CN106608926B

CN106608926B - Catalytic component for olefinic polymerization and its preparation method and application and catalyst and its application for olefinic polymerization

Info

Publication number: CN106608926B
Application number: CN201510706715.3A
Authority: CN
Inventors: 赵瑾; 夏先知; 高富堂; 刘月祥; 谭扬; 任春红; 凌永泰; 李威莅; 彭人琪
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2015-10-27
Filing date: 2015-10-27
Publication date: 2019-09-27
Anticipated expiration: 2035-10-27
Also published as: CN106608926A

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 internal electron donor compound a and internal electron donor compound b, the internal electron donor compound a is glycol ester compounds, and the internal electron donor compound b is 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

Catalytic component for olefinic polymerization and its preparation method and application and be used for alkene The catalyst of polymerization and its application

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 State that internal electron donor contains internal electron donor compound a and internal electron donor compound b, the internal electron donor compound a are Glycol ester compounds, the internal electron donor compound b are diether compounds；The preparation step of the magnesium halide alcohol adduct carrier It include: under elevated pressure, magnesium halide alcohol adduct melt to be passed through into structural unit with hole and is contacted 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 interior Electron donor compound a and internal electron donor compound b, the internal electron donor compound a are glycol ester compounds, described interior Electron donor compound b is diether compounds；The preparation step of the magnesium halide alcohol adduct carrier includes: under elevated pressure, by halogen Change magnesium alcoholate melt to contact across structural unit with hole 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；

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 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, when the internal electron donor contains the internal electron donor compound a and the internal electron donor Just certain synergistic effect can be generated when compound b, on the basis of the dosage of the internal electron donor, the internal electron donor Total dosage of compound a and the internal electron donor compound b can be 80-100 weight %.Moreover, the present inventor It was found that when the molar ratio of the internal electron donor compound a and the internal electron donor compound b dosage is (0.55-50): 1, Preferably (0.65-10): when 1, can cooperate with and deploy more preferably, to obtain the vertical higher catalyst of structure capacity of orientation, thus The olefin polymer with high isotactic index and low ash content can be obtained.

According to the present invention, the internal electron donor compound a is glycol ester compounds shown in formula I,

In formula I, R₁And R₂It is identical or different, it is each independently C₁-C₁₀Linear or branched alkyl group, C₃-C₂₀Substitution or Unsubstituted naphthenic base, C₆-C₂₀Substituted or unsubstituted aryl, C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀'s One of substituted or unsubstituted alkaryl, aromatic ring in the aryl, aralkyl or alkaryl optionally by selected from halogen, C₁-C₆Linear or branched alkyl group and C₁-C₆One of alkoxy or a variety of substitutions；In formula I, the content of bracket " [] " Indicate that successively key connects n carbon atom, and each carbon atom also connects with 2 substituent group keys, i.e., n carbon atom is shared in bracket And R¹、R²、R³…R²ⁿEqual 2n substituent group.

R₃、R₄、R₅、R₆And R¹-R²ⁿIt is identical or different, it is each independently hydrogen, halogen, C₁-C₂₀Linear chain or branched chain alkane Base, C₃-C₂₀Substituted or unsubstituted naphthenic base, C₆-C₂₀Substituted or unsubstituted aryl, C₇-C₂₀It is substituted or unsubstituted Alkaryl, C₇-C₂₀Substituted or unsubstituted aralkyl, C₂-C₁₀Linear chain or branched chain alkylene and C₁₀-C₂₀Condensed ring virtue One of base, R₃、R₄、R₅、R₆And R¹-R²ⁿOptionally contain hetero atom, the hetero atom is nitrogen, oxygen, sulphur, silicon, halogen and phosphorus One of or it is a variety of；

Alternatively, R₃、R₄、R₅、R₆And R¹-R²ⁿIn two or more be mutually bonded, with formed saturation or it is unsaturated Ring；

