CN109111537A

CN109111537A - Catalytic component and its catalyst for olefinic polymerization

Info

Publication number: CN109111537A
Application number: CN201710484889.9A
Authority: CN
Inventors: 张锐; 谭忠; 周奇龙; 徐秀东; 尹珊珊; 李凤奎; 于金华; 宋维玮
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: 2017-06-23
Filing date: 2017-06-23
Publication date: 2019-01-01
Anticipated expiration: 2037-06-23
Also published as: CN109111537B

Abstract

The present invention relates to a kind of catalytic components and its catalyst for olefinic polymerization.The catalytic component includes magnesium, titanium, halogen and internal electron donor compound, wherein the internal electron donor compound includes 2- carbonic ester phenyl ketone compounds shown at least one logical formula (I).Have the advantages that hydrogen regulation performance is good, polymerization activity is high and stereotaxis ability is good etc. provided by the present invention for the catalyst of olefinic polymerization.When catalyst of the invention is used for olefin polymerization, resulting polymers have preferable isotacticity, higher melt index, wider molecular weight distribution and higher bulk density.New catalyst provided by the invention has excellent comprehensive performance, has wide application prospect.

Description

Catalytic component and its catalyst for olefinic polymerization

Technical field

The invention belongs to catalyst technical fields, and in particular to a kind of catalytic component and its catalysis for olefinic polymerization Agent.

Background technique

It is using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basis, i.e., known in the field Ziegler-Natta catalyst can be used for CH2=CHR olefin polymerization, especially have 3 carbon or more Alpha-olefine polymerizing in available higher yields and higher stereospecificity polymer.Wherein, internal electron donor compound It is one of essential ingredient in Ziegler-Natta catalyst component.Since second generation Z-N catalyst, every generation is urged The development of agent is all with the successful application of novel internal electron donor for mark, from monocarboxylic acid esters compound, such as benzene first Acetoacetic ester, to binary aromatic carboxylic acid's ester type compound widely used at present, such as n-butyl phthalate or adjacent benzene first Sour diisobutyl ester, then to 1,3-, bis- ethers (CN1020448C), succinate compound (CN1313869) and 1,3- diol-lipid (CN1213080C) compound, internal electron donor can assign catalyst different property, and also exactly the development of internal electron donor promotees Polyolefin catalyst has been set to be continuously updated the replacement.

In addition to above a few class electron donor compounds, in recent years, a kind of internal electron donor containing carbonate group is obtained More and more concerns, CN102762603A and CN102712704A provide intramolecular and contain change there are two carbonate group Close polyolefin catalyst of the object as internal electron donor, mainly aromatic catechol, pair of naphthalenediol and '-biphenyl diphenol Carbonic ester.Interior electron in WO2015185495A1 also contains double manganese ester group, is double carbonic acid of 2,4- pentanediol structure Ester.In addition to double manganese ester compound, the internal electron donor in molecule simultaneously containing carbonate group and other functional groups also has report Road contains carbonate group and ehter bond in the internal electron donor that CN103764689A is provided, has been separated by two between two groups Carbon atom.It is reported respectively in EP2636687A1 and WO2015185489A1 simultaneously containing carbonate group and alcohol ester group Compound and contain the compound of carbonate group and amide ester group simultaneously as electron donor, compound is all by aliphatic Glycol is obtained as initial feed reaction.But these compounds for containing carbonate group have as internal electron donor Certain deficiency, such as cost of material is higher, molecular weight distribution is not wide (CN102762603A, CN102712704A), melting Index is lower (CN103764689A), or active too low (WO2015185495A1, WO2015185489A1).

Although having done a large amount of research work in Ziegler-Natta catalyst field, for preparing higher performance It is required that Ziegler-Natta catalyst, it is still desirable to some new or improved method.Therefore, presently, there are the problem of be Urgent need researchs and develops that a kind of activity is high, stereoselectivity is good, hydrogen response is good and the use of polymer molecular weight wider distribution In the catalytic component and its catalyst of olefinic polymerization.

Summary of the invention

The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide one kind to be used for olefinic polymerization Catalytic component and its catalyst.The present inventor catalyst component for olefin polymerization and its catalyst technical field into The experimental study gone extensively and profoundly, discovery is using 2- carbonic ester phenyl ketone compounds shown in logical formula (I) as interior to electricity The catalyst of high comprehensive performance can be obtained in sub- compound.When for olefin polymerization, activity height, the hydrogen tune of the catalyst Sensibility is good, and gained polyolefin resin stereoselectivity is good, molecular weight distribution is wider.

For this purpose, first aspect present invention provides a kind of catalytic component for olefinic polymerization, it includes magnesium, titanium, halogen Element and internal electron donor compound, wherein the internal electron donor compound includes 2- carbonic acid shown at least one logical formula (I) Ester phenyl ketone compounds；

In logical formula (I), R₁And R₂It is identical or not identical, it is each independently selected from substituted or unsubstituted C₁-C₂₀Alkane Base, C₃-C₂₀Naphthenic base, C₆-C₂₀Aryl or C₇-C₂₀Aralkyl；It is preferred that R₁And R₂It is each independently selected from substitution or does not take The C in generation₁-C₆Alkyl, C₃-C₁₀Naphthenic base or C₆-C₁₀Aryl；More preferable R₁And R₂Be each independently selected from substitution or not Substituted C₁-C₆Alkyl；Further preferred R₁And R₂It is each independently selected from methyl, ethyl, n-propyl, isopropyl, positive fourth Base, isobutyl group, n-pentyl, isopentyl, n-hexyl or isohesyl.

Heretofore described " substitution " refers to that the hydrogen on each group is replaced by halogen atom, alkyl or alkoxy.

