CN104558312B - The preparation method and its polymer of a kind of olefin polymer - Google Patents

Abstract

The invention discloses a kind of preparation method of olefin polymer and its polymer.This method includes, in the presence of olefin polymerization catalysis, by formula CH₂The alkene that=CHR is represented carries out polymerisation；The olefin polymerization catalysis contains catalyst solid constituent A, organo-aluminum compound B and organo-silicon compound C；The weight ratio that the catalyst solid constituent A contains magnesium, titanium, halogen, internal electron donor a and internal electron donor b, the internal electron donor a and the internal electron donor b is less than 1:1；Wherein, the internal electron donor a and internal electron donor b is met

Description

The preparation method and its polymer of a kind of olefin polymer

Technical field

The present invention relates to a kind of preparation method of olefin polymer and its polymer.

Background technology

The molecular weight distribution of polymer（MWD）Influence its mechanical performance and processing characteristics.High molecular weight moieties are in very great Cheng The long term mechanical strength of polymer is determined on degree, and low molecular weight part largely determines its extrusion performance.

The polymer of wide molecular weight distribution can be obtained using specific olefin polymerization catalysis.

CN1313869 and CN1398270 disclose a kind of succinate internal electron donor, are prepared using the internal electron donor Z-N catalyst can be used for preparing and have the polypropylene of molecular weight distribution with width.

The Z-N catalyst that cyano group succinate disclosed in CN101993507A makees internal electron donor can also be used for preparing width The polyolefin of molecular weight distribution.

CN1334826 is disclosed prepares wide molecular weight distribution by two parts catalyst to the different responding abilities of hydrogen The scheme of polyethylene.

In addition, special external electron donor also contributes to prepare the broader polyolefin of molecular weight distribution, such as this area Molecular weight distribution can be obtained when known dicyclopentyl dimethoxyl silane is as Z-N catalyst external electron donors broader poly- Alkene.However, often relatively low to hydrogen sensitive degree during these catalyst preparation polymer, i.e., identical density of hydrogen when prepare it is poly- The melt index of compound is relatively low.

Wide molecular weight distribution polyolefin can also be obtained by special polymerization technique.Such as doing for so-called asymmetric hydrogenation Method, i.e., it is specific such as anti-first by controlling the consumption of chain-transferring agent hydrogen to be distributed come regulatory molecule amount in multiple reactor The polymer for obtaining HMW in device using a small amount of hydrogen is answered, and is come in second reactor using the hydrogen of higher concentration The relatively low polymer moieties of molecular weight are obtained, so as to obtain the polymer of wide molecular weight distribution；It can also use so-called The method of asymmetric plus external electron donor, i.e., regulate and control polymerization using the polymer molecular weight difference of different external electron donors acquisition Thing molecular weight distribution, specifically uses the external electron donor such as bicyclopentyl for obtaining macromolecule part such as in first reactor Dimethoxysilane, and using the external electron donor such as tetraethoxysilane for obtaining small molecular mass moieties in another reactor, So as to obtain the polymer of wide molecular weight distribution.But these schemes are relatively difficult to achieve in a reactor, polymerization process It is complicated.

In addition, being the processing request for meeting injecting products, especially thin wall parts, polymer generally requires higher melt Flow rate-MFR（Or melt index-MI）.Olefin polymer such as polypropylene melt flow rate is improved generally using following Method：（1）After polymerisation, degradation agent is added in the polymer, generally using one or more peroxide, certain Under reaction condition, the macromolecular chain in polymer is occurred molecular breakdown, be improved the MFR of product.This is typically referred to as For controllable rheology technology.（2）Increase the consumption of molecular weight regulator hydrogen in the course of the polymerization process, so as to reach the mesh for improving MFR 's.（3）In the course of the polymerization process using the sensitive catalyst system of molecular-weight adjusting.By selecting different catalysts component, helping and urge The combination of agent and external electron donor so that polymerisation catalyst system is to molecular weight regulator（Hydrogen is commonly used molecule Measure conditioning agent）Become more sensitive, in the presence of a small amount of hydrogen, high MFR polymeric articles can be obtained.

High MFR polymer is produced using controllable rheology technology, i.e., a small amount of peroxide degradation agent is added into polymer, no The manufacturing cost of product can only be increased, product is also resulted in and produce niff, so as to limit its application.In addition, can The polymer segment of HMW is often broken first in control rheological technique, so that polymer molecular weight distribution narrow.

Improving the method for the high MFR polymeric articles of hydrogen usage production also has significant limitation.On the one hand, due to device The reason for pressure design, limit the addition of hydrogen；On the other hand, hydrogen usage is excessive can also bring problems with：Catalysis Agent activity is greatly reduced；Polymer isotacticity declines, and end article rigidly declines；Further, in gathering for being radiated using liquid propene Close in technique, a large amount of hydrogen in polymerization system（Hydrogen is a kind of fixed gas）Presence make it that propylene condensation is difficult, directly affect Produce load, causes production capacity to decline.

In a word, aforementioned production method is difficult while preparing both has high melt flow rate (MFR), high isotactic, while molecular weight The wide olefin polymer of distribution.But when producing injection homopolymer or anti-impact polymer, it is often desirable to polymer both had High melt flow rate (MFR) and high isotacticity, while there is wide molecular weight distribution.This polymer is considered as existing good and added Intensity and rigidity that work performance has also had.

Accordingly, it is desirable to provide one kind can be prepared while having high melt flow rate (MFR), high isotactic and wide molecular weight point The method of the olefin polymer of cloth.

The content of the invention

The invention aims to overcome the shortcoming of prior art there is provided the preparation method of olefin polymer and its gather Compound.

To achieve these goals, the invention provides a kind of preparation method of olefin polymer, this method includes, in alkene In the presence of polymerized hydrocarbon catalyst, by formula CH₂The alkene that=CHR is represented carries out polymerisation；The olefin polymerization catalysis contains There are catalyst solid constituent A, organo-aluminum compound B and organo-silicon compound C；The catalyst solid constituent A contain magnesium, titanium, The weight ratio of halogen, internal electron donor a and internal electron donor b, the internal electron donor a and the internal electron donor b be less than 1:1；Wherein, the internal electron donor a and the internal electron donor b meet following condition：In polymerizing condition, organo-aluminum compound In the case of B and organo-silicon compound C identicals during polypropylene, by being only urging for the internal electron donor a containing internal electron donor Agent solid constituent A0, the organo-aluminum compound B and the organo-silicon compound C composition polymerization catalyst obtain poly- third The melt flow rate (MFR) MFR11 of alkene and catalyst solid constituent B0, institute by containing internal electron donor being only the internal electron donor b State the polyacrylic melt flow rate (MFR) that the polymerization catalyst of organo-aluminum compound B and organo-silicon compound C compositions is obtained MFR21 is metThe temperature of the polymerisation is 85-130 DEG C.

Present invention also offers polyolefin made from method provided by the present invention, wherein, the polyolefin is polypropylene, is gathered The melt flow rate (MFR) MFR of propylene is more than 45g/10min, M_Z+1/ Mn is more than 45, and isotactic index II is more than 94.5%.

The olefin polymerization catalysis that the present invention is provided can be had height simultaneously when carrying out high temperature olefinic polyreaction The olefin polymer of melt flow rate (MFR), high isotactic and wide molecular weight distribution.In the olefin polymerization catalysis that the present invention is provided From specific two kinds of internal electron donors a and b, and under specific amount ratio, andUnder conditions of, Ke Yigeng Be conducive to while being had the olefin polymer of high melt flow rate (MFR), high isotactic and wide molecular weight distribution.

In addition, in the application of the olefin polymerization catalysis of the invention provided in olefin polymerization, having pre- complexing and pre- The high temperature polymerization of polymerization technique can be more beneficial for polymerization while being had high melt flow rate (MFR), high isotactic and wide molecule Measure the olefin polymer of distribution.

Other features and advantages of the present invention will be described in detail in subsequent embodiment part.

Embodiment

The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The invention provides a kind of preparation method of olefin polymer, this method includes, in depositing for olefin polymerization catalysis Under, by formula CH₂The alkene that=CHR is represented carries out polymerisation；The olefin polymerization catalysis contains catalyst solid constituent A, organo-aluminum compound B and organo-silicon compound C；The catalyst solid constituent A contains magnesium, titanium, halogen, internal electron donor a Weight ratio with internal electron donor b, the internal electron donor a and the internal electron donor b is less than 1:1；Wherein, given in described Electron a and the internal electron donor b meet following condition：In polymerizing condition, organo-aluminum compound B and organo-silicon compound C In the case of identical during polypropylene, by the catalyst solid constituent A0, the institute that containing internal electron donor are only the internal electron donor a State the polyacrylic melt flow rate (MFR) that the polymerization catalyst of organo-aluminum compound B and organo-silicon compound C compositions is obtained MFR11 with by the catalyst solid constituent B0 for containing internal electron donor being only the internal electron donor b, the organo-aluminum compound B The polyacrylic melt flow rate (MFR) MFR21 obtained with the organo-silicon compound C polymerization catalysts constituted is metThe temperature of the polymerisation is 85-130 DEG C；Preferably, the temperature of the polymerisation is 85-110 DEG C, More preferably 85-95 DEG C.