N is the integer of 0-10, as n=0, in glycol ester compounds shown in formula I, and substituent group R₃、R₄Carbon atom it is straight Connecing with substituent group is R₅、R₆Carbon atom bonding connect；

In the present invention, C₁-C₂₀The example of linear or branched alkyl group can include but is not limited to: methyl, ethyl, positive third Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, 1- ethyl propyl, 2- methyl butyl, 3- methyl fourth Base, 2,2- dimethyl propyl, n-hexyl, 2- methyl amyl, 3- methyl amyl, 4- methyl amyl, n-heptyl, 2- methylhexyl, 3- methylhexyl, 4- methylhexyl, 5- methylhexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, tetrahydro geranyl, positive ten Dialkyl group, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-octadecane base, NSC 77136 base and just Eicosyl.

In the present invention, C₃-C₂₀The example of substituted or unsubstituted naphthenic base can include but is not limited to: cyclopropyl, ring Butyl, cyclopenta, cyclohexyl, 4- methylcyclohexyl, 4- ethylcyclohexyl, 4- n-propyl cyclohexyl, 4- normal-butyl cyclohexyl, ring Undecyl and cyclo-dodecyl.

In the present invention, C₆-C₂₀The example of substituted or unsubstituted aryl can include but is not limited to: phenyl, methylbenzene Base, ethylphenyl, 4- tert-butyl-phenyl etc..

In the present invention, C₇-C₂₀Substituted or unsubstituted aralkyl refer to that carbon atom number is that 7-20 taking with aryl The alkyl group of Dai Ji.C₇-C₂₀The example of substituted or unsubstituted aralkyl can include but is not limited to: 3- phenyl propyl, Benzyl etc..

In the present invention, C₇-C₂₀Substituted or unsubstituted alkaryl refer to that carbon atom number is that 7-20 taking with alkyl The aryl group of Dai Ji.C₇-C₂₀The example of substituted or unsubstituted alkaryl can include but is not limited to: aminomethyl phenyl, second Base phenyl etc..

In the present invention, C₁-C₆The example of alkoxy can include but is not limited to: methoxyl group, ethyoxyl, positive propoxy, Isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy and own oxygen Base.

In the present invention, C₂-C₁₀The example of linear chain or branched chain alkylene can include but is not limited to: vinyl, propylene Base, cyclobutenyl, pentenyl, octenyl etc..

In the present invention, C₁₀-C₂₀The example of fused ring aryl can include but is not limited to: naphthalene, anthryl, phenanthryl, pyrenyl Deng.

According to the present invention, the example of the internal electron donor compound a can include but is not limited to: 1,3-PD hexichol Formic acid esters, 2- methyl-1,3-propanediol dibenzoate, 2- ethyl -1,3- propylene glycol dibenzoate, 2- propyl -1,3- third Bisbenzoate, 2- butyl -1,3- propylene glycol dibenzoate, 2,2- dimethyl -1,3- propylene glycol dibenzoate, 2- Ethyl -2- butyl -1,3- propylene glycol dibenzoate, 2,2- diethyl -1,3- propylene glycol dibenzoate, 2- methyl -2- third Base -1,3- propylene glycol dibenzoate, 2- isopropyl -2- isopentyl -1,3- propylene glycol dibenzoate, 2,4-PD hexichol Formic acid esters, 3- methyl -2,4-PD dibenzoate, 3- ethyl -2,4-PD dibenzoate, 3- propyl -2,4- penta Bisbenzoate, 3- butyl -2,4-PD dibenzoate, 3,3- dimethyl -2,4-PD dibenzoate, 2- Methyl-1,3- glycol dibenzoate, 2,2- dimethyl -1,3- glycol dibenzoate, 2- ethyl -1,3- pentanediol two Benzoic ether, 2- butyl -1,3- glycol dibenzoate, 2- methyl-1,3- glycol dibenzoate, 2- ethyl -1,3- Glycol dibenzoate, 2- propyl -1,3- glycol dibenzoate, 2- butyl -1,3- glycol dibenzoate, 2,2- Dimethyl -1,3- glycol dibenzoate, 2- methyl-1,3- glycol dibenzoate, 2,2- dimethyl -1,3- pentanediol Dibenzoate, 2- ethyl -1,3- glycol dibenzoate, 2- butyl -1,3- glycol dibenzoate, 2,2,4- front three Base -1,3- glycol dibenzoate, 3- methyl -3- butyl -2,4-PD dibenzoate, 2,2- dimethyl -1,5- penta Bisbenzoate, 1,6-HD dibenzoate, 6- heptene -2,4- heptandiol dibenzoate, 2- methyl -6- heptan Alkene -2,4- heptandiol dibenzoate, 3- methyl -6- heptene -2,4- heptandiol dibenzoate, 4- methyl -6- heptene -2,4- Heptandiol dibenzoate, 5- methyl -6- heptene -2,4- heptandiol dibenzoate, 6- methyl -6- heptene -2,4- heptandiol Dibenzoate, 3- ethyl -6- heptene -2,4- heptandiol dibenzoate, 4- ethyl -6- heptene -2,4- heptandiol hexichol first Acid esters, 5- ethyl -6- heptene -2,4- heptandiol dibenzoate, 6- ethyl -6- heptene -2,4- heptandiol dibenzoate, 3- Propyl -6- heptene -2,4- heptandiol dibenzoate, 4- propyl -6- heptene -2,4- heptandiol dibenzoate, 5- propyl -6- Heptene -2,4- heptandiol dibenzoate, 6- propyl -6- heptene -2,4- heptandiol dibenzoate, heptene -2 3- butyl -6-, 4- heptandiol dibenzoate, 4- butyl -6- heptene -2,4- heptandiol dibenzoate, 5- butyl -6- heptene -2,4- heptan two Alcohol dibenzoate, 6- butyl -6- heptene -2,4- heptandiol dibenzoate, 3,5- dimethyl -6- heptene -2,4- heptandiol Dibenzoate, 3,5- diethyl -6- heptene -2,4- heptandiol dibenzoate, 3,5- dipropyl -6- heptene -2,4- heptan two Alcohol dibenzoate, 3,5- dibutyl -6- heptene -2,4- heptandiol dibenzoate, 3,3- dimethyl -6- heptene -2,4- heptan Bisbenzoate, 3,3- diethyl -6- heptene -2,4- heptandiol dibenzoate, 3,3- dipropyl -6- heptene -2,4- Heptandiol dibenzoate, 3,3- dibutyl -6- heptene -2,4- heptandiol dibenzoate, 3,5- heptandiol dibenzoate, 2- methyl -3,5- heptandiol dibenzoate, 3- methyl -3,5- heptandiol dibenzoate, 4- methyl -3,5- heptandiol hexichol Formic acid esters, 5- methyl -3,5- heptandiol dibenzoate, 6- methyl -3,5- heptandiol dibenzoate, 3- ethyl -3,5- heptan Bisbenzoate, 4- ethyl -3,5- heptandiol dibenzoate, 5- ethyl -3,5- heptandiol dibenzoate, 3- third Base -3,5- heptandiol dibenzoate, 4- propyl -3,5- heptandiol dibenzoate, 3- butyl -3,5- heptandiol dibenzoic acid Ester, 2,3- dimethyl -3,5- heptandiol dibenzoate, 2,4- dimethyl -3,5- heptandiol dibenzoate, 2,5- diformazan Base -3,5- heptandiol dibenzoate, 2,6- dimethyl -3,5- heptandiol dibenzoate, 3,3- dimethyl -3,5- heptandiol Dibenzoate, 4,4- dimethyl -3,5- heptandiol dibenzoate, 6,6- dimethyl -3,5- heptandiol dibenzoate, 2, 6- dimethyl -3,5- heptandiol dibenzoate, 3,4- dimethyl -3,5- heptandiol dibenzoate, 3,5- dimethyl -3,5- Heptandiol dibenzoate, 3,6- dimethyl -3,5- heptandiol dibenzoate, 4,5- dimethyl -3,5- heptandiol hexichol first Acid esters, 4,6- dimethyl -3,5- heptandiol dibenzoate, 4,4- dimethyl -3,5- heptandiol dibenzoate, 6,6- diformazan Base -3,5- heptandiol dibenzoate, 2- methyl -3- ethyl -3,5- heptandiol dibenzoate, 2- methyl -4- ethyl -3,5- Heptandiol dibenzoate, 2- methyl -5- ethyl -3,5- heptandiol dibenzoate, 3- methyl -3- ethyl -3,5- heptandiol Dibenzoate, 3- methyl -4- ethyl -3,5- heptandiol dibenzoate, 3- methyl -5- ethyl -3,5- heptandiol hexichol first Acid esters, 4- methyl -3- ethyl -3,5- heptandiol dibenzoate, 4- methyl -4- ethyl -3,5- heptandiol dibenzoate, 4- Methyl -5- ethyl -3,5- heptandiol dibenzoate, 2- methyl -3- propyl -3,5- heptandiol dibenzoate, 2- methyl -4- Propyl -3,5- heptandiol dibenzoate, 2- methyl -5- propyl -3,5- heptandiol dibenzoate, propyl -3 3- methyl -3-, 5- heptandiol dibenzoate, 3- methyl -4- propyl -3,5- heptandiol dibenzoate, 3- methyl -5- propyl -3,5- heptan two Alcohol dibenzoate, 4- methyl -3- propyl -3,5- heptandiol dibenzoate, 4- methyl -4- propyl -3,5- heptandiol hexichol Formic acid esters, 4- methyl -5- propyl -3,5- heptandiol dibenzoate etc..

Under preferable case, the internal electron donor compound a is glycol ester compounds shown in formula IV,

In formula IV, R₇、R₈、R₉、R₁₀、R₁₁And R₁₂It is identical or different, it is each independently hydrogen or C₁-C₂₀Linear chain or branched chain Alkyl.

Under most preferred case, the internal electron donor compound a is 2,4- glycol dibenzoate and/or 3,5- heptan two Alcohol dibenzoate.

According to the present invention, the internal electron donor compound b is diether compound shown in formula II,

In formula II, 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 V,

In formula V, 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 internal electron donor compound b can include but is not limited to: 2- (2- ethyl hexyl Base) -1,3- dimethoxy propane, 2- isopropyl -1,3- dimethoxy propane, 2- butyl -1,3- dimethoxy propane, 2- Zhong Ding Base -1,3- dimethoxy propane, 2- cyclohexyl -1,3- dimethoxy propane, 2- phenyl -1,3- dimethoxy propane, 2- (2- benzene Base ethyl) -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, 2, 2- bicyclopentyl -1,3- dimethoxy propane, 2,2- diethyl -1,3- dimethoxy propane, 2,2- dipropyl -1,3- dimethoxy Base propane, 2,2- diisopropyl -1,3- dimethoxy propane, 2,2- dibutyl -1,3- dimethoxy propane, 2- methyl -2- third Base -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 - Bis- (2- the cyclohexyl-ethyl) -1,3- dimethoxy propanes of 2- cyclohexyl -1,3- dimethoxy propane, 2,2-, 2- methyl -2- isobutyl Base -1,3- dimethoxy propane, 2- methyl -2- (2- ethylhexyl) -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- Dimethoxy propane, 2,2- diphenyl -1,3- dimethoxy propane, 2,2- dibenzyl -1,3- dimethoxy propane, 2,2- are bis- (cyclohexyl methyl) -1,3- dimethoxy propane, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propane, 2- (1- methyl fourth Base) -2- isopropyl -1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2- phenyl -2- be different Propyl -1,3- dimethoxy propane, 2- phenyl -2- sec-butyl -1,3- dimethoxy propane, 2- benzyl -2- isopropyl -1,3- two Methoxy propane, 2- cyclopenta -2- isopropyl -1,3- dimethoxy propane, 2- cyclopenta -2- sec-butyl 1,3- dimethoxy third Alkane, 2- cyclohexyl -2- isopropyl -1,3- dimethoxy propane, 2- cyclohexyl -2- sec-butyl -1,3- dimethoxy propane, 2- are different Propyl -2- sec-butyl -1,3- dimethoxy propane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propane, 9,9- bis- Methoxy fluorenes.

Under most preferred case, the internal electron donor compound b is 2- isopropyl -2- isopentyl -1,3- dimethoxy third Alkane 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-aZ_aAnd/or Ti (OR ')_4-bZ_bSubstance, 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 -5 to -25 DEG C), magnesium halide alcohol adduct is then added Carrier, and be stirred at such a temperature 10-60 minutes, it is warming up to later reaction temperature (i.e. about 60-130 DEG C), and anti-at this It is maintained 0.5-10 hours at a temperature of answering.It is described interior to electricity in the preparation method of the catalytic component for olefinic polymerization Donor compound is one or more of before and after, during the reacting of the magnesium halide alcohol adduct carrier and titanium compound It is added in period.Period before the reacting of the magnesium halide alcohol adduct carrier and titanium compound refers in the magnesium halide Alcohol adduct carrier be added reactor in after and the period before being warming up to reaction temperature.

In the present invention, when preparing the catalytic component, the internal electron donor compound a, internal electron donor chemical combination Object b can be added to by several times or simultaneously in the mixture of the magnesium halide alcohol adduct carrier and the titanium compound.Will be described Internal electron donor compound a, internal electron donor compound b are added to the magnesium halide alcohol adduct carrier by several times and the titanizing is closed When in the mixture of object, the internal electron donor compound a both can first be added, add the internal electron donor compound b； The internal electron donor compound b can also first be added, add the internal electron donor compound a.

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:(20- 200): (0.04-0.8), preferably 1:(50-180): (0.05-0.5), preferably 1:(70-150): (0.1-0.4).

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 C_1-8Alkyl, and wherein one or two group can be with For halogen；The C_1-8The 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:(1-500), 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=CHR_1-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 2,4- glycol dibenzoate 0.005mol and 2- isopropyl -2- isopentyl -1,3- dimethoxy is added in temperature in temperature-rise period Base propane 0.006mol, is warming up to 110 DEG C, to temperature after after constant temperature 1h, filter and remove liquid, titanium tetrachloride is added to carry out titanium processing, Then it is washed five times with hexane, spheric catalyst C1 is obtained after vacuum drying.

(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, Cyclohexyl Methyl Dimethoxysilane (CHMMS) hexane solution (the concentration 0.1mmol/ml of CHMMS), The anhydrous hexane of 10ml and the spherical catalyst components C1 of 4mg.The additional amount of Cyclohexyl Methyl Dimethoxysilane is come with Al/Si It indicates, is shown in Table 2.Autoclave is closed, the liquid propene of 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

(1) preparation of the catalytic component of olefinic polymerization is used for using carrier S 2 prepared by preparation embodiment 2:

Prepare catalyst component for olefin polymerization according to the method for embodiment 1, unlike carrier be S2, and 2,4- pentanediol Dibenzoate 0.003mol and 2- isopropyl -2- isopentyl -1,3- dimethoxy propane 0.0046mol, obtains catalyst group Divide C2.

(2) propylene polymerization:

Polypropylene is prepared according to the method for embodiment 1, except that replacing catalytic component using catalytic component C2 C1.It the results are shown in Table 2.

Embodiment 3

Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, 2,4- glycol dibenzoates 0.01mol and 2- isopropyl -2- isopentyl -1,3- dimethoxy propane 0.001mol, obtains catalytic component C3.

(2) propylene polymerization:

Polypropylene is prepared according to the method for embodiment 1, except that replacing catalytic component using catalytic component C3 C1.It the results are shown in Table 2.

Embodiment 4

Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, 2,4- pentanediol hexichol first is not added 3,5- heptandiol dibenzoate 0.0045mol and 2- isopropyl -2- isopentyl -1,3- dimethoxy propane is added in acid esters 0.006mol obtains catalytic component C4.

(2) propylene polymerization:

Polypropylene is prepared according to the method for embodiment 1, except that replacing catalytic component using catalytic component C4 C1.It the results are shown in Table 2.

Comparative example 1

Chlorination magnesium alcoholate is by the preparation of method disclosed in CN1330086A embodiment 1.

Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, preparing catalytic component process In, 2,4- glycol dibenzoate 0.005mol is only added in internal electron donor, obtains catalytic component DC1.

Polypropylene is prepared according to the method for embodiment 1.It the results are shown in Table 2.

Comparative example 2

The preparation of chlorination magnesium alcoholate is the same as comparative example 1.

Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, preparing catalytic component process In, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane 0.006mol is only added in internal electron donor, obtains catalytic component DC2。

And polypropylene is prepared according to the method for embodiment 1, except that replacing catalyst group using catalytic component DC2 Divide C1.It the results are shown in Table 2.

Comparative example 3

The preparation of spherical catalyst components: in glass reaction bottle of the 300ml being sufficiently displaced from by high pure nitrogen with stirring In, the titanium tetrachloride of 90ml and the hexane of 10ml is added, is cooled to -20 DEG C, spherical chlorination magnesium alcoholate carrier 8g is added, is stirring It mixes down, slowly heating, is added diisobutyl phthalate 0.006mol, is continuously heating to 110 DEG C stage by stage, arrives constant temperature after temperature It after 1h, filters and removes liquid, titanium tetrachloride is added to carry out titanium processing, filter and remove liquid, then washed with hexane, after vacuum drying Obtain spherical catalyst components DC3.

And polypropylene is prepared according to the method for embodiment 1, unlike, in propylene polymerization processes, using catalyst group DC3 is divided to replace catalytic component C1.It the results are shown in Table 2.

Comparative example 4

The preparation of chlorination magnesium alcoholate is the same as preparation comparative example 1.

The preparation of spherical catalyst components obtains spherical catalyst components DC4 with embodiment 1.

Propylene polymerization is the same as embodiment 1.It the results are shown in Table 2.

Comparative example 5

The preparation of spherical catalyst components obtains spherical catalyst components DC5 with embodiment 2.

Table 2

Infusing: ╲ indicates that, without adding external electron donor, Al/ED refers to the triethyl aluminum and cyclohexyl methyl being added when polymerization The molar ratio of dimethoxysilane.

From embodiment 1-4 as can be seen that its polymerization activity of catalyst of the invention is super compared with the data of comparative example 1-3 Height, and it is apparently higher than the catalyst containing only single internal electron donor；When external electron donor is not added, obtained polymer also has Higher isotacticity, and hydrogen response is good.From embodiment 1-2 as can be seen that using this compared with the data of comparative example 4-5 The catalyst of the preparation method preparation of carrier, founds structure capacity of orientation and hydrogen response is higher in invention.

Embodiment 5-8

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, catalytic component C5-C8 is prepared using carrier S 3-S6, the results are shown in Table 3.

Comparative example 6

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, catalytic component DC6 is prepared using carrier DS2, the results are shown in Table 3.

Table 3

It can be seen that there is the catalyst obtained using support preparation method of the invention high vertical structure to determine by the result of table 3 Tropism and hydrogen response.

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

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 internal electron donor chemical combination Object a and internal electron donor compound b, the internal electron donor compound a are glycol ester compounds, the internal electron donor chemical combination Object b is diether compounds；The preparation step of the magnesium halide alcohol adduct carrier includes: that under elevated pressure, magnesium halide alcohol adduct is melted Body passes through structural unit with hole and contacts with liquid cooling medium；

Wherein, the condition of the pressurization include: pressure be 0.05-1MPa, the pressure be by atmospheric pressure be 0MPa in terms of it is opposite Pressure；The structural unit with hole is stratum reticulare；The aperture in the hole is 10-1800 μm.

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, 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 1, wherein the stratum reticulare includes 1-20 layers；Every thickness degree is respectively 0.01- 0.35mm。

6. preparation method according to claim 5, wherein the stratum reticulare includes 2-8 layers；Every thickness degree is respectively 0.05- 0.25mm。

7. preparation method according to claim 1, wherein the stratum reticulare is metal net layer.

8. preparation method according to claim 1, wherein 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, R C₁-C₁₂Alkyl, C₃-C₁₀Naphthenic base or C₆-C₁₀Aryl；

9. preparation method according to claim 8, wherein m 2.4-3.5；N is 0.005-0.2；R is C₁-C₄Alkyl.

10. preparation method according to claim 1 or 8, wherein the preparation step packet of the magnesium halide alcohol adduct melt It 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；

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 12, wherein the inert liquid medium is C₄-C₁₀Alkane, kerosene, In paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil It is one or more.

14. preparation method according to claim 12, 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, wherein the liquid cooling medium is unreactive hydrocarbons solvent.

17. preparation method according to claim 16, wherein the liquid cooling medium is pentane, hexane, heptane, vapour One of oil and petroleum ether are a variety of；The temperature of the liquid cooling medium is (- 10 DEG C)-(- 40 DEG C).

18. preparation method according to claim 1, wherein on the basis of the dosage of the internal electron donor, it is described in give Total dosage of electron compound a and the internal electron donor compound b are 80-100 weight %；The internal electron donor chemical combination The molar ratio of object a and the internal electron donor compound b dosage is (0.55-50): 1.

19. preparation method according to claim 18, wherein the internal electron donor compound a and the interior electron The molar ratio of body compound b dosage is (0.65-10): 1.

20. preparation method according to claim 1,

Wherein, the internal electron donor compound a is glycol ester compounds shown in formula I, and the internal electron donor compound b is Diether compounds shown in formula II,

In formula I, R₁And R₂It is identical or different, it is each independently C₁-C₁₀Linear or branched alkyl group, C₃-C₂₀Substitution or do not take The naphthenic base in generation, C₆-C₂₀Substituted or unsubstituted aryl, C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀Substitution Or one of unsubstituted alkaryl, the aromatic ring in the aryl, aralkyl or alkaryl are optionally selected from halogen, C₁-C₆ Linear or branched alkyl group and C₁-C₆One of alkoxy or a variety of substitutions；

R₃、R₄、R₅、R₆And R¹-R²ⁿIt is identical or different, it is each independently hydrogen, halogen, C₁-C₂₀Linear or branched alkyl group, C₃- C₂₀Substituted or unsubstituted naphthenic base, C₆-C₂₀Substituted or unsubstituted aryl, C₇-C₂₀Substituted or unsubstituted alkane virtue Base, C₇-C₂₀Substituted or unsubstituted aralkyl, C₂-C₁₀Linear chain or branched chain alkylene and C₁₀-C₂₀Fused ring aryl in One kind, R₃、R₄、R₅、R₆And R¹-R²ⁿOptionally contain hetero atom, the hetero atom is one in nitrogen, oxygen, sulphur, silicon, halogen and phosphorus Kind is a variety of；

Alternatively, R₃、R₄、R₅、R₆And R¹-R²ⁿIn two or more be mutually bonded, to form ring；

N is the integer of 0-10；

In formula II, 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.

21. preparation method according to claim 1, wherein 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.

22. the catalytic component for olefinic polymerization that method described in any one of claim 1-21 is prepared.

23. 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 22；

(ii) at least one alkyl aluminum compound；And

(iii) optionally, at least one external electron donor.

24. for being used for olefinic polymerization described in the catalytic component of olefinic polymerization or claim 23 described in claim 22 Application of the catalyst in olefin polymerization.