The example of 2- carbonic ester phenyl ketone compounds shown in suitable logical formula (I) includes but is not limited to:

2- methyl carbonic acetophenone, 2- ethyl carbonate ester acetophenone, 2- n-propyl carbonic ester acetophenone, 2- isopropyl carbon Acid esters acetophenone, 2- allyl carbonate acetophenone, 2- n-butyl carbonate ester acetophenone, 2- isobutyl group carbonic ester acetophenone, 2- Tertiary butyl carbonic ester acetophenone, 2- n-pentyl carbonic ester acetophenone, 2- isopentyl carbonic ester acetophenone, 2- tertiary amyl carbonic ester benzene Ethyl ketone, 2- n-hexyl carbonic ester acetophenone, 2- isohesyl carbonic ester acetophenone, 2- spy's hexyl carbonate acetophenone, 2- n-heptyl The different heptyl carbonic ester acetophenone of carbonic ester acetophenone, 2-, 2- spy's heptyl carbonic ester acetophenone；2- methyl carbonic propiophenone, 2- Ethyl carbonate ester propiophenone, 2- n-propyl carbonic ester propiophenone, 2- butylperoxyisopropyl carbonate propiophenone, 2- allyl carbonate phenylpropyl alcohol Ketone, 2- n-butyl carbonate ester propiophenone, 2- isobutyl group carbonic ester propiophenone, 2- tertiary butyl carbonic ester propiophenone, 2- n-pentyl carbon Acid esters propiophenone, 2- isopentyl carbonic ester propiophenone, 2- tertiary amyl carbonic ester propiophenone, 2- n-hexyl carbonic ester propiophenone, 2- Isohesyl carbonic ester propiophenone, 2- spy's hexyl carbonate propiophenone, 2- n-heptyl carbonic ester propiophenone, the different heptyl carbonic ester benzene of 2- Acetone, 2- spy's heptyl carbonic ester propiophenone；2- methyl carbonic phenyl propyl ketone, 2- ethyl carbonate ester phenyl propyl ketone, 2- n-propyl carbonic acid Ester phenyl propyl ketone, 2- butylperoxyisopropyl carbonate phenyl propyl ketone, 2- allyl carbonate phenyl propyl ketone, 2- n-butyl carbonate ester phenyl propyl ketone, 2- are different Butylcarbonate phenyl propyl ketone, 2- tertiary butyl carbonic ester phenyl propyl ketone, 2- n-pentyl carbonic ester phenyl propyl ketone, 2- isopentyl carbonic ester benzene fourth Ketone, 2- tertiary amyl carbonic ester phenyl propyl ketone, 2- n-hexyl carbonic ester phenyl propyl ketone, 2- isohesyl carbonic ester phenyl propyl ketone, 2- spy's hexyl carbon Acid esters phenyl propyl ketone, 2- n-heptyl carbonic ester phenyl propyl ketone, the different heptyl carbonic ester phenyl propyl ketone of 2-, in 2- spy's heptyl carbonic ester phenyl propyl ketone It is one or more.

It is preferably selected from 2- methyl carbonic acetophenone, 2- ethyl carbonate ester acetophenone, 2- n-propyl carbonic ester acetophenone, 2- Butylperoxyisopropyl carbonate acetophenone, 2- allyl carbonate acetophenone, 2- n-butyl carbonate ester acetophenone, 2- isobutyl group carbonic ester benzene Ethyl ketone, 2- n-pentyl carbonic ester acetophenone, 2- isopentyl carbonic ester acetophenone, 2- n-hexyl carbonic ester acetophenone, 2- isohesyl Carbonic ester acetophenone, 2- n-heptyl carbonic ester acetophenone, the different heptyl carbonic ester acetophenone of 2-；2- methyl carbonic propiophenone, 2- Ethyl carbonate ester propiophenone, 2- n-propyl carbonic ester propiophenone, 2- butylperoxyisopropyl carbonate propiophenone, 2- allyl carbonate phenylpropyl alcohol Ketone, 2- n-butyl carbonate ester propiophenone, 2- isobutyl group carbonic ester propiophenone, 2- n-pentyl carbonic ester propiophenone, 2- isopentyl carbon Acid esters propiophenone, 2- n-hexyl carbonic ester propiophenone, 2- isohesyl carbonic ester propiophenone, 2- n-heptyl carbonic ester propiophenone, 2- Different heptyl carbonic ester propiophenone；2- methyl carbonic phenyl propyl ketone, 2- ethyl carbonate ester phenyl propyl ketone, 2- n-propyl carbonic ester benzene fourth Ketone, 2- butylperoxyisopropyl carbonate phenyl propyl ketone, 2- allyl carbonate phenyl propyl ketone, 2- n-butyl carbonate ester phenyl propyl ketone, 2- isobutyl group carbon Acid esters phenyl propyl ketone, 2- n-pentyl carbonic ester phenyl propyl ketone, 2- isopentyl carbonic ester phenyl propyl ketone, 2- n-hexyl carbonic ester phenyl propyl ketone, 2- One of isohesyl carbonic ester phenyl propyl ketone, 2- n-heptyl carbonic ester phenyl propyl ketone, the different heptyl carbonic ester phenyl propyl ketone of 2- are a variety of.

Be most preferably selected from 2- methyl carbonic acetophenone, 2- ethyl carbonate ester acetophenone, 2- n-propyl carbonic ester acetophenone, 2- butylperoxyisopropyl carbonate acetophenone, 2- allyl carbonate acetophenone, 2- n-butyl carbonate ester acetophenone, 2- isobutyl group carbonic ester Acetophenone, 2- n-pentyl carbonic ester acetophenone, 2- isopentyl carbonic ester acetophenone, 2- n-hexyl carbonic ester acetophenone, 2- dissident Base carbonic ester acetophenone；2- methyl carbonic propiophenone, 2- ethyl carbonate ester propiophenone, 2- n-propyl carbonic ester propiophenone, 2- Butylperoxyisopropyl carbonate propiophenone, 2- allyl carbonate propiophenone, 2- n-butyl carbonate ester propiophenone, 2- isobutyl group carbonic ester benzene Acetone, 2- n-pentyl carbonic ester propiophenone, 2- isopentyl carbonic ester propiophenone, 2- n-hexyl carbonic ester propiophenone, 2- isohesyl Carbonic ester propiophenone；2- methyl carbonic phenyl propyl ketone, 2- ethyl carbonate ester phenyl propyl ketone, 2- n-propyl carbonic ester phenyl propyl ketone, 2- are different Propyl carbonate phenyl propyl ketone, 2- allyl carbonate phenyl propyl ketone, 2- n-butyl carbonate ester phenyl propyl ketone, 2- isobutyl group carbonic ester benzene fourth Ketone, 2- n-pentyl carbonic ester phenyl propyl ketone, 2- isopentyl carbonic ester phenyl propyl ketone, 2- n-hexyl carbonic ester phenyl propyl ketone, 2- isohesyl carbon One of acid esters phenyl propyl ketone is a variety of.