According to the present invention, the internal electron donor a and internal electron donor b contained in the catalyst solid constituent can have spy Fixed weight ratio, being more beneficial for obtaining has the high melt flow rate (MFR) wide olefin polymer of molecular weight distribution again.Preferable case Under, the internal electron donor a and internal electron donor b weight ratio is 0.05-0.43：1.

According to the present invention, the catalyst solid constituent A0 for comprising only internal electron donor a is formed.With containing catalyst solid constituent A0 olefin polymerization catalysis polypropylene, the polyacrylic melt flow rate (MFR) of gained is MFR11；The size of MFR11 values depends on In the number of the hydrogen usage as chain-transferring agent.

Form the catalyst solid constituent B0 for comprising only internal electron donor b.Gathered with the alkene of the B0 containing catalyst solid constituent Polymerization catalyst propylene is closed, the polyacrylic melt flow rate (MFR) of gained is MFR21；The size of MFR21 values depends on turning as chain Move agent hydrogen usage number.

Prepare electron donor in high melt flow rate (MFR) and the wide polymer of molecular weight distribution, the catalyst solid constituent Compound a and b also need to meet following condition：It is identical with hydrogen amount when polymerize, preferablyMost preferably

Polymer prepared by the activated centre polymerization for being so appreciated that to be formed by internal electron donor a has low melt Flow rate, as the high molecular weight moieties in polymer；And polymerization prepared by the activated centre polymerization of internal electron donor b formation Thing has high melt flow rate (MFR), as the low molecular weight part in polymer.It is wide so as to assign final polymeric articles Molecular weight distribution, while having higher melt flow rate (MFR).

In the present invention, the internal electron donor a can be selected especially insensitive to be responded to external electron donor first, it is described Internal electron donor b responds especially sensitive to external electron donor.It can be selected according to following methods：

Well known in the art, dicyclopentyl dimethoxyl silane is as external electron donor in use, institute under the same terms The polymer obtained has relatively low melt flow rate (MFR), i.e., especially insensitive to the hydrogen as chain-transferring agent；And tetraethoxy-silicane Alkane as during external electron donor pair then on the contrary, the polymer of gained has extra high melt flow rate (MFR) under the same terms, i.e., Hydrogen is especially sensitive.

The internal electron donor a is especially insensitive to external electron donor response to be referred to：Above-mentioned catalytic agent solid constituent A0, Under identical specific aggregation condition and polymerization procedure, gained is poly- during using dicyclopentyl dimethoxyl silane as external electron donor The melt flow rate (MFR) MFR12 of compound, with using tetraethoxysilane as the melt flow of resulting polymers during external electron donor Dynamic speed MFR13 ratio is

The internal electron donor b is especially sensitive to external electron donor response to be referred to：Contain catalysis in olefin polymerization catalysis Agent solid constituent B0, under identical specific aggregation condition and polymerization procedure, using dicyclopentyl dimethoxyl silane as outer The melt flow rate (MFR) MFR22 of resulting polymers during electron donor, with using tetraethoxysilane as external electron donor when institute The melt flow rate (MFR) MFR23 ratio of polymer is

Specific aggregation condition includes：Bulk propylene polymerization is carried out in 5L polymeric kettles.Polymerization temperature is 70 DEG C, hydrogen/the third Alkene ratio is 7.3 × 10^-3Mol/mol, co-catalyst is organo-aluminum compound B, is used as the organo-silicon compound of external electron donor；Have Machine aluminium compound/organo-silicon compound=25mol/mol；Ti=500mol/mol in organo-silicon compound/catalyst solid constituent； The polyacrylic melt flow rate (MFR) that polymerization is obtained is determined in accordance with GB/T3682-2000.

More specifically：5 liters of autoclaves for being connected with catalyst feeder, propylene and hydrogen feed line are filled with gas-phase propene Split and change.The hexane solution of 5mL triethyl aluminums is added into catalyst feeder at room temperature（The concentration of triethyl aluminum is 0.5mol/L）, 1mL organo-silicon compound hexane solution（Concentration is 0.1mol/L）, 10mL anhydrous n-hexanes and catalyst it is solid Body component（Make the mol ratio for the Ti content and triethyl aluminum wherein counted using titanium elements as 500:1）, mix 2 minutes（Pre- complexing）Afterwards It is added to autoclave.Autoclave is closed, 4.0 standards is introduced and rises hydrogen and 2.0L liquid propene；Under agitation will in 20 minutes Temperature rises to 70 DEG C.Polymerisation stops stirring after 1 hour at 70 DEG C, removes unpolymerized propylene monomer, it is poly- that collection is obtained Compound.

Specific internal electron donor a and internal electron donor b evaluation is shown in description of the invention embodiment with selection course.

According to the present invention, the content of each component contained in the catalyst solid constituent can so that there is no particular limitation, It can be conducive to carrying out the high melt flow rate (MFR) of olefinic polymerization acquisition and the wide olefin polymer of molecular weight distribution.It is preferred that feelings Under condition, on the basis of the gross weight of the catalyst solid constituent, in the catalyst solid constituent, the titanium in terms of titanium elements Content is that 1-8 weight %, the content of magnesium in terms of magnesium elements are that 10-70 weight %, the content of halogen in terms of halogens are 20-85 weights % is measured, the content of the total amount of the internal electron donor a and internal electron donor b is 2-30 weight %；Preferably, it is solid with the catalyst On the basis of the gross weight of body component, in the catalyst solid constituent, the Ti content counted using titanium elements as 1.6-6 weight %, with The content of magnesium of magnesium elements meter is that 15-40 weight %, the content of halogen in terms of halogens are 30-80 weight %, the interior electron The content of body a and internal electron donor b total amount is 3-20 weight %.

, according to the invention it is preferred in the case of, the internal electron donor a can be formula（I）Shown compound, formula（II）It is shown Compound and formula（III）At least one of shown compound；

Formula（I）In：R₁And R₂It is identical or differ, and be each independently hydrogen or C1-C14 straight or brancheds alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkaryls or C7-C10 aralkyl；R₃And R₄It is identical or differ, and each solely It is on the spot alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls or the C7-C20 aralkyls of C1-C10 straight or brancheds Base；

Formula（II）In：R₅And R₆It is identical or differ, and it is each independently the alkyl of C1-C10 straight or brancheds, C3- C10 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls or C7-C20 aralkyl, optionally contain hetero atom；R₇-R₁₀It is identical or not It is identical, and it is each independently alkyl, C2-C14 alkylenes, C3-C10 cycloalkyl, the C6- of hydrogen or C1-C14 straight or brancheds C10 aryl, C7-C10 alkaryls or C7-C10 aralkyl；Work as R₇-R₉When being all hydrogen simultaneously, R₁₀Uncle position selected from C3-C20 is branched Secondary alkyl, tertiary alkyl, cycloalkyl, aryl, aryl alkyl or alkylaryl；

Formula（III）In：R₁₁And R₁₂It is identical or differ, and it is each independently selected from halogen, substituted or unsubstituted straight chain Or C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, the C2-C10 alkene of side chain Alkyl or C10-C20 fused ring aryls；R₁₃-R₁₈It is identical or differ, and it is each independently selected from hydrogen, halogen, substitution or unsubstituted The C1-C20 alkyl of straight or branched, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, C2-C10 alkylenes or C10-C20 fused ring aryls, or optionally R₁₃-R₁₈In at least two link up cyclization.

