CN106608934B

CN106608934B - Catalytic component and its preparation method and application and catalyst system and its application and olefine polymerizing process for olefinic polymerization

Info

Publication number: CN106608934B
Application number: CN201510708211.5A
Authority: