result of table 1, the present invention can prepare the adduction of different-grain diameter
Object carrier, and narrower particle size distribution, big partial size (D50 > 60 μm) the adduct carrier especially prepared still have relatively narrow granularity
Distribution.
Embodiment 1
The embodiment is used to illustrate catalytic component for olefinic polymerization and preparation method thereof and for olefinic polymerization
Catalyst and its application.
(1) preparation of the catalytic component of olefinic polymerization is used for using carrier S 1 prepared by preparation embodiment 1:
In glass reaction bottle of the 300ml being sufficiently displaced from by high pure nitrogen with stirring, the titanium tetrachloride of 90ml is added
With the hexane of 10ml, -20 DEG C are cooled to, spherical chlorination magnesium alcoholate carrier S 18g is added, under stiring, is slowly risen stage by stage
2- isopropyl -2- isopentyl -1,3- dimethoxy propane 0.008mol is added in temperature-rise period, is warming up to 110 DEG C, arrives for temperature
It after temperature after constant temperature 1h, filters and removes liquid, add titanium tetrachloride to carry out titanium processing, then washed five times, after vacuum drying with hexane
Obtain spheric catalyst C1.
(2) propylene polymerization:
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
Triethyl aluminum, 0.01mmol Cyclohexyl Methyl Dimethoxysilane (CHMMS), the anhydrous hexane of 10ml and the spherical catalyst of 4mg
Agent component.Autoclave is closed, the liquid propene of hydrogen 1.5NL and 2.3L is added.70 DEG C are warming up to, is polymerize 1 hour.It the results are shown in Table 2.
Embodiment 2
The embodiment is used to illustrate catalytic component for olefinic polymerization and preparation method thereof and for olefinic polymerization
Catalyst and its application.
The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not
With the additional amount of hydrogen is 6.5L during propylene polymerization, the results are shown in Table 2.
Embodiment 3
The embodiment is used to illustrate catalytic component for olefinic polymerization and preparation method thereof and for olefinic polymerization
Catalyst and its application.
(1) it is used for the preparation of the catalytic component of olefinic polymerization using carrier S 2 prepared by preparation embodiment 2, and is added without
2- isopropyl -2- isopentyl -1,3- dimethoxy propane, is added 0.009mol 9, and 9- dimethoxy-methyl fluorenes obtains catalyst
Component C2, remaining is the same as embodiment 1.
Propylene polymerization is the same as embodiment 1.
Embodiment 4
The embodiment is used to illustrate catalytic component for olefinic polymerization and preparation method thereof and for olefinic polymerization
Catalyst and its application.
Catalytic component and progress propylene polymerization according to the method preparation of embodiment 3 for olefinic polymerization, institute is not
With the additional amount of hydrogen is 6.5L during propylene polymerization, the results are shown in Table 2.
Comparative example 1
The comparative example is used to illustrate the catalytic component of reference for olefinic polymerization and preparation method thereof and gathers for alkene
The catalyst of conjunction and its application.
Chlorination magnesium alcoholate is by method preparation disclosed in preparation comparative example 1.
Catalyst component for olefin polymerization DC1 is prepared according to the method for embodiment 1.
Polypropylene is prepared according to the method for embodiment 1, the results are shown in Table 2.
Comparative example 2
The comparative example is used to illustrate the catalytic component of reference for olefinic polymerization and preparation method thereof and gathers for alkene
The catalyst of conjunction and its application.
Catalytic component and progress propylene polymerization according to the method preparation of comparative example 1 for olefinic polymerization, institute is not
With the additional amount of hydrogen is 6.5L during propylene polymerization, the results are shown in Table 2.
Comparative example 3
The comparative example is used to illustrate the catalytic component of reference for olefinic polymerization and preparation method thereof and gathers for alkene
The catalyst of conjunction and its application.
Chlorination magnesium alcoholate is by method preparation disclosed in preparation comparative example 1.
The preparation of spherical catalyst components DC2 is the same as embodiment 3.
Propylene polymerization is the same as embodiment 1.
Comparative example 4
The comparative example is used to illustrate the catalytic component of reference for olefinic polymerization and preparation method thereof and gathers for alkene
The catalyst of conjunction and its application.
Catalytic component and progress propylene polymerization according to the method preparation of comparative example 3 for olefinic polymerization, institute is not
With the additional amount of hydrogen is 6.5L during propylene polymerization, the results are shown in Table 2.
Table 2
It can be seen that the catalyst prepared using carrier of the invention compared with comparative example according to embodiment, have more
High hydrogen response and vertical structure directionality.
Embodiment 5-8
Catalytic component and progress propylene polymerization according to the method preparation of embodiment 1-2 for olefinic polymerization, institute
Unlike, catalytic component C3-C6 is prepared using carrier S 3-S6, the results are shown in Table 3.
Comparative example 5
Catalytic component and progress propylene polymerization according to the method preparation of embodiment 1-2 for olefinic polymerization, institute
Unlike, catalytic component DC3 is prepared using carrier DS2, the results are shown in Table 3.
Table 3
It can be seen that by the result of table 3 after being used for catalyst using carrier prepared by preparation method of the invention, catalyst
Vertical structure directionality and hydrogen response all increase.