The content of catalytic component according to the present invention, the total weight based on catalytic component, the titanium is 1.0wt%-8.0wt%, preferably 1.6wt%-6.0wt%；The content of the magnesium is 10.0wt%-70.0wt%, preferably 15.0wt%-40.0wt%；The content of the halogen is 20.0wt%-90.0wt%, preferably 30.0wt%-85.0wt%； The content of the internal electron donor compound is 2.0wt%-30.0wt%, preferably 3.0wt%-20.0wt%.

Catalytic component of the present invention includes that the reaction of magnesium compound, titanium compound and internal electron donor compound produces Object, i.e., the preparation method of catalytic component of the present invention can be titanium compound, magnesium compound and internal electron donor chemical combination Object haptoreaction under certain condition.The internal electron donor compound includes 2- carbonic ester shown at least one logical formula (I) Phenyl ketone compounds.It is used to prepare the titanium compound of the catalytic component, magnesium compound and internal electron donor compound Dosage is not particularly limited, and can be the conventional substances and dosage of this field.

In some embodiments of the invention, electricity is given within the internal electron donor compound and the molar ratio of magnesium compound Donor compound: magnesium is calculated as 0.01-3.0, preferably 0.02-0.3.

In some preferred embodiments of the invention, the magnesium compound includes logical formula (III) compound represented, leads to One of alcohol adduct shown in hydrate shown in formula (IV) and logical formula (V) is a variety of；

MgR₅R₆ (III)

MgR₅R₆·qH₂O (IV)

MgR₅R₆·pR₀H₂O (V)。

In logical formula (III)-(V), R₅And R₆It is identical or not identical, it is each independently selected from halogen, C₁-C₅Alkyl or Alkoxy.The halogen is chlorine, bromine or iodine.

In logical formula (IV), q 0.1-6.0, preferably 2.0-3.5；

In logical formula (V), R₀Selected from C₁-C₁₈Alkyl, preferably C₁-C₅Alkyl；P is 0.1-6.0, preferably 2.0- 3.5。

In some preferred embodiments of the invention, the magnesium compound be selected from dimethoxy magnesium, diethoxy magnesium, Dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two oxygroup magnesium, two (2- first Base) oxygroup magnesium, methoxy magnesium chloride, 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 bromination Magnesium, butoxy magnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, the alcohol adduct of magnesium dichloride, magnesium dibromide alcohol adduct At least one of with the alcohol adduct of magnesium diiodide.

In some most preferred embodiments of the invention, the magnesium compound is diethoxy magnesium or magnesium dichloride.

In some preferred embodiments of the invention, the titanium compound includes changing shown at least one logical formula (VI) Close object；

TiX_m(OR₇)_4-m (VI)

In logical formula (VI), R₇For C₁-C₂₀Alkyl, preferably C₁-C₅Alkyl；X is halogen；1≤m≤4 and m are whole Number, such as 1,2,3 or 4.The halogen is chlorine, bromine or iodine.

In some preferred embodiments of the invention, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, the tetraiodo Change titanium, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, in one ethanolato-titanium of dichlorodiethyl oxygroup titanium and trichlorine It is at least one.

In some most preferred embodiments of the invention, the titanium compound is titanium tetrachloride.

Alkene of the invention is prepared by making titanium compound, magnesium compound and internal electron donor compound reaction in the present invention The method of polymerized hydrocarbon catalytic component can be carried out by the conventional method for preparing alkene catalyst component in this field.Such as it can To prepare catalyst component for olefin polymerization of the invention by following methods.

Method one prepares catalytic component referring to CN102453150B method according to the following steps.(1) by alkoxyl magnesium or alkane Oxygroup halogenated magnesium compound, in the presence of inert diluent with interior electronics required by titanium compound and formula (1) to donor compound into Row haptoreaction；(2) it is washed to obtain ingredient of solid catalyst with atent solvent by the solid that step (1) obtains.

As the specific example of above-mentioned alkoxyl magnesium, can enumerate dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, Oxygroup magnesium, two (2- methyl) the oxygroup magnesium of diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two Or mixtures thereof Deng, the preferably mixture of diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesiums.The alkoxyl magnesium The preparation method for closing object, can be prepared by method well known in the art, such as prepare magnesium metal and fatty alcohol 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 Method preparation well known in the art, such as mixes Grignard Reagent butylmagnesium chloride to prepare with purity titanium tetraethoxide and tetraethoxy-silicane Ethyoxyl magnesium chloride.

In step (1), the inert diluent is selected from C₆~C₁₀Alkane or at least one of aromatic hydrocarbons.Described The specific example of inert diluent can be used one of hexane, heptane, octane, decane, benzene,toluene,xylene or they Mixture；The preferred toluene of the present invention.For the sequence of contact, there is no particular limitation, such as can be in the presence of inert diluent Under contact each ingredient, can also dilute each ingredient with atent solvent in advance be such that their contact.Do not have for the number of contact yet It is special to limit, it can contact once, can also contact repeatedly.

The ingredient of solid catalyst obtained by the above haptoreaction can be washed with atent solvent, such as: hydrocarbon compound. The specific example of the atent solvent can be selected from one of hexane, heptane, octane, decane, benzene,toluene,xylene or they Mixture.It is preferably hexane in the present invention.

In the present invention, for the method for washing, there is no particular limitation, preferably the modes such as decantation, filtering.Atent solvent Usage amount, wash time, washing times be not particularly limited, the compound relative to 1 mole of magnesium rubs usually using 1~1000 You, preferably 10~500 moles of solvent usually washs 1~24 hour, preferably 10~6 hours.In addition from the homogeneity of washing It sets out in terms of detersive efficiency, is preferably stirred in washing operation.It should be noted that resulting solid catalyst group Dividing can save in the dry state or save in atent solvent.

The dosage of each ingredient used in method one, in terms of every mole of magnesium, 0.5-100 moles of the usage amount of titanium compound, Preferably 1-50 moles；The usage amount of inert diluent is usually 0.5-100 moles, and preferably 1-50 moles；Electron donor The total amount for closing object is usually 0.005-10 moles, and preferably 0.01-1 moles.

The Contact Temperature of each component is usually -40~200 DEG C, preferably -20~150 DEG C；Time of contact is usually 1 Minute~20 hours, preferably 5 minutes~8 hours.

Magnesium dihalide is dissolved in organic epoxy compound object, organic phosphorus referring to the method for patent CN85100997 by method two In the dicyandiamide solution of compound and inert diluent composition, mixes after forming homogeneous solution with titanium compound, deposited in precipitation additive Under, solids is precipitated；Then the solids is contacted again with internal electron donor, is attached to it on solids and obtains solid and urge Agent component.

The precipitation additive used in method two can be at least one of organic acid anhydride, organic acid, ether and ketone.It is described The specific example of organic acid anhydride can in acetic anhydride, phthalic anhydride, succinic anhydride and maleic anhydride etc. at least The specific example of one kind, the organic acid can be at least one in acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid etc. Kind, the specific example of the ether can be at least one of methyl ether, ether, propyl ether, butyl ether and amyl ether, and the ketone can be third At least one of ketone, methyl ethyl ketone and benzophenone.

The organic epoxy compound object used in method two can be for selected from ethylene oxide, propylene oxide, epoxy butane, fourth At least one in allene oxide object, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether etc. Kind, 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 inert diluent used in method two can be used in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene It is at least one.

The dosage of each ingredient used in method two, in terms of every mole of magnesium halide, organic epoxy compound object 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 moles；Titanium compound It can be 0.5-20 moles, preferably 5-15 moles；Helping and component is precipitated to be 0.01-0.3 moles, preferably 0.02-0.08 Mole；Electronic donor compound total amount can be 0-10 moles, preferably 0.02-0.3 moles.

Method three prepares catalytic component referring to the preparation method of CN1091748.Chlorination magnesium alcoholate melt white oil with Disperse in the dispersion of silicone oil through high-speed stirred, form emulsion, be discharged into coolant liquid CTC (Centell Technology Corporation) speed cooling and shaping, forms magnesium chloride Alcohol adduct microballoon.Coolant liquid is the lower inert hydrocarbon solvent of boiling point, such as petroleum ether, pentane, hexane, heptane.Gained chlorination Magnesium alcoholate microballoon is washed, it is dry be ball type carrier, the molar ratio of alcohol and magnesium chloride is 2-3, preferably 2-2.5.Carrier Partial size is 10-300 microns, best with 30-150 microns.

It with excessive titanium tetrachloride in the above-mentioned ball type carrier of low-temperature treatment, gradually heats up, is added during processing to electricity Daughter is repeatedly washed after processing with atent solvent, obtains the spheric catalyst of solid powdery after dry.Titanium tetrachloride and chlorination The molar ratio of magnesium is 20-200, preferably 30~60；Initiated process temperature is -30~0 DEG C, is preferred with -25~-20 DEG C；Finally Treatment temperature is 80~136 DEG C, is preferred with 100~130 DEG C.

Gained spheric catalyst has the feature that Ti content 1.5-3.5wt%, ester content 6.0-20.0wt%, chlorine contain Measure 52-60wt%, content of magnesium 10-20wt%, atent solvent content 1-6wt%.

Method four: the method referring to disclosed in CN1506384 prepares catalyst.First by organic alcohol compound and magnesium chemical combination Object is mixed by 2-5 molar ratio and atent solvent, is warming up to 120-150 DEG C, forms homogeneous solution, is selectively added to be used as and is helped precipitation Phthalic anhydride, silicon-containing compound or the other auxiliary agents for helping to obtain good particle of agent；It then will according to titanium/magnesium molar ratio 20-50 Alcohol adduct and titanium compound haptoreaction 2-10h, reaction temperature -15~-40 DEG C are warming up to 90- in the presence of precipitation additive 110℃；Electron donor compound of the present invention is added according to magnesium/ester molar ratio 2-10, it is small in 100-130 DEG C of reaction 1-3 When, filter to isolate solid particle；(alternative repeat 2-3 times) is according to titanium/magnesium molar ratio 20-50 by solid particle and titanium again Compound 100-130 DEG C haptoreaction 1.5-3 hours, filter to isolate solid particle；Finally use 50-80 DEG C of atent solvent Solid particle is washed, obtains catalytic component after dry.

In above-mentioned four kinds of any methods for preparing catalyst component for olefin polymerization of the invention, can will be described in Electron donor can be used alone, can also two kinds or more be used in mixed way.

In above-mentioned four kinds of any methods for preparing catalyst component for olefin polymerization of the invention, internal electron donor It can be added before magnesium compound is contacted with titanium compound or in contact process, as being first added to internal electron donor in method one In alkoxyl magnesium or Alkoxymagnesium halides in the suspension of inert diluent, then olefinic polymerization is mixed with titanium compound and is urged Agent；Internal electron donor is added in magnesium halide solution before magnesium halide solution is contacted with titanium compound in method two.

Second aspect of the present invention provides a kind of catalyst for olefinic polymerization, and it includes following components:

Component a, catalytic component as described in the first aspect of the invention；

Component b, alkyl aluminum compound；

Wherein, the molar ratio of component b and component a is with aluminium: titanium is calculated as (5-5000): 1, preferably (20-1000): 1, it is more excellent It is selected as (50-500): 1.

Catalyst according to the present invention, the component b alkyl aluminum compound can be common for field of olefin polymerisation The alkyl aluminum compound of the various co-catalysts that can be used as Ziegler-natta catalyst.

In some preferred embodiments of the invention, the component b alkyl aluminum compound includes at least one general formula (VII) compound represented；

AlR'_n'X'_3-n' (VII)

In logical formula (VII), R' is selected from H, C₁-C₂₀Alkyl or C₆-C₂₀Aryl, X' is halogen, 1≤n'≤3 and n' For integer.

In some preferred embodiments of the invention, the alkyl aluminum compound be selected from trimethyl aluminium, triethyl aluminum, Triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, At least one of sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.

Catalyst according to the present invention also includes component c, external donor compound in the catalyst.This hair In bright, the type and content of the external donor compound are not particularly limited.The component c external donor compound It can be the external electron donor of the common various co-catalysts that can be used as Ziegler-natta catalyst of field of olefin polymerisation Compound.

In some preferred embodiments of the invention, the molar ratio of the component c and component b are with silicon: aluminium is calculated as 1: (0.1-500).In some preferred embodiments of the invention, the molar ratio of the component c and component b are with silicon: aluminium is calculated as 1:(1-300).In some further preferred embodiments of the invention, the molar ratio of the component c and component b are with silicon: aluminium It is calculated as 1:(3-100).

In some preferred embodiments of the invention, the component c external donor compound includes at least one logical Formula (VIII) compound represented:

R^1" _m"R^2" _n"Si(OR^3")_4-m"-n" (VIII)

In logical formula (VIII), R^1"And R^2"It is identical or not identical, it is each independently selected from H, halogen, C₁-C₂₀Alkyl or Halogenated alkyl, C₃-C₂₀Naphthenic base or C₆-C₂₀Aryl；R^3"Selected from C₁-C₂₀Alkyl or halogenated alkyl, C₃-C₂₀Naphthenic base Or C₆-C₂₀Aryl；The integer that m " and n " is 0-3, and m "+n " < 4.

In some preferred embodiments of the invention, the component c external donor compound is selected from trimethyl first Oxysilane, trimethylethoxysilane, trimethylbenzene oxygroup triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, diformazan Base dimethoxysilane, dimethyl diethoxysilane, ethylisopropyl base dimethoxysilane, propyl iso-propyl dimethoxy silicon Alkane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, two tertiary fourths Base dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tert-butyl dimethylamine oxygen Base silane, ter /-butylisopropyl dimethoxysilane, tert-butyl butyldimethoxysilane, tert-butyl isobutyl group dimethoxy silicon Alkane, tert-butyl (sec-butyl) dimethoxysilane, t-butyl amyl dimethoxysilane, tert-butyl nonyl dimethoxysilane, Tert-butyl hexyl dimethoxysilane, tert-butyl heptyl dimethoxysilane, tert-butyl octyl dimethoxysilane, the tert-butyl last of the ten Heavenly stems Base dimethoxysilane, methyl-t-butyldimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl-ethyl dimethoxy Base silane, Cyclohexylpropyl dimethoxysilane, cyclohexyl isobutyl group dimethoxysilane, Dicyclohexyldimethoxysilane, Cyclohexyl t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, cyclopenta Propyldimethoxy-silane, cyclopenta t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl two Methoxy silane, bis- (2- methylcyclopentyl) dimethoxysilanes, dimethoxydiphenylsilane, diphenyl diethoxy silicon Alkane, phenyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl three Ethoxysilane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxy Silane, trimethoxysilane, tert-butyl trimethoxy silane, sec-butyl trimethoxy silane, amyl trimethoxy silicon Alkane, isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, diphenyl dimethoxy silicon Alkane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl trimethoxy silane, second Alkenyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, 2- ethyl piperidine base -2- tert-butyl Dimethoxysilane, (the fluoro- 2- propyl of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilane and (the fluoro- 2- third of 1,1,1- tri- At least one of base)-methyl dimethoxysilane.

In some further preferred embodiments of the invention, the component c external donor compound is selected from two rings Dicyclopentyldimetoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclohexyl methyl dimethoxy At least one of silane, methyl-t-butyldimethoxysilane and tetramethoxy-silicane.

Third aspect present invention provides a kind of pre-polymerized catalyst for olefinic polymerization comprising such as the present invention first Catalytic component described in aspect or catalyst as described in respect of the second aspect of the invention and alkene carry out the resulting pre-polymerization of prepolymerization Object；Wherein, the pre-polymerization multiple of the prepolymer is 5-1000g olefin polymer/g catalytic component, preferably 10-500g alkene Polymer/g catalytic component；It is preferred that alkene used in prepolymerization is ethylene or propylene.

In some embodiments of the invention, the prepolymerized temperature is -20 to 80 DEG C, preferably 10-50 DEG C.

Fourth aspect present invention provides a kind of olefine polymerizing process, and the alkene is as described in the first aspect of the invention Catalytic component, catalyst as described in respect of the second aspect of the invention or pre-polymerized catalyst as described in the third aspect of the present invention It is polymerize under effect.The general formula of the alkene is CH₂=CHR, wherein R is hydrogen, C₁-C₆Alkyl or phenyl.

Olefine polymerizing process provided by the invention can be used for the homopolymerization of alkene, can be used for carrying out in a variety of alkene Combined polymerization.The alkene is selected from ethylene, propylene, 1- n-butene, 1- n-pentene, 1- n-hexylene, the positive octene of 1- and 4- methyl-1-pentene At least one of alkene.Preferably, the alkene can for ethylene, propylene, 1- n-butene, 4-methyl-1-pentene and 1- just oneself At least one of alkene.It is preferred that the alkene is propylene.

When preparing polyolefin, each component in catalyst of the present invention, i.e., catalytic component provided by the invention, work It can first be contacted before contacting olefinic monomer for the organo-aluminum compound and external donor compound of co-catalyst, It is referred to as " pre-contact " or " pre- complexing " in the industry；Can also three components be added separately in olefinic monomer to carry out polymerizeing again it is anti- It answers, i.e., does not implement " pre-contact ".The olefine polymerizing process provided according to the present invention, each component is adopted in preferred alkenes polymerization catalyst With the method for " pre-contact ".The time of " pre-contact " be 0.1-30min, preferably 1-10 minutes；The temperature of " pre-contact " is -20 DEG C to 80 DEG C, preferably 10-50 DEG C.

Catalyst of the present invention is first carried out in the presence of a small amount of olefinic monomer a degree of prepolymerization obtain it is pre- Polymerization catalyst, then pre-polymerized catalyst is further contacted with olefinic monomer and is reacted to obtain olefin polymer.This skill Art is in the field of business to be referred to as " prepolymerization " technique, facilitates polymerization catalyst activity and raising of polymer bulk density etc..According to Olefine polymerizing process provided by the invention can use " prepolymerization " technique, can not also use " prepolymerization " technique, preferably adopt With " prepolymerization " technique.

Olefine polymerizing process according to the present invention, the polymerizing condition can be this field normal condition, the use of catalyst Amount can be the dosage of the various catalyst of the prior art.

The present invention is by using 2- carbonic ester phenyl ketone compounds shown in logical formula (I) as internal electron donor chemical combination The catalyst of high comprehensive performance can be obtained in object.When for olefin polymerization, activity height, the hydrogen response of the catalyst Good, gained polyolefin resin stereoselectivity is good, molecular weight distribution is wider.

Specific embodiment

To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only Serve illustrative, it is not limited to application range of the invention.

Test method used in the present invention is as follows:

(1) yield (%) of catalytic component=(gained catalyst quality/magnesium chloride used quality) × 100%；

(2) 721 spectrophotometric determinations the Ti content in catalytic component (wt%): are used；

(3) purity of internal electron donor compound is measured using gas-chromatography (GC)；

(4) it melt index (MI): is measured according to GB/T3682-2000；

(5) acrylic polymers isotacticity index (II): measured using heptane extraction process: 2g dry polymer samples are put It is after being extracted 6 hours in extractor with boiling heptane, residue is dry to the resulting polymer weight (g) of constant weight and 2 (g) Ratio is isotacticity；

(6) polymer molecular weight distribution MWD (MWD=Mw/Mn): PL-GPC220 is used, using trichloro-benzenes as solvent, 150 (standard specimen: polystyrene, flow velocity: 1.0mL/min, pillar: 3 × Plgel10 μm of 300 × 7.5nm of Ml × ED-B) is measured at DEG C；

(7) active (Ac) is calculated: catalyst activity=(the polyolefin quality of preparation)/(catalyst solid constituent quality) kg/g；

(8) bulk density (BD) measures: will prepare resulting polymer powders in funnel from 10cm height freely falling body Into 100mL container, polymer powders weight is M g in weighing container, then polymer bulk density is M/100g/cm³。

Embodiment

Embodiment 1

One, the synthesis of internal electron donor compound (compound 1:2- n-pentyl carbonic ester acetophenone)

300g 2- hydroxy acetophenone, 226.3g anhydrous pyridine, 10g 4-dimethylaminopyridine are added to 300mL drying The in the mixed solvent of tetrahydrofuran and 200mL chloroform.397.6g n-amyl chlorocarbonate is added in 200mL chloroform, Then it is added dropwise and enters in reaction system, keep temperature to stablize between 10-20 DEG C during being added dropwise.After being added dropwise, it is warming up to 50 DEG C stirring 3-4 hours, subsequent 80 DEG C of reactions 8-10 hours.Reaction was completed, cooling, is filtered to remove solid salt, is spin-dried for solvent, adds Enter 200mL ethyl acetate, 400mL water is adjusted to pH=5-6 using 10% hydrochloric acid, and liquid separation, ethyl acetate aqueous phase extracted is twice (100mL, 80mL), merges organic phase, and anhydrous magnesium sulfate dries, filters, is spin-dried for solvent and obtains crude product.Vacuum distillation obtains final Product 396.1g, yield 68%, purity 99.65% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.9-0.94(t,-O(CH₂)₄CH₃),1.37-1.40(m,- OCH₂CH₂CH₂CH₂CH₃),1.73-1.78(m,-OCH₂CH₂CH₂CH₂CH₃),2.55(s,-C(O)CH₃),4.24-4.29(t,- OCH₂CH₂CH₂CH₂CH₃),7.18-7.81(m,-C₆H₄)。

Two, the preparation of catalytic component

(1) it the configuration of alcohol adduct solution: is repeating that it is anhydrous to sequentially add 15.0g in displaced reaction kettle by High Purity Nitrogen Magnesium chloride, 60mL toluene, 63.5mL isooctanol, under conditions of speed of agitator 300rpm, temperature are 110 DEG C, reaction 2.0 is small When, obtain the solution of stable and uniform.Add 0.8mL 3,5- heptandiol dibenzoate, two isobutyl of 3.0mL phthalic acid Ester reacts 1.5 hours under conditions of speed of agitator 300rpm, temperature are 110 DEG C.2.25mL butyl titanate is added, Under conditions of speed of agitator 300rpm, temperature are 110 DEG C, react 1.5 hours.Toluene 90mL is added, in speed of agitator Under conditions of 300rpm, temperature are 110 DEG C, reaction is cooled to room temperature after 0.5 hour to get alcohol adduct solution.

(2) preparation of catalytic component: above-mentioned alcohol adduct solution 72mL is added to and is sufficiently displaced from through nitrogen, equipped with 60mL In the reactor of titanium tetrachloride and 40mL toluene, come into full contact with them at -25 DEG C 1.5 hours by stirring, it is small through 3 after When be warming up to 110 DEG C, constant temperature 1 hour after cooling and filters pressing after 108mL toluene and 12mL titanium tetrachloride stir 1 hour is added, then 12mL titanium tetrachloride and 108mL toluene is added, is warming up to 100 DEG C, 1.1g compound 1:2- n-pentyl carbonic ester acetophenone is added (molar ratio of compound 1 and magnesium compound is with compound 1: magnesium is calculated as 0.083), constant temperature 1 hour.110 DEG C are warming up to, is added 72mL toluene and 48mL titanium tetrachloride stir 1 hour, obtained solids are washed 1 time with 120mL toluene after filters pressing, 150mL Hexane washs 4 times.Filters pressing is shifted and dry, obtains catalyst component for olefin polymerization 1.

Three, propylene polymerization

Catalytic component 1 obtained above is subjected to propylene polymerization at different conditions.Method particularly includes: in a 5L high It presses in kettle, after gas-phase propene is sufficiently displaced from, the hexane solution (concentration of triethyl aluminum of 5mL triethyl aluminum is added at room temperature For the hexane solution of 0.5mmol/mL), l mL Cyclohexyl Methyl Dimethoxysilane (CHMMS), (concentration of CHMMS is 0.10mmol/mL), 10mL anhydrous hexane and 10mg catalytic component 1.Closing autoclave, introducing 0.18mol hydrogen and 2.4L's Liquid propene；Temperature is risen to 70 DEG C in 10 minutes under stiring.At 70 DEG C after polymerization reaction 1 hour, stop stirring, removes Unpolymerized propylene monomer, collected polymer.It is dried in vacuo 1 hour at 70 DEG C, weighing calculates catalyst activity.Polymerization result It is shown in Table 1.

Embodiment 2

One, the synthesis of internal electron donor compound (compound 2:2- n-butyl carbonate ester acetophenone)

Using the synthetic method of similar compound 1, n-amyl chlorocarbonate is changed to butyl chloroformate, 2- is being prepared just Butylcarbonate acetophenone 383.5g, yield 73.6%, purity 98.81% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.94-0.99(t,-O(CH₂)₃CH₃),1.42-1.50(m,- OCH₂CH₂CH₂CH₃),1.72-1.77(m,-OCH₂CH₂CH₂CH₃),2.56(s,-C(O)CH₃),4.26-4.30(m,- OCH₂CH₂CH₂CH₃),7.19-7.53(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced in step (2) It is changed to compound 2 (molar ratio of compound 2 and magnesium compound is with compound 2: magnesium is calculated as 0.088), obtains catalytic component 2.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 2, polymerization result is shown in Table 1.

Embodiment 3

One, the synthesis of internal electron donor compound (compound 3:2- isobutyl group carbonic ester acetophenone)

Using the synthetic method of similar compound 1, n-amyl chlorocarbonate is changed to isobutyl chlorocarbonate, it is different that 2- is prepared Butylcarbonate acetophenone 282.6g, yield 55.6%, purity 98.7% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.98-1.00(t,-OCH₂CH(CH₃)₂),(m,-OCH₂CH (CH₃)₂),2.53(s,-C(O)CH₃),4.04-4.06(d,-OCH₂CH(CH₃)₂),7.17-7.80(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 3 (molar ratio of compound 3 and magnesium compound is with compound 3: magnesium is calculated as 0.088), obtains catalytic component 3.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 3, polymerization result is shown in Table 1.

Embodiment 4

One, the synthesis of internal electron donor compound (compound 4:2- n-propyl carbonic ester acetophenone)

Using the synthetic method of similar compound 1, n-amyl chlorocarbonate is changed to n-propyl chloroformate, 2- is being prepared just Propyl carbonate acetophenone 152.3g, yield 58.3%, purity 99.85% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.98-1.03(t,-O(CH₂)₂CH₃),1.74-1.81(m,- OCH₂CH₂CH₃),2.56(s,-C(O)CH₃),4.21-4.25(m,-OCH₂CH₂CH₃),7.18-7.82(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 4 (molar ratio of compound 4 and magnesium compound is with compound 4: magnesium is calculated as 0.093), obtains catalytic component 4.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 4, polymerization result is shown in Table 1.

Embodiment 5

One, the synthesis of internal electron donor compound (compound 5:2- allyl carbonate acetophenone):

Using the synthetic method of similar compound 1, n-amyl chlorocarbonate is changed to allyl chlorocarbonate, 2- alkene is prepared Propyl carbonate acetophenone 187.3g, yield 61.3%, purity 99.2% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):2.55(s,-C(O)CH₃), 4.73-4.76 (m ,-OCH₂CH= CH₂),5.29-5.46(m,-OCH₂CH=CH₂),5.93-6.05(m,-OCH₂CH=CH₃),7.18-7.82(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 5 (molar ratio of compound 5 and magnesium compound is with compound 5: magnesium is calculated as 0.094), obtains catalytic component 5.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 5, polymerization result is shown in Table 1.

Embodiment 6

One, the synthesis of internal electron donor compound (compound 6:2- butylperoxyisopropyl carbonate acetophenone):

Using the synthetic method of similar compound 1, n-amyl chlorocarbonate is changed to isopropyl chlorocarbonate, it is different that 2- is prepared Propyl carbonate acetophenone 207.3g, yield 52.6%, purity 98.9% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):1.39-1.41(d,-OCH(CH₃)₂),2.57(s,-C(O) CH₃),4.97-5.02(m,-OCH(CH₃)₂),7.20-7.83(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 6 (molar ratio of compound 6 and magnesium compound is with compound 6: magnesium is calculated as 0.093), obtains catalytic component 6.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 6, polymerization result is shown in Table 1.

Embodiment 7

One, the synthesis of internal electron donor compound (compound 7:2- n-butyl carbonate ester propiophenone):

Using the synthetic method of similar compound 1,2- hydroxy acetophenone is changed to 2- hydroxypropiophenonepreparation, by chloro-carbonic acid positive penta Ester is changed to butyl chloroformate, and 2- n-butyl carbonate ester propiophenone 243.8g, yield 63.7%, purity 99.0% is prepared (GC)。

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.95-0.99(t,-O(CH₂)₃CH₃),1.16-1.19(t,-C (O)CH₂CH₃),1.44-1.49(m,-OCH₂CH₂CH₂CH₃), 1.71-1.78 (m ,-OCH₂CH₂CH₂CH₃),2.90-2.95(q,- C(O)CH₂CH₃),4.27-4.30(t,-OCH₂CH₂CH₂CH₃),7.19-7.79(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 7 (molar ratio of compound 7 and magnesium compound is with compound 7: magnesium is calculated as 0.083), obtains polymerization catalyst component 7.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 7, polymerization result is shown in Table 1.

Embodiment 8

One, the synthesis of internal electron donor compound (compound 8:2- n-butyl carbonate ester phenyl propyl ketone):

Using the synthetic method of similar compound 1,2- hydroxy acetophenone is changed to 2- hydroxyphenyl butanone, by chloro-carbonic acid positive penta Ester is changed to butyl chloroformate, and 2- n-butyl carbonate ester phenyl propyl ketone 181.6g, yield 50.4%, purity 99.2% is prepared (GC)。

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.95-0.99(t,-O(CH₂)₃CH₃,-(O)CCH₂CH₂CH₃), 1.42-1.51(t,-OCH₂CH₂CH₂CH₃),1.68-1.78(m,-OCH₂CH₂CH₂CH₃,-(O)CCH₂CH₂CH₃), 2.86-2.89 (m,-(O)CCH₂CH₂CH₃),4.26-4,30(q,-OCH₂CH₂CH₂CH₃₃),7.19-7.78(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 8 (molar ratio of compound 8 and magnesium compound is with compound 8: magnesium is calculated as 0.079), obtains catalytic component 8.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 8, polymerization result is shown in Table 1.

Embodiment 9

One, the synthesis of internal electron donor compound (compound 9:2- allyl carbonate phenyl propyl ketone):

Using the synthetic method of similar compound 1,2- hydroxy acetophenone is changed to 2- hydroxyphenyl butanone, by chloro-carbonic acid positive penta Ester is changed to allyl chlorocarbonate, and 2- allyl carbonate phenyl propyl ketone 192.8g, yield 61.3%, purity 98.9% is prepared (GC)。

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.92-0.97(t,-C(O)CH₂CH₂CH₃), 1.66-1.74 (m,-C(O)CH₂CH₂CH₃), 2.83-2.88 (t ,-C (O) CH₂CH₂CH₃), 4.72-4.74 (d ,-OCH₂CH=CH₂),5.27- 5.44(m,-OCH₂CH=CH₂),5.94-5.99(m,-OCH₂CH=CH₃),7.17-7.76(m,-C₆H₄)。

Two, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, compound 1 is replaced with into compound 9 (molar ratio of compound 9 and magnesium compound is with compound 9: magnesium is calculated as 0.084), obtains catalytic component 9.

Three, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 9, polymerization result is shown in Table 1.

Comparative example 1

One, the preparation method is the same as that of Example 1 for catalytic component, the difference is that, internal electron donor is changed to adjacent benzene two Formic acid di-n-butyl (DNBP), obtains catalytic component 10.

Two, the method for propylene polymerization is with embodiment 1, the difference is that, catalytic component 1 is replaced with into catalytic component 10, polymerization result is shown in Table 1.

Table 1

As can be seen from Table 1,2- carbonic ester phenyl shown in the logical formula (I) using specific structure of the present invention The catalyst that ketone compounds are prepared as the catalytic component of internal electron donor compound, is catalyzed for non-phthalic acid ester class Agent improves the safety of catalyst, and activity is very high, and the bulk density and melt index of obtained polymer are higher (to urge The hydrogen tonality of agent is higher), molecular weight distribution is wider.

It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair It is bright to can be extended to other all methods and applications with the same function.

Claims

1. a kind of catalytic component for olefinic polymerization, it includes magnesium, titanium, halogen and internal electron donor compounds, wherein institute Stating internal electron donor compound includes 2- carbonic ester phenyl ketone compounds shown at least one logical formula (I)；

In logical formula (I), R₁And R₂It is identical or not identical, it is each independently selected from substituted or unsubstituted C₁-C₂₀Alkyl, C₃- C₂₀Naphthenic base, C₆-C₂₀Aryl or C₇-C₂₀Aralkyl.

2. catalytic component according to claim 1, which is characterized in that in logical formula (I), R₁And R₂It selects each independently From substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀Naphthenic base or C₆-C₁₀Aryl；It is preferred that R₁And R₂It selects each independently From substituted or unsubstituted C₁-C₆Alkyl.

3. catalytic component according to claim 1 or 2, which is characterized in that the total weight based on catalytic component, it is described The content of titanium is 1.0wt%-8.0wt%, preferably 1.6wt%-6.0wt%；The content of the magnesium is 10.0wt%- 70.0wt%, preferably 15.0wt%-40.0wt%；The content of the halogen is 20.0wt%-90.0wt%, preferably 30.0wt%-85.0wt%；The content of the internal electron donor compound is 2.0wt%-30.0wt%, preferably 3.0wt%- 20.0wt%.

4. catalytic component described in any one of -3 according to claim 1, which is characterized in that the catalytic component includes Magnesium compound, titanium compound and the interior electron including 2- carbonic ester phenyl ketone compounds shown at least one logical formula (I) The reaction product of body compound；

Wherein, the internal electron donor compound and the molar ratio of magnesium compound are with internal electron donor compound: magnesium is calculated as 0.01- 3.0, preferably 0.02-0.3.

5. catalytic component according to claim 4, which is characterized in that the magnesium compound includes shown in logical formula (III) Compound, one of alcohol adduct shown in hydrate and logical formula (V) shown in logical formula (IV) or a variety of；

MgR₅R₆ (III)

MgR₅R₆·qH₂O (IV)

MgR₅R₆·pR₀H₂O (V)

In logical formula (III)-(V), R₅And R₆It is identical or not identical, it is each independently selected from halogen, C₁-C₅Alkyl or alcoxyl Base；

In logical formula (IV), q 0.1-6.0, preferably 2.0-3.5；

In logical formula (V), R₀Selected from C₁-C₁₈Alkyl, preferably C₁-C₅Alkyl；P is 0.1-6.0, preferably 2.0-3.5.

6. catalytic component according to claim 4 or 5, which is characterized in that the titanium compound includes at least one logical Formula (VI) compound represented；

TiX_m(OR₇)_4-m (VI)

In logical formula (VI), R₇For C₁-C₂₀Alkyl, preferably C₁-C₅Alkyl；X is halogen；1≤m≤4 and m are integer.

7. a kind of catalyst for olefinic polymerization, it includes following components:

Component a, the catalytic component as described in any one of claim 1-6；

Component b, alkyl aluminum compound；

Wherein, the molar ratio of component b and component a is with aluminium: titanium is calculated as (5-5000): 1, preferably (20-1000): 1, more preferably (50-500):1。

8. catalyst according to claim 7, which is characterized in that the component b alkyl aluminum compound includes at least one Logical formula (VII) compound represented；

AlR'_n'X'_3-n' (VII)

In logical formula (VII), R' is selected from H, C₁-C₂₀Alkyl or C₆-C₂₀Aryl, X' is halogen, 1≤n'≤3 and n' is whole Number.

9. catalyst according to claim 7 or 8, which is characterized in that it also include component c in the catalyst, it is outer to electricity The molar ratio of donor compound, the component c and component b are with silicon: aluminium is calculated as 1:(0.1-500), preferably 1:(1-300), more Preferably 1:(3-100).

10. catalyst according to claim 9, which is characterized in that the component c external donor compound includes general formula (VIII) at least one of compound represented:

R¹"_m"R²"_n"Si(OR^3")_4-m"-n" (VIII)

In logical formula (VIII), R¹" and R²" it is identical or not identical, it is each independently selected from H, halogen, C₁-C₂₀Alkyl or halogenated Alkyl, C₃-C₂₀Naphthenic base or C₆-C₂₀Aryl；R³" it is selected from C₁-C₂₀Alkyl or halogenated alkyl, C₃-C₂₀Naphthenic base or C₆-C₂₀Aryl；The integer that m " and n " is 0-3, and m "+n " < 4.

11. a kind of pre-polymerized catalyst for olefinic polymerization comprising the catalysis as described in any one of claim 1-6 Agent component or catalyst and the alkene progress resulting prepolymer of prepolymerization as described in any one of claim 7-10；Its In, the pre-polymerization multiple of the prepolymer is 5-1000g olefin polymer/g catalytic component, preferably 10-500g olefinic polymerization Object/g catalytic component；It is preferred that alkene used in prepolymerization is ethylene or propylene.

12. a kind of olefine polymerizing process, the alkene is in the catalytic component, such as described in any one of claim 1-6 Under the action of catalyst described in any one of claim 7-10 or pre-polymerized catalyst as claimed in claim 11 into Row polymerization, the general formula of the alkene are CH₂=CHR, wherein R is hydrogen, C₁-C₆Alkyl or aryl.