In the present invention, it is preferable that formula（I）Shown compound can be selected from following at least one：2,3- diisopropyls -2- Cyano group dimethyl succinate, 2,3- diisopropyl -2- cyano group diethyl succinate, 2,3- diisopropyl -2- cyano group succinic acid two N-propyl, 2,3- diisopropyl -2- cyano group diisopropyl ester amber acid, 2,3- diisopropyl -2- cyano group succinic acid di-n-butyl, 2, 3- diisopropyl -2- cyano group succinic acid diisobutyl ester, 2,3- diisopropyl -2- cyano group succinic acid -1- methyl esters -4- ethyl esters（R₁=first Base, R₂=ethyl）, 2,3- diisopropyl -2- cyano group succinic acid -1- ethyl ester -4- methyl esters（R₁=ethyl, R₂=methyl）, 2,3- bis- it is different Propyl group -2- cyano group succinic acid -1- N-butyl -4- ethyl esters（R₁=normal-butyl, R₂=ethyl）, 2,3- diisopropyl -2- cyano group fourth two Acid -1- ethyl ester -4- N-butyls（R₁=ethyl, R₂=normal-butyl）, 2,3- diisobutyl -2- cyano group dimethyl succinate, 2,3- bis- it is different Butyl -2- cyano group diethyl succinate, 2,3- diisobutyl -2- cyano group succinic acid di-n-propyl ester, 2,3- diisobutyl -2- cyano group Diisopropyl ester amber acid, 2,3- diisobutyl -2- cyano group succinic acid di-n-butyl, 2,3- diisobutyl -2- cyano group succinic acid two Isobutyl ester, 2,3- diisobutyl -2- cyano group succinic acid -1- methyl esters -4- ethyl esters（R₁=methyl, R₂=ethyl）, 2,3- diisobutyls- 2- cyano group succinic acid -1- ethyl ester -4- methyl esters（R₁=ethyl, R₂=methyl）, the positive fourths of 2,3- diisobutyl -2- cyano group succinic acid -1- Ester -4- ethyl esters（R₁=normal-butyl, R₂=ethyl）, 2,3- diisobutyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyls（R₁=second Base, R₂=normal-butyl）, 2,3- di-sec-butyl -2- cyano group dimethyl succinate, 2,3- di-sec-butyl -2- cyano group succinic acid diethyls Ester, 2,3- di-sec-butyl -2- cyano group succinic acid di-n-propyl ester, 2,3- di-sec-butyl -2- cyano group diisopropyl ester amber acid, 2,3- bis- Sec-butyl -2- cyano group succinic acid di-n-butyl, 2,3- di-sec-butyl -2- cyano group succinic acid diisobutyl ester, 2,3- di-sec-butyls -2- Cyano group succinic acid -1- methyl esters -4- ethyl esters（R₁=methyl, R₂=ethyl）, 2,3- di-sec-butyl -2- cyano group succinic acid -1- ethyl esters -4- Methyl esters（R₁=ethyl, R₂=methyl）, 2,3- di-sec-butyl -2- cyano group succinic acid -1- N-butyl -4- ethyl esters（R₁=normal-butyl, R₂= Ethyl）, 2,3- di-sec-butyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyls（R₁=ethyl, R₂=normal-butyl）, the rings penta of 2,3- bis- Base -2- cyano group dimethyl succinate, 2,3- bicyclopentyl -2- cyano group diethyl succinate, 2,3- bicyclopentyl -2- cyano group fourth two Sour di-n-propyl ester, 2,3- bicyclopentyl -2- cyano group diisopropyl ester amber acid, the positive fourth of 2,3- bicyclopentyl -2- cyano group succinic acid two Ester, 2,3- bicyclopentyl -2- cyano group succinic acid diisobutyl ester, 2,3- bicyclopentyl -2- cyano group succinic acid -1- methyl esters -4- ethyl esters （R₁=methyl, R₂=ethyl）, 2,3- bicyclopentyl -2- cyano group succinic acid -1- ethyl ester -4- methyl esters（R₁=ethyl, R₂=methyl）、2, 3- bicyclopentyl -2- cyano group succinic acid -1- N-butyl -4- ethyl esters（R₁=normal-butyl, R₂=ethyl）, 2,3- bicyclopentyl -2- cyano group Succinic acid -1- ethyl ester -4- N-butyls（R₁=ethyl, R₂=normal-butyl）, 2,3- dicyclohexyl -2- cyano group dimethyl succinate, 2,3- Dicyclohexyl -2- cyano group diethyl succinate, 2,3- dicyclohexyl -2- cyano group succinic acid di-n-propyl ester, 2,3- dicyclohexyls -2- Cyano group diisopropyl ester amber acid, 2,3- dicyclohexyl -2- cyano group succinic acid di-n-butyl, 2,3- dicyclohexyl -2- cyano group fourth two Sour diisobutyl ester, 2,3- dicyclohexyl -2- cyano group succinic acid -1- methyl esters -4- ethyl esters（R₁=methyl, R₂=ethyl）, the hexamethylenes of 2,3- bis- Base -2- cyano group succinic acid -1- ethyl ester -4- methyl esters（R₁=ethyl, R₂=methyl）, 2,3- dicyclohexyl -2- cyano group succinic acid -1- just Butyl ester -4- ethyl esters（R₁=normal-butyl, R₂=ethyl）, 2,3- dicyclohexyl -2- cyano group succinic acid -1- ethyl ester -4- N-butyls（R₁=second Base, R₂=normal-butyl）.Wherein, preferably 2,3- diisopropyls -2- cyano group diethyl succinate, 2,3- diisopropyl -2- cyano group fourths Diacid di-n-propyl ester, 2,3- diisopropyl -2- cyano group diisopropyl ester amber acid, 2,3- diisopropyl -2- cyano group succinic acid two are just Butyl ester, 2,3- diisopropyl -2- cyano group succinic acid diisobutyl esters.2,3- diisopropyl -2- cyano group succinic acid two is particularly preferred Ethyl ester.

In the present invention, it is preferable that formula（II）Shown compound can be selected from following at least one：Double (the 2- ethyls of 2,3- Butyl) butanedioic acid diethyl ester, 2,3- diethyl -2- isopropyl butanedioic acids diethyl ester, 2,3- diisopropyl butanedioic acid diethyls Base ester, 2,3- di-t-butyl butanedioic acids diethyl ester, 2,3- diisobutyl butanedioic acids diethyl ester, 2,3- (double trimethyl first silicon Alkyl) butanedioic acid diethyl ester, 2- (3,3,3,3- trifluoro propyls) -3- methylsuccinic acids diethyl ester, 2,3- di neo-pentyl ambers Amber acid diethyl ester, 2,3- diisoamyl butanedioic acids diethyl ester, 2,3- (1- trifluoromethyl-ethyls) butanedioic acid diethyl ester, 2- isopropyl -3- isobutyl group butanedioic acids diethyl ester, the 2- tert-butyl group -3- isopropyl butanedioic acids diethyl ester, 2- isopropyl -3- rings Hexyl butanedioic acid diethyl ester, 2- isopentyl -3- cyclohexyl butanedioic acids diethyl ester, 2,2,3,3- methylsuccinic acid diethyl Ester, 2,2,3,3- tetraethyl butanedioic acids diethyl ester, 2,2,3,3- tetrapropyl butanedioic acids diethyl ester, 2,3- diethyl -2,3- Double (2- ethyl-butyls) the butanedioic acid diisobutyl esters of diisopropyl disuccinic acid diethyl ester, 2,3-, 2,3- diethyl -2- isopropyls Base di-iso-octyl succinate, 2,3- diisopropyls di-iso-octyl succinate, 2,3- di-t-butyl butanedioic acid diisobutyls ester, 2,3- Diisobutyl butanedioic acid diisobutyl ester, 2,3- (double trimethyl silyls) butanedioic acid diisobutyls ester, 2- (3,3,3,3- tri- Fluoropropyl) -3- methylsuccinic acid diisobutyls ester, 2,3- di neo-pentyl butanedioic acid diisobutyls ester, 2,3- diisoamyl ambers Sour diisobutyl ester, 2,3- (1- trifluoromethyl-ethyls) butanedioic acid diisobutyls ester, 2- isopropyl -3- isobutyl groups butanedioic acid two Isobutyl, the 2- tert-butyl group -3- isopropyl butanedioic acid diisobutyls ester, 2- isopropyl -3- cyclohexyl butanedioic acid diisobutyls ester, 2- isopentyl -3- cyclohexyl butanedioic acid diisobutyls ester, 2,2,3,3- methylsuccinic acid diisobutyls ester, 2,2,3,3- tetraethyls Butanedioic acid diisobutyl ester, 2,2,3,3- tetrapropyl butanedioic acid diisobutyls ester, the amber of 2,3- diethyl -2,3- diisopropyls two Sour diisobutyl ester.Particularly preferred 2,3- diisopropyl butanedioic acid diethyl esters.

In the present invention, it is preferable that formula（III）Shown compound can be selected from following at least one：2- isopropyls -2- is different The propylene glycol dibenzoate of amyl group -1,3,2,4-PD dibenzoate, 3- methyl -2,4-PD dibenzoate, 3- Ethyl -2,4-PD dibenzoate, 2,2- dimethyl -2,4-PD dibenzoate, 3,5- heptandiol dibenzoic acids Ester, 4- methyl -3,5- heptandiols dibenzoate, 4- ethyl -3,5- heptandiol dibenzoates.Particularly preferred 2,4-PD At least one of dibenzoate, 3,5 heptandiol dibenzoates and the heptandiol dibenzoate of 4- ethyls -3,5.

, according to the invention it is preferred in the case of, the internal electron donor b can be formula（IV）Shown compound,

Formula（IV）In：R₁₉And R₂₀It is identical or differ, and it is each independently the alkyl of C1-C12 straight or brancheds, C3- One kind in C10 cycloalkyl and C6-C20 alkaryls, substitution or unsubstituted aryl；R₂₁-R₂₄All hydrogen, or wherein three Individual is hydrogen, and another is one kind in the alkoxy of halogen, the alkyl of C1-C4 straight or brancheds and C1-C4 straight or brancheds.

In the present invention, it is preferable that the internal electron donor b can be for diethyl phthalate, phthalic acid two just Butyl ester, diisobutyl phthalate, DHP, dibutyl phthalate (DHP) and diisooctyl phthalate At least one of.

According to the present invention, the catalyst solid constituent A be titanium compound, magnesium compound, internal electron donor a and it is interior to electricity Daughter b reaction product.

In the present invention, under preferable case, the magnesium compound can be formula（VIII）Shown magnesium compound, formula（VIII） The hydrate and formula of shown magnesium compound（VIII）At least one of shown alcohol adducts of magnesium compound,

MgR⁴R⁵Formula（VIII）

Formula（VIII）In, R⁴And R⁵Halogen, C1-C8 straight or branched alkoxyl and C1-C8 can be each independently One kind in straight or branched alkyl.

In the present invention, formula（VIII）The hydrate of shown magnesium compound refers to MgR⁴R⁵·pH₂O, wherein, p is 0.1-6, Preferably 2-3.5.In the present invention, formula（VIII）The alcohol adducts of shown magnesium compound refer to MgR⁴R⁵·qR⁶OH, wherein, R⁶ For C1-C18 alkyl, preferably C1-C8 alkyl, more preferably methyl, ethyl, n-propyl and isopropyl；Q is 0.1-6, excellent Elect 2-3.5 as.

Preferably, the magnesium compound can be dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy Epoxide magnesium, two (2- ethyls) epoxide magnesium, the methoxyl group chlorine of magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two Change magnesium, methoxyl group magnesium bromide, methoxyl group magnesium iodide, ethyoxyl magnesium chloride, ethyoxyl magnesium bromide, ethyoxyl magnesium iodide, propoxyl group Magnesium chloride, propoxyl group magnesium bromide, propoxyl group magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, methyl Magnesium chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, amyl group magnesium chloride, phenyl-magnesium-chloride, magnesium dichloride, dibrominated In magnesium, magnesium diiodide, the alcohol adducts of magnesium dichloride, the alcohol adducts of the alcohol adducts of dibrominated magnesium and magnesium diiodide at least It is a kind of.Most preferably, the magnesium compound contains in diethoxy magnesium, butylmagnesium chloride, ethyoxyl magnesium chloride and magnesium dichloride At least one.

In the present invention, the titanium compound can be formula（IX）Shown compound,

TiX_m(OR⁷)_4-mFormula（IX）

Formula（IX）In, X is halogen, R⁷For C1-C20 alkyl, m is 0-4 integer.The halogen can for chlorine, bromine or Iodine.

Preferably, formula（IX）In, X is halogen, R⁷For C1-C5 alkyl, the titanium compound can be for for example：Four chlorinations Titanium, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and three At least one of ethanolato-titanium of chlorine one.Most preferably, the titanium compound is titanium tetrachloride.

In the present invention, the catalyst solid constituent A can prepare alkene catalyst component by this area routine Method carry out.The catalyst solid constituent of the present invention can be for example prepared by one of following methods.

1）Method one：Alkoxyl magnesium or Alkoxymagnesium halides are suspended in inert diluent and form suspension, then should Suspension contacts to obtain solids dispersion, commonly referred to as mother liquor with above-mentioned titanium compound, internal electron donor a and b mixing.Will Mother liquor is filtered, and gained solid matter is suspended in progress contact processing in the solution containing titanium tetrachloride, and commonly referred to as titanium is handled；Then Through filtering, washing can be prepared by the catalyst solid constituent of the present invention.

As the specific example of above-mentioned alkoxyl magnesium, can enumerate dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, Diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two hexyloxy magnesium, two (2- ethyls) hexyloxy magnesium Deng or its mixture, preferably diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesiums mixture.The alkoxyl magnesium The preparation method of compound, can be prepared by method well known in the art, as disclosed in patent CN101906017A by magnesium metal with Fatty alcohol is prepared in the presence of a small amount of iodine.

As the specific example of above-mentioned Alkoxymagnesium halides, methoxy magnesium chloride, ethyoxyl magnesium chloride, the third oxygen can be enumerated Base magnesium chloride, butoxy magnesium chloride etc., preferably ethyoxyl magnesium chloride.The preparation method of the alkoxy magnesium compound, can be by Prepared by method well known in the art, such as mix to prepare with purity titanium tetraethoxide and tetraethoxy-silicane by RMgBr butylmagnesium chloride Ethyoxyl magnesium chloride.

In the above method one inert diluent used in the formation of mother liquor can using hexane, heptane, octane, decane, benzene, At least one of toluene and dimethylbenzene.

The consumption of each composition used in the formation of mother liquor in method one, in terms of every mole of magnesium elements, titanium compound makes 0.5-100 moles of consumption, preferably 1-50 moles；The usage amount of inert diluent is usually 0.5-100 moles, preferably 1-50 Mole；Interior electron donor a and b total amount is usually 0.005-10 moles, preferably 0.01-1 moles.

The Contact Temperature of each component is usually -40 DEG C to 200 DEG C during the formation of mother liquor in method one, is preferably -20 DEG C to 150 DEG C；Time of contact is usually -20 hours 1 minute, preferably -8 hours 5 minutes.

Described in method one in titanium processing procedure, alternative addition inert diluents in the solution containing titanium tetrachloride are used At least one of agent, such as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.

In method one in titanium processing procedure, the consumption containing each composition in titanium tetrachloride solution is used, with every mole of magnesium member Element meter, preferably 0.5-100 moles of the usage amount of titanium compound, 1-50 moles；The usage amount of inert diluent is usually 0-100 Mole, preferably 0-50 moles.

Titanium number of processes is 0-10 times, preferably 1-5 times in method one.

In method one in titanium processing procedure, alternative adds above-mentioned interior electron donor a and b, wherein internal electron donor a and B total consumption is usually 0.005-10 moles, preferably 0.01-1 moles.

Titanium treatment temperature is usually 0-200 DEG C in method one, preferably 30-150 DEG C；Time of contact is usually 1 minute -20 Hour, preferably -6 hours 5 minutes.

2）Method two：By magnesium dihalide be dissolved in organic epoxy compound thing, organic phosphorus compound, aliphatic alcohols compound with In the dicyandiamide solution of inert diluent composition, contacted instead with above-mentioned titanium compound, internal electron donor a and b after forming homogeneous solution Should, in the presence of precipitation additive, solids is separated out, mother liquor is formed；Mother liquor is filtered, gained solid matter is suspended in containing four chlorinations Contact processing is carried out in the solution of titanium, hereinafter known as titanium is handled；Then through filtering, washing can be prepared by the catalyst of the present invention Solid constituent.

The precipitation additive used in method two is not particularly limited, as long as solid particle can be made to separate out shaping.Can be with The example enumerated has：At least one of organic acid anhydride, organic acid, ester, ether and ketone.The specific example of the organic acid anhydride can be with For at least one of acetic anhydride, phthalic anhydride, succinic anhydride and maleic anhydride etc., the concrete example of the organic acid Son can be at least one of acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid etc., and the specific example of the ester can be with It is different for dibutyl phthalate, 2,4-PD dibenzoate, 3- ethyls -2,4-PD dibenzoate, 2,3- bis- In propyl group -1,4- butanediols dibenzoate, 3,5- heptandiols dibenzoate and 4- ethyl -3,5- heptandiol dibenzoates At least one, the specific example of the ether can be methyl ether, ether, propyl ether, butyl ether, amyl ether, 2- isopropyl -2- isopentyl two At least one of methoxy propane and 9,9- (dimethoxy methyl) fluorenes, the ketone can be in acetone, MEK and benzophenone At least one.

The organic epoxy compound thing used in method two can be selected from oxirane, expoxy propane, epoxy butane, fourth At least one in allene oxide thing, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether etc. Plant, preferably epoxychloropropane.

The organic phosphorus compound used in method two can be the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid, The specific example of the organic phosphorus compound can be enumerated：Orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, positive phosphorus Triphenyl phosphate ester, Trimethyl phosphite, triethyl phosphite, tributyl phosphite or phosphorous acid benzene methyl etc., preferably orthophosphoric acid three Butyl ester.

The aliphatic alcohols compound used in method two can be C1-C20 straight or branched alkane unitary or polynary The straight or branched unitary fatty alcohol of fatty alcohol, preferably C1-C10, specific example can be enumerated：Methanol, ethanol, propyl alcohol, isopropyl Alcohol, butanol, isobutanol, amylalcohol, hexanol, enanthol, (2- ethyls) hexyl alcohol, octanol, nonyl alcohol, decyl alcohol etc., preferably (2- ethyls) oneself Base alcohol.

The inert diluent that mother liquor is used in being formed in method two can use hexane, heptane, octane, decane, benzene, toluene At least one of with dimethylbenzene.

Mother liquor forms the consumption of the middle each composition used, in terms of every mole of halogenation magnesium elements, organic epoxidation in method two Compound can be 0.2-10 moles, preferably 0.5-4 moles；Organic phosphorus compound can be 0.1-3 moles, preferably 0.3- 1.5 mole；Fat alcohol compound can be 0.2-10 moles, preferably 0.5-3 moles；Titanium compound can rub for 0.5-20 You, preferably 5-15 moles；It can be 0.01-0.3 moles, preferably 0.02-0.2 moles to help precipitation component；Interior electron donor a Total consumption with b can be 0-10 moles, preferably 0.02-0.3 moles.

The Contact Temperature of each component is usually -40 DEG C to 200 DEG C during the formation of mother liquor in method two, is preferably -20 DEG C to 150 DEG C；Time of contact is usually -20 hours 1 minute, preferably -8 hours 5 minutes.

Described in method two in titanium processing procedure, alternative addition inert diluents in the solution containing titanium tetrachloride are used At least one of agent, such as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.

In method two in titanium processing procedure, the consumption containing each composition in titanium tetrachloride solution is used, with every mole of magnesium member Element meter, preferably 0.5-100 moles of the usage amount of titanium compound, 1-50 moles；The usage amount of inert diluent is usually 0-100 Mole, preferably 0-50 moles.

Titanium number of processes is 0-10 times, preferably 1-5 times in method two.

In method two in titanium processing procedure, alternative adds above-mentioned interior electron donor a and b, wherein internal electron donor a and B total consumption is usually 0.005-10 moles, preferably 0.01-1 moles.

Titanium treatment temperature is usually 0-00 DEG C in method two, preferably 30-150 DEG C；Time of contact is usually 1 minute -20 Hour, preferably -6 hours 5 minutes.

3）Method three：The alcohol adducts of magnesium dihalide are suspended in inert diluent and form suspension, then this is suspended Liquid contacts to obtain solids dispersion, hereinafter known as mother liquor with above-mentioned titanium compound, internal electron donor a and b mixing.By mother Liquid is filtered, and gained solid matter is suspended in progress contact processing in the solution containing titanium tetrachloride, and hereinafter known as titanium is handled；Then Through filtering, washing can be prepared by the catalyst solid constituent of the present invention.

The alcohol adducts of magnesium dihalide can be made by the following method described in the above method three：Mixed not with adduct Molten atent solvent（Such as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene）In the presence of, by alcohol（As methanol, ethanol, Propyl alcohol or isopropanol etc.）Emulsion is mixed to form with magnesium halide, disperses the rapid chilling of the emulsion, gained spheric granules is dihalo- Change the alcohol adducts of magnesium.

In the above method three inert diluent used in the formation of mother liquor can using hexane, heptane, octane, decane, benzene, At least one of toluene and dimethylbenzene.

The consumption of each composition used in the formation of mother liquor in method three, in terms of every mole of magnesium elements, titanium compound makes 0.5-100 moles of consumption, preferably 1-50 moles；The usage amount of inert diluent is usually 0.5-100 moles, preferably 1-50 Mole；Interior electron donor a and b total amount is usually 0.005-10 moles, preferably 0.01-1 moles.

The Contact Temperature of each component is usually -40 DEG C to 200 DEG C during the formation of mother liquor in method three, is preferably -20 DEG C to 150 DEG C；Time of contact is usually -20 hours 1 minute, preferably -8 hours 5 minutes.

Described in method three in titanium processing procedure, alternative addition inert diluents in the solution containing titanium tetrachloride are used At least one of agent, such as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.

In method three in titanium processing procedure, the consumption containing each composition in titanium tetrachloride solution is used, with every mole of magnesium member Element meter, preferably 0.5-100 moles of the usage amount of titanium compound, 1-50 moles；The usage amount of inert diluent is usually 0-100 Mole, preferably 0-50 moles.

Titanium number of processes is 0-10 times, preferably 1-5 times in method three.

In method three in titanium processing procedure, alternative adds above-mentioned interior electron donor a and b, wherein internal electron donor a and B total consumption is usually 0.005-10 moles, preferably 0.01-1 moles.

Titanium treatment temperature is usually 0-200 DEG C in method three, preferably 30-150 DEG C；Time of contact is usually 1 minute -20 Hour, preferably -6 hours 5 minutes.

, according to the invention it is preferred in the case of, aluminium element and the organo-silicon compound C in the organo-aluminum compound B The mol ratio Al/Si of middle element silicon is 0.1-500:1；Preferably, Al/Si is 1-300:1；It is highly preferred that Al/Si is 3-100: 1。

, according to the invention it is preferred in the case of, aluminium element and the catalyst solid constituent in the organo-aluminum compound B The mol ratio Al/Ti of titanium elements in A is 5-5000:1；Preferably, Al/Ti is 20-1000:1；It is highly preferred that Al/Ti is 50-500:1。

According to the present invention, it is neat that the organo-aluminum compound B can be that commonly use in field of olefin polymerisation various can act as The organo-aluminum compound of the co-catalyst of Ge Le-Natta catalyst.Under preferable case, the organo-aluminum compound B can be Formula（VI）Shown compound,

AlR'_yX'_3-yFormula（V）

Formula（V）In, R' can be the aryl of hydrogen, C1-C20 alkyl or C6-C20, and X' is halogen, and y is 1-3 integer.

Preferably, the organo-aluminum compound B can be selected from least one of following compound：Trimethyl aluminium, three second Base aluminium, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, the isobutyl of a chlorine two Base aluminium, sesquialter ethylmercury chloride aluminium or ethyl aluminum dichloride；More preferably triethyl aluminum and/or triisobutyl aluminium.

According to the present invention, the organo-silicon compound C is formula（VI）Shown silicon-containing compound and/or formula（VII）Shown ammonia Base silane,

R¹″_m″R²″_n″Si(OR³″)_4-m″-n″Formula（VI）

Wherein, R¹" and R²" to be identical or different, and the one kind being each independently selected from following functional group：Halogen, hydrogen are former Son, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；R³" one in following functional group Kind：C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；M " and n " is respectively 0-3 integer, And m "+n "<4；

R¹″′_m″′Si(N R²″′R³″′)_n″′(OR⁴″′)_{4-m″′-n″′}Formula（VII）

Wherein, R¹" ' one kind in following functional group：Halogen, hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；R²" ' and R³" ' be is identical or different, and is each independently selected from following functional group One kind：Hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；R⁴" ' selected from following One kind in functional group：C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；M " ' is 0-3's Integer, n " ' be 1-3 integer.

Preferably, formula（VI）Shown silicon-containing compound is selected from least one of following compound：Trimethyl methoxy silicon Alkane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, two tertiary fourths Base dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tert-butyl group dimethylamine oxygen Base silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, Cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, two rings Dicyclopentyldimetoxy silane, cyclopentyl cyclohexyl dimethoxysilane, double (2- methylcyclopentyls) dimethoxysilanes, diphenyl Dimethoxysilane, diphenyl diethoxy silane, phenyl triethoxysilane, MTMS, the ethoxy of methyl three Base silane, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, Isopro-pyltriethoxysilane, butyl trimethoxy silane, butyl triethoxysilane, trimethoxysilane, isobutyl Ethyl triethoxy silicane alkane, amyltrimethoxysilane, isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl Trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, the second of phenyl three TMOS, vinyltrimethoxy silane, VTES, tetramethoxy-silicane, tetraethoxysilane or four Butoxy silane；

It is highly preferred that formula（VI）Shown silicon-containing compound is selected from least one of following compound：Bicyclopentyl two Methoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, Dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, propyl-triethoxysilicane, isobutyl triethoxy silane Or tetraethoxysilane.Particularly preferred formula（VI）Shown silicon-containing compound is selected from least one of following compound：Propyl group Triethoxysilane, isobutyl triethoxy silane or tetraethoxysilane.

Preferably, formula（VII）Shown amino silane compounds are selected from least one of following compound：Diethylamino Triethoxysilane, double (diethylamino) diisoamyl silane, double (trans- perhydro quinolyl) dimethoxysilanes are double (cis- Be all-trans quinolyl) dimethoxysilane, double (ethylamino) bicyclopentyl silane；Particularly preferred diethyl amino ethyl triethoxy silicane Alkane.

According to organo-silicon compound C of the present invention, can be above-mentioned organo-silicon compound C be used alone or Two or more above-mentioned organo-silicon compound C compound use.

In the present invention, a kind of preferred embodiment, the temperature of the polymerisation is 85-95 DEG C；The olefinic polymerization is urged Agent contains catalyst solid constituent A, organo-aluminum compound B and organo-silicon compound C；Wherein, the organo-silicon compound C is N-propyl triethoxysilane, diisopropyl dimethoxy silane, diethylamino triethoxysilane and diisobutyl diformazan At least one of TMOS, the internal electron donor a is 2,3- diisopropyl -2- cyano group diethyl succinate, 2,3- bis- Isopropyl butanedioic acid diethyl ester, 2,4-PD dibenzoate, 3,5- heptandiols dibenzoate and 4- ethyls -3,5- heptan At least one of bisbenzoate, the internal electron donor b is diethyl phthalate, the positive fourth of phthalic acid two In ester, diisobutyl phthalate, DHP, dibutyl phthalate (DHP) and diisooctyl phthalate At least one；Also, the internal electron donor a and internal electron donor b weight ratio is 0.05-0.43:1, it is described to have The mol ratio of aluminium and the organo-silicon compound C in machine aluminium compound B is 3-100:Aluminium in 1, the organo-aluminum compound B Mol ratio with the titanium in the catalyst solid constituent A is 50-500:1.Polymerization formula CH2=CHR can be more beneficial for represent Alkene when obtain have high melt flow rate (MFR), high isotactic, while the wide olefin polymer of molecular weight distribution.

According to the present invention, the olefin polymerization process can include the alkene for making one or more alkene be provided with the present invention Polymerization catalyst is contacted, and at least one of described alkene is by formula CH₂The alkene that=CHR is represented, wherein, R can for hydrogen or C1-C6 alkyl；Preferably, the alkene can be selected from following at least one：Ethene, propylene, 1- n-butenes, 1- positive penta Alkene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene；It is highly preferred that the alkene can be selected from ethene, propylene and 1- fourths At least one of alkene.

The homopolymerization of the alkene can be carried out in the present invention, the combined polymerization of the alkene can also be carried out.

Polymeric reaction temperature is improved in certain limit, the hydrogen response of catalyst can be improved, i.e., identical hydrogen usage When polymer melt flow rate (MFR) increase, this is conducive to preparing high melt-flow-rate-polymer of the present invention.In addition, Polymeric reaction temperature is improved in certain limit, polymer isotacticity can also increase, be conducive to polymer to obtain preferably firm Property.However, polymeric reaction temperature can not be raised significantly；For catalyst solid constituent of the present invention, when polymerization temperature liter After high to more than 95 DEG C, although catalyst hydrogen response is further improved, but polymerization activity declines to a great extent, and polymer isotactic Index also begins to that downward trend is presented.Therefore, according to application of the present invention, the temperature of the olefin polymerization process is 85- 130 DEG C, more preferably preferably 85-110 DEG C, 85-95 DEG C.

In addition to polymerization temperature, other conditions of olefin polymerization process of the present invention can be that polymerization time is 0.1-5 Hour, pressure is 0.01-10MPa.Preferably the time is 0.5-4 hours, and pressure is 0.5-5MPa.The olefin polymerization catalysis Consumption can for prior art catalyst consumption.

In the present invention, methods described can also be included the olefin polymerization catalysis each component of the present invention, i.e., institute of the present invention Catalyst solid constituent A, organo-aluminum compound B and the organo-silicon compound C stated first carries out pre-terminated before contact olefinic monomer Touch or pre- complexing, then contact progress polymerisation with olefinic monomer again.The time of pre-contact is 0.1-30min, preferably 1-10 Minute；The temperature of pre-contact is -20 DEG C to 80 DEG C, preferably 10 DEG C -50 DEG C.

In the present invention, the application can also include the olefin polymerization catalysis by the present invention first in a small amount of olefinic monomer In the presence of carry out prepolymerization and obtain pre-polymerized catalyst, then pre-polymerized catalyst further contact into progress instead with olefinic monomer Should.

The prepolymerization contributes to raising of polymerization catalyst activity and polymer bulk density etc..According to of the present invention Application, can use the prepolymerization, the prepolymerization can not also be used.

It is preferred to use the prepolymerization.The prepolymerized multiplying power, can be used by monomer during progress prepolymerization and Ben Fa The inventory of the olefin polymerization catalysis of bright offer is calculated as polymer（Such as polypropylene PP）Mass ratio with catalyst is 2- 3000gPP/gCat, preferably 3-2000gPP/gCat；Prepolymerized temperature is -20-80 DEG C, preferably 10-50 DEG C.

In the present invention, a kind of preferred embodiment, application of the olefin polymerization catalysis in olefin polymerization process can With including pre- complexing, prepolymerization and olefinic polymerization.

Present invention also offers polyolefin made from method provided by the present invention, the polyolefin is polypropylene, polypropylene Melt flow rate (MFR) MFR be more than 45g/10min, M_Z+1/ Mn is more than 45, and isotactic index II is more than 94.5%；Preferably, Melt flow rate (MFR) MFR is 60-120g/10min, M_Z+1/ Mn is 60-80, and isotactic index II is 95.5-97%.

In the present invention, gel permeation chromatography commonly used in the art can be used（GPC）Characterize the molecule of polymer Amount distribution.Characterized with GPC, the weight average molecular weight Mw, number-average molecular weight Mn, Z-average molecular weight M of polymer can be obtained_ZAnd M_Z+1.It is logical Conventional Mw/Mn represents the molecular weight distribution of polymer, and its value is bigger, molecular weight distribution is wider.Because number-average molecular weight is to small Molecular weight fractions are more sensitive, and Z-average molecular weight is more sensitive to macromolecule part, for special catalyst of the present invention System, using M_Z+1/ Mn can preferably reflect polymer prepared by the olefin polymerization catalysis that provides of the present invention in wide molecular weight Advantage in terms of distribution.

The present invention will be described in detail by way of examples below.

Test and evaluation in following examples are carried out by the following method：

1）Ti content in catalyst solid constituent in terms of titanium elements is by 721 spectrophotometers（An He alliances（Tianjin）Science and technology Development Co., Ltd）Determine；

2）The melt flow rate (MFR) of polymer（Melt index）It is to use to be purchased from the limited public affairs of the new experimental instrument and equipment in Changchun The model XRZ-00 fusion index instruments of department method according to specified in GB/T3682-2000 is determined；

3）Malvern Mastersizer^TM2000 n-hexane dispersant laser diffractometries measure alkoxyl magnesium and catalyst Grain size, size distribution（Wherein, SPAN=（D90-D10）/D50）.

4）In catalyst component for olefin polymerization internal electron donor content be measured using Waters600E liquid chromatograies or Agilent7890 gas Chromatographic Determinations.

5）Polymer molecular weight distribution MWD（MWD=Mw/Mn）Assay method include：PL-GPC220 is used with trichloro-benzenes It is measured for solvent at 150 DEG C（Standard specimen：Polystyrene, flow velocity：1.0ml/min, pillar：3xPlgel10um MlxED- B300x7.5nm）.

6）The method of testing of polymer isotacticity includes：2 grams of dry polymer samples, were placed in extractor with heptan of seething with excitement After alkane is extracted 6 hours, by residue drying to constant weight, isotacticity is calculated by below equation：

Isotacticity（%）Polymer quality/2 × 100 after=extracting.

Preparation example 1

This preparation example prepares alkoxyl magnesium carrier for explanation.

Be sufficiently displaced from nitrogen after the 16L voltage-resistant reactors with agitator, added into reactor 10L ethanol, 300mL2- ethyl hexanols, 11.2g iodine, 8g magnesium chlorides and 640g magnesium powders.Stirring makes system be warming up to 75 DEG C of back flow reactions simultaneously, Untill there is no hydrogen discharge.Stop reaction, washed with 3L ethanol, filter, dry, obtain alkoxyl magnesium carrier a1.Institute Obtain alkoxyl magnesium carrier D50=30.2um, Span values 0.81.

Preparation example 2

This preparation example prepares catalyst solid constituent A0 for explanation.

Take 650g alkoxyl magnesium carriers a1, toluene 3250mL and 2- cyano group -2,3- diisopropyl diethyl succinates（With reference to It is prepared by the preparation method in CN101811983A）72mL is configured to suspension.It is pressure-resistant in the 16L that displacement is repeated by high pure nitrogen In reactor, toluene 2600mL and titanium tetrachloride 3900mL is added, 80 DEG C are warming up to.Then the suspension prepared is added into kettle In, constant temperature 1 hour, then 2- cyano group -2,3- diisopropyl diethyl succinate 108mL are added into reactor, it is to slowly warm up to 110 DEG C, constant temperature 2 hours, press filtration obtains solid content.Gained solid content adds toluene 5070mL and titanium tetrachloride 3380mL mixed liquor In 110 DEG C of stir process 1 hour, it is processed as 3 times.Press filtration, the solid of gained is washed 4 times with hexane, each 6000mL, pressure Filter, dry, produce catalyst solid constituent A0.The Ti content counted in gained catalyst solid constituent A0 using titanium elements is 3.2 weight % is measured, 2- cyano group -2,3- diisopropyl diethyl succinates content is 7.9 weight %.

Preparation example 3

This preparation example prepares catalyst solid constituent B0 for explanation.

According to the method for preparation example 2, unlike, " 2- cyano group -2,3- diisopropyls diethyl succinate " is changed into " adjacent Phthalic acid di-n-butyl ".

The Ti content counted in gained catalyst solid constituent B0 using titanium elements is 2.7 weight %, n-butyl phthalate Content is 10.8 weight %.

Preparation example 4

This preparation example prepares catalyst solid constituent A1 for explanation.

According to the method for preparation example 2, unlike, " 2- cyano group -2,3- diisopropyls diethyl succinate " is changed into " 3, 5- heptandiol dibenzoates（Prepared with reference to preparation method in CN1213080C）”.

The Ti content counted in gained catalyst solid constituent A1 using titanium elements is 3.8 weight %, 3,5- heptandiol dibenzoic acids Ester content is 7.5 weight %.

Preparation example 5

This preparation example prepares catalyst solid constituent A2 for explanation.

According to the method for preparation example 2, unlike, " 2- cyano group -2,3- diisopropyls diethyl succinate " is replaced with " 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes（Prepared with reference to preparation method in CN1036846C）”.

Titanium atom content is 2.5 weight %, 2- isopropyl -2- isopentyl -1,3- diformazans in gained catalyst solid constituent A2 Epoxide propane content is 13.4 weight %.

Evaluate example

This evaluation example is used for the evaluation and selection for illustrating internal electron donor a, b.

5 liters of autoclaves for being connected with catalyst feeder, propylene and hydrogen feed line are sufficiently displaced from gas-phase propene.Room The hexane solution of 5mL triethyl aluminums is added under temperature into catalyst feeder（The concentration of triethyl aluminum is 0.5mol/L）, 1mL has The hexane solution of organic silicon compound（Concentration is 0.1mol/L）, 10mL anhydrous hexanes and catalyst solid constituent（Make wherein with titanium The Ti content of element meter and the mol ratio of triethyl aluminum are 500:1）, mix 2 minutes（Pre- complexing）After be added to autoclave.Close Autoclave, introduces 4.0 standards and rises hydrogen and 2.0L liquid propene；Temperature is risen to 70 DEG C in 20 minutes under agitation.70 Polymerisation stops stirring after 1 hour at DEG C, removes unpolymerized propylene monomer, and collection obtains polymer P.

Polymerization activity, the polymer molten fluid of catalyst solid constituent A0, A1, A2, B0 in different organo-silicon compound C Dynamic speed（MFR）, polymer isotacticity（II）It is shown in Table 1.The polymerization activity of wherein catalyst is calculated by following formula：

Polymerization activity=polymer P quality（Kilogram）/ catalyst solid constituent quality（g）

Table 1

Polymer MFR of the different catalysts solid constituent in table 1 when using DCPDMS and TEOS is calculated Catalyst solid constituent A0, A1, A2'sValue is with catalyst solid constituent B0'sValue, can reflect containing not Catalyst with internal electron donor a or b is to external electron donor（That is organo-silicon compound）Responding ability, be specifically shown in Table 2.

Table 2

The data in Tables 1 and 2, catalyst solid constituent A0, A1, A2 respond especially unwise to external electron donor Sense, i.e.,And catalyst solid constituent B0 is especially sensitive to external electron donor response, i.e.,I.e. Internal electron donor a used is 2- cyano group -2,3- diisopropyls diethyl succinate, 3,5- heptandiol dibenzoic acids in A0, A1, A2 Ester, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes respond insensitive to external electron donor；And used in B0 it is interior to Electron b is that dibutyl phthalate responds sensitivity to external electron donor.Therefore, 2- cyano group -2,3- diisopropyl succinic acid Diethylester, 3,5- heptandiols dibenzoate, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes meet as the present invention Electron donor a condition in the catalyst solid constituent；And n-butyl phthalate then meets as of the present invention Electron donor b condition in catalyst solid constituent.

In addition, data can also be seen that when making external electron donor using n-PTES in Tables 1 and 2, A0 MFR11 （Evaluate example 3）With B0 MFR21（Evaluate example 11）Ratio be 11.6, meetCondition, then used in A0 2- cyano group -2,3- diisopropyl diethyl succinates may be used as internal electron donor a in the present invention, and the adjacent benzene two in B0 Formic acid di-n-butyl can be used as the internal electron donor b in the present invention.However, A2 MFR11 under the same conditions（Evaluate example 8）For 46.4, itself and B0 MFR21 ratio are 2.3, are unsatisfactory forMore it is unsatisfactory forCondition, therefore 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes cannot act as the internal electron donor a in the present invention.

Preparation example 6-7 is used for the catalyst solid for illustrating to prepare using the internal electron donor a and b that are determined by above-mentioned evaluation example Component.

Preparation example 6

This preparation example prepares catalyst solid constituent A11 for explanation.

Take 650g alkoxyl magnesium carriers a1, toluene 3250mL and 2- cyano group -2,3- diisopropyl diethyl succinates 32mL It is configured to suspension.In the pressure-resistant reactors of 16L of displacement are repeated by high pure nitrogen, toluene 2600mL and titanium tetrachloride are added 3900mL, is warming up to 80 DEG C, then adds the suspension prepared in kettle, constant temperature 1 hour, then the adjacent benzene of addition into reactor Dioctyl phthalate di-n-butyl 148mL, is to slowly warm up to 110 DEG C, constant temperature 2 hours, and press filtration obtains solid content.Gained solid content adds toluene 5070mL and titanium tetrachloride 3380mL mixed liquor were processed as 3 times in 110 DEG C of stir process 1 hour.Press filtration, gained is consolidated Body is washed 4 times with hexane, each 6000mL, and press filtration, drying produce catalyst solid constituent A11.Gained catalyst solid constituent The titanium atom content counted in A11 using titanium elements is as 3.3 weight %, 2- cyano group -2,3- diisopropyl diethyl succinate contents 1.1 weight %, n-butyl phthalate content is 6.7 weight %.

Preparation example 7

This preparation example prepares catalyst solid constituent A12 for explanation.

In the reactor of displacement is repeated by High Purity Nitrogen, 52.5mmol anhydrous magnesium chlorides, 328mmol toluene are sequentially added With 140mmol2- ethyl hexanols, under conditions of speed of agitator 450rpm, temperature is 110 DEG C, react 3.0 hours, obtain stabilization Uniform alcohol adduct solution；Add 3,5- heptandiol dibenzoates 0.8mmol, diisobutyl phthalate 5.6mmol With butyl titanate 2.2mmol, stir 60 minutes, be cooled to room temperature, obtain mixture.

Said mixture is added to and is sufficiently displaced from through nitrogen, equipped with -20 DEG C of 1.0mol titanium tetrachlorides and 190mmol first In the reactor of benzene, them is fully contacted at -20 DEG C by stirring, after 5 hours, be warming up to 110 DEG C, in temperature-rise period Solid precipitation is separated out, diisobutyl phthalate 5.6mmol is added, reacted 1 hour, after reaction terminates, liquid is filtered out Obtain solid；Obtained solid is contacted 1 hour, after filtering with 680mmol toluene and 437mmol titanium tetrachlorides at 110 DEG C Repeat and reacted once with the Solids At Low Temperatures at 110 DEG C with 680mmol toluene and 437mmol titanium tetrachlorides.By consolidating for obtaining Body thing is washed 5 times with 919mmol hexanes, is then dried, and obtains catalyst solid constituent A12.In catalyst solid constituent A12 The Ti content counted using titanium elements is 2.2 weight %, and 3,5- heptandiol dibenzoic acid ester contents are 2.1 weight %, phthalic acid two Isobutyl ester content is 9.1 weight %.

Example 1 below -6 is used to illustrate prepared by the catalyst solid constituent A11 and A12 that select preparation example 6-7 to obtain Olefin polymerization catalysis prepares polyacrylic method.

Embodiment 1

3.5 liters of autoclaves for being connected with catalyst feeder, propylene and hydrogen feed line are sufficiently displaced from gas-phase propene. Introduce 4.0 standards and rise hydrogen and 2.0L liquid propene.The hexane for being separately added into 5mL triethyl aluminums into autoclave at room temperature is molten Liquid（The concentration of triethyl aluminum is 0.5mol/L）, 1mL n-propyl triethoxysilanes（n-PTES）Hexane solution（N-PTES's Concentration is 0.1mol/L）, 10mL anhydrous hexanes and catalyst solid constituent A11（Make the Ti content wherein in terms of titanium elements and three The mol ratio of aluminium ethide is 500:1）, 300mL propylene flushing catalyst addition tube line.Autoclave is closed, 5 points are stirred at room temperature Clock（Equivalent to pre-polymerization）；Temperature is risen to 85 DEG C in 20 minutes under agitation.Polymerisation stops stirring after 1 hour at 85 DEG C, Unpolymerized propylene monomer is removed, collection obtains polymer P.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Embodiment 2

According to the method for embodiment 1, unlike, with " diisopropyl trimethoxy silane/n-propyl triethoxysilane （1/9mol/mol）" replacement " n-propyl triethoxysilane（n-PTES）”.Propylene polymerization is carried out, the polymerization that polymerization is obtained is collected Produce product.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Embodiment 3

According to the method for embodiment 1, unlike, with " diethylamino triethoxysilane（With reference to CN100427513C It is prepared by middle preparation method）" replacement " n-propyl triethoxysilane ", " introduce 4.1 to mark with " introduce 1.8 standards and rise hydrogen " replacement Standard rises hydrogen ".Propylene polymerization is carried out, the polymeric articles that polymerization is obtained are collected.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Comparative example 1

According to the method for embodiment 1, unlike, with " catalyst solid constituent A0 " substitutes " catalyst solid constituent A11”.Propylene polymerization is carried out, the polymeric articles that polymerization is obtained are collected.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Comparative example 2

According to the method for embodiment 1, unlike, with " catalyst solid constituent B0 " substitutes " catalyst solid constituent A11”.Propylene polymerization is carried out, the polymeric articles that polymerization is obtained are collected.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Embodiment 4

3.5 liters of autoclaves for being connected with catalyst feeder, propylene and hydrogen feed line are sufficiently displaced from gas-phase propene. The hexane solution of 5mL triethyl aluminums is added into catalyst feeder at room temperature（The concentration of triethyl aluminum is 0.5mol/L）、1mL Diisopropyl dimethoxy silane（DIPDMS）Hexane solution（DIPDMS concentration is 0.1mol/L）, 10mL anhydrous hexanes and Catalyst solid constituent A12（Make the mol ratio for the Ti content and co-catalyst wherein counted using titanium elements as 500:1）, mix 2 points Clock（Pre- complexing）After be added to autoclave.Autoclave is closed, 4.0 standards is introduced and rises hydrogen and 2.0L liquid propene；In room temperature Lower stirring 5 minutes（Equivalent to pre-polymerization）；Temperature is risen to 95 DEG C in 20 minutes under agitation.Polymerisation 1 hour at 95 DEG C Afterwards, stop stirring, remove unpolymerized propylene monomer, collection obtains polymer P.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Embodiment 5

According to the method for embodiment 3, unlike, with " 2.7 standards rise hydrogen " replacement " 1.8 standards rise hydrogen ", with " two Isobutyl group dimethoxysilane " replacement " diisopropyl dimethoxy silane ".Propylene polymerization is carried out, the polymerization that polymerization is obtained is collected Produce product.

Calculating obtains polymer.Polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And it is poly- Compound bulk density（BD）, molecular weight distribution, as a result as shown in table 3.

Embodiment 6

According to the method for embodiment 3, unlike, with " diisoamyl dimethoxysilane/tetraethoxysilane（1/ 9mol/mol）" replacement " diisopropyl dimethoxy silane ".Propylene polymerization is carried out, the polymeric articles that polymerization is obtained are collected.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Comparative example 3

According to the method for embodiment 1, unlike, with " catalyst solid constituent A1 " substitutes " catalyst solid constituent A11”.Propylene polymerization is carried out, the polymeric articles that polymerization is obtained are collected.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Comparative example 4

According to the method for embodiment 1, unlike, with " catalyst solid constituent A12 " substitutes " catalyst solid constituent A11 ", with " 70 DEG C of polymerization temperature " replacement " 85 DEG C of polymerization temperature ".Propylene polymerization is carried out, the polymerization produce that polymerization is obtained are collected Product.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

Comparative example 5

According to the method for comparative example 4, unlike, with " catalyst solid constituent A12 " substitutes " catalyst solid constituent A11”；With " 1mL diisopropyl dimethoxy silanes " replacement " 1mL n-propyl triethoxysilanes（n-PTES）”.Carry out propylene Polymerization, collects the polymeric articles that polymerization is obtained.

Calculate polymerization activity, melt flow rate（MFR）, polymer isotacticity（II）And polymer bulk density （BD）, molecular weight distribution, as a result as shown in table 3.

From table 3, the preparation method of the olefin polymer provided using the present invention can be containing specific interior to electricity Daughter a and b and a：, will be logical in the presence of olefin polymerization catalysis of the b weight than specific and specific organo-silicon compound C Formula CH₂The alkene that=CHR is represented is polymerize in single reactor at high temperature, and prepare has high melt flow rate (MFR) simultaneously （MFR>45g/10min）, wide molecular weight distribution（M_Z+1/Mn>45）It is high with isotactic index（>94.5%）Polymeric articles.And In comparative example 1-3, specific olefin polymerization catalysis is not used（Only internal electron donor a or b）, or in comparative example 4-5 gather Close reaction not carry out at high temperature, then melt flow rate (MFR) occurs in the polymeric articles obtained（Comparative example 1 and 5）, molecular weight Distribution（Comparative example 2）Or isotactic index（Comparative example 3 and 4）The deficiency of aspect, i.e., can not obtain while having high melt flows speed Rate, wide molecular weight distribution, and the high polymeric articles of isotactic index.

Claims (13)

1. a kind of preparation method of olefin polymer, this method includes, in the presence of olefin polymerization catalysis, by formula CH₂= The alkene that CHR is represented carries out polymerisation；The olefin polymerization catalysis contains catalyst solid constituent A, organo-aluminum compound B With organo-silicon compound C；The catalyst solid constituent A contains magnesium, titanium, halogen, internal electron donor a and internal electron donor b, institute The weight ratio for stating the internal electron donor a and internal electron donor b is less than 1:1；

Wherein, the internal electron donor a and the internal electron donor b meet following condition：In polymerizing condition, organo-aluminum compound In the case of B and organo-silicon compound C identicals during polypropylene, by being only urging for the internal electron donor a containing internal electron donor Agent solid constituent A0, the organo-aluminum compound B and the organo-silicon compound C composition polymerization catalyst obtain poly- third The melt flow rate (MFR) MFR11 of alkene and catalyst solid constituent B0, institute by containing internal electron donor being only the internal electron donor b State the polyacrylic melt flow rate (MFR) that the polymerization catalyst of organo-aluminum compound B and organo-silicon compound C compositions is obtained MFR21 is metMelt flow rate (MFR) MFR21 and the MFR11 method according to specified in GB/T3682-2000 are surveyed It is fixed；

The temperature of the polymerisation is 85-130 DEG C；

The internal electron donor a is in compound shown in formula (I), compound shown in formula (II) and compound shown in formula (III) At least one, the internal electron donor b is compound shown in formula (IV),

In formula (I)：R₁And R₂It is identical or differ, and it is each independently alkyl, the C3-C10 of hydrogen or C1-C14 straight or brancheds Cycloalkyl, C6-C10 aryl, C7-C10 alkaryls or C7-C10 aralkyl；R₃And R₄It is identical or differ, and be each independently Alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls or the C7-C20 aralkyl of C1-C10 straight or brancheds；

In formula (II)：R₅And R₆It is identical or differ, and it is each independently the alkyl of C1-C10 straight or brancheds, C3-C10 rings Alkyl, C6-C20 aryl, C7-C20 alkaryls or C7-C20 aralkyl, optionally contain hetero atom；R₇-R₁₀It is identical or differ, And it is each independently alkyl, C2-C14 alkylenes, C3-C10 cycloalkyl, the C6-C10 virtues of hydrogen or C1-C14 straight or brancheds Base, C7-C10 alkaryls or C7-C10 aralkyl；Work as R₇-R₉When being all hydrogen simultaneously, R₁₀Uncle position selected from C3-C20 is branched secondary Alkyl, tertiary alkyl, cycloalkyl, aryl, aryl alkyl or alkylaryl；

In formula (III)：R₁₁And R₁₂It is identical or differ, and it is each independently selected from halogen, substituted or unsubstituted straight chain or branch C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, the C2-C10 alkylenes of chain Or C10-C20 fused ring aryls；R₁₃-R₁₈It is identical or differ, and be each independently selected from hydrogen, it is halogen, substituted or unsubstituted straight C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, the C2-C10 of chain or side chain Alkylene or C10-C20 fused ring aryls, or optionally R₁₃-R₁₈In at least two link up cyclization；

In formula (IV)：R₁₉And R₂₀It is identical or differ, and it is each independently the alkyl of C1-C12 straight or brancheds, C3-C10 rings One kind in alkyl and C6-C20 alkaryls, substitution or unsubstituted aryl；R₂₁-R₂₄All hydrogen, or wherein three be Hydrogen, another is one kind in the alkoxy of halogen, the alkyl of C1-C4 straight or brancheds and C1-C4 straight or brancheds.

2. according to the method described in claim 1, wherein, the temperature of the polymerisation is 85-110 DEG C.

3. method according to claim 2, wherein, the temperature of the polymerisation is 85-95 DEG C.

4. according to the method described in claim 1, wherein, the internal electron donor a and internal electron donor b weight ratio is 0.05-0.43:1。

5. according to the method described in claim 1, wherein,

6. according to the method described in claim 1, wherein, aluminium element in the organo-aluminum compound B with it is described siliconated The mol ratio of element silicon in compound C is 0.1-500:Aluminium element in 1, the organo-aluminum compound B is consolidated with the catalyst The mol ratio of titanium elements in body component A is 5-5000:1.

7. according to the method described in claim 1, wherein, on the basis of the gross weight of the catalyst solid constituent A, described In catalyst solid constituent A, the Ti content in terms of titanium elements is that 1-8 weight %, the content of magnesium in terms of magnesium elements are 10-70 weights Amount %, the content of halogen counted using halogens as 20-85 weight %, the total amount of the internal electron donor a and internal electron donor b Content is 2-30 weight %.

8. according to the method described in claim 1, wherein, the internal electron donor a be 2- cyano group -2,3- diisopropyl succinic acid Diethylester, 2,3- diisopropyl butanedioic acids diethyl ester, 2,4-PD dibenzoate, 3,5- heptandiols dibenzoate and At least one of 4- ethyl -3,5- heptandiol dibenzoates.

9. according to the method described in claim 1, wherein, the internal electron donor b be diethyl phthalate, O-phthalic Sour di-n-butyl, diisobutyl phthalate, DHP, dibutyl phthalate (DHP) and phthalic acid two At least one of different monooctyl ester.

10. the method according to any one in claim 1-7, wherein, the organo-aluminum compound B is shown in formula (V) Compound,

AlR′_yX′_3-yFormula (V)

In formula (V), R ' is the aryl of hydrogen, C1-C20 alkyl or C2-C20, and X ' is halogen, and y is 1-3 integers.

11. according to the method described in claim 1, wherein, the organo-silicon compound C be silicon-containing compound shown in formula (VI) And/or amino silane shown in formula (VII),

R¹”_m”R²”_n”Si(OR³”)_4-m”-n”Formula (VI)

Wherein, R¹" and R²" to be identical or different, and the one kind being each independently selected from following functional group：Halogen, hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；R³" one kind in following functional group： C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；M " and n " is respectively 0-3 integer, and m " +n”<4；

R¹”'_m”'Si(N R²”'R³”')_n”'(OR⁴”')_{4-m”'-n”'}Formula (VII)

Wherein, R¹" ' one kind in following functional group：Halogen, hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 Aryl or C1-C20 haloalkyls；R²" ' and R³" ' to be identical or different, and one be each independently selected from following functional group Kind：Hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；R⁴" ' it is selected from following function One kind in group：C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl or C1-C20 haloalkyls；M " ' is 0-3 integer, N " ' is 1-3 integer.

12. according to the method described in claim 1, wherein, the catalyst solid constituent is titanium compound, magnesium compound, interior Electron donor a and internal electron donor b reaction product.

13. according to the method described in claim 1, wherein, time of the polymerisation is 0.1-5 hour, and the polymerization is instead The pressure answered is 0.01-10MPa.