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, it 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 (23)
1. a kind of preparation method of the catalytic component for olefinic polymerization, this method comprises: by magnesium halide alcohol adduct carrier, titanium
Compound and internal electron donor carry out haptoreaction, which is characterized in that the internal electron donor contains diether compounds；It is described
The preparation step of magnesium halide alcohol adduct carrier includes: under elevated pressure, magnesium halide alcohol adduct melt to be passed through structure list with hole
Member is contacted with liquid cooling medium, and the condition of the pressurization includes: that pressure is 0.05-1MPa, and the aperture in the hole is 10-1800
μm,
The general formula of the carrier is shown below:
MgXY–mROH–nE–pH2O；
Wherein, m 1-5；
Wherein, n 0-0.3；
Wherein, p 0-0.08；
Wherein, X is halogen；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxy, C6-C14Aryl or C6-C14Aryloxy group；
Wherein, R C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
2. preparation method according to claim 1, wherein the condition of the pressurization includes: that pressure is 0.1-0.5MPa.
3. preparation method according to claim 1 or 2, wherein the aperture in the hole is 20-800 μm.
4. preparation method according to claim 3, wherein the aperture in the hole is 30-150 μm.
5. preparation method according to claim 3, wherein the structural unit with hole is stratum reticulare.
6. preparation method according to claim 5, wherein the stratum reticulare includes 1-20 layers；Every thickness degree is respectively 0.01-
0.35mm。
7. preparation method according to claim 6, wherein the stratum reticulare includes 2-8 layers；Every thickness degree is respectively 0.05-
0.25mm。
8. preparation method according to claim 5, wherein the stratum reticulare is metal net layer.
9. preparation method according to claim 1, wherein m 2.4-3.5, n 0.005-0.2, R C1-C4Alkyl.
10. preparation method according to claim 1, wherein the preparation step of the magnesium halide alcohol adduct melt includes:
In confined conditions, magnesium halide MgXY, alcohol roh, optionally electron donor compound E and inert liquid medium are mixed,
Mixture is heated to 100-160 DEG C under stiring；
Wherein, X is halogen；
Wherein, Y is halogen, C1-C14Alkyl, C1-C14Alkoxy, C6-C14Aryl or C6-C14Aryloxy group；
Wherein, R C1-C12Alkyl, C3-C10Naphthenic base or C6-C10Aryl；
Wherein, E is the electron donor compound containing oxygen atom in addition to alcohol.
11. preparation method according to claim 10, wherein R C1-C4Alkyl.
12. preparation method according to claim 10, wherein the inert liquid medium is silicone oil and/or inert fluid
Hydrocarbon solvent.
13. preparation method according to claim 10, wherein the inert liquid medium is C4-C10Alkane, kerosene,
One of vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil and methyl phenyl silicone oil are a variety of.
14. preparation method according to claim 10, wherein the inert liquid medium is silicone oil.
15. preparation method according to claim 10, wherein by 1mol on the basis of the MgXY that magnesium is counted, the dosage of alcohol roh
For 1-5.5mol, the dosage of E is 0.001-0.32mol.
16. preparation method according to claim 1 or 2, wherein the liquid cooling medium is unreactive hydrocarbons solvent；It is described
The temperature of liquid cooling medium is (- 10 DEG C)-(- 40 DEG C).
17. preparation method according to claim 1 or 2, wherein the liquid cooling medium be pentane, hexane, heptane,
One of gasoline or petrol ether is a variety of.
18. preparation method according to claim 1 or 2, wherein described on the basis of the dosage of the internal electron donor
Total dosage of diether compounds is 80-100 weight %.
19. preparation method according to claim 1 or 2, wherein the diether compounds are I compound represented of formula,
In formula I, R '1、R’2、R’3、R’4、R’5And R '6It is identical or different, it is each independently hydrogen, halogen, C1-C20Straight chain or
Branched alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substitution or
Unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl；
R’7And R '8It is identical or different, it is each independently C1-C20Linear or branched alkyl group, C3-C20It is substituted or unsubstituted
Naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20Substitution or not
One of substituted alkaryl；
Alternatively, R '1、R’2、R’3、R’4、R’5And R '6In two or more be mutually bonded, to form ring.
20. preparation method according to claim 1 or 2, wherein this method comprises: by magnesium halide alcohol adduct carrier and titanium
Compound reaction, and the one or more before and after, during the magnesium halide alcohol adduct carrier is reacted with titanium compound
The internal electron donor is added in period and carries out the haptoreaction.
21. the catalytic component for olefinic polymerization that method described in any one of claim 1-20 is prepared.
22. a kind of catalyst for olefinic polymerization, the catalyst contain:
(i) catalytic component, the catalytic component are the catalytic component that olefinic polymerization is used for described in claim 21；
(ii) at least one alkyl aluminum compound；And
(iii) optionally, at least one external electron donor.
23. for being used for olefinic polymerization described in the catalytic component of olefinic polymerization or claim 22 described in claim 21
Application of the catalyst in olefin polymerization.
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| CN102796127A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN102796210A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method |
| CN102796212A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method |
| CN104109081A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for improving quality of glycol product prepared by using synthetic gas |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796127A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN102796210A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method |
| CN102796212A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method |
| CN104109081A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for improving quality of glycol product prepared by using synthetic gas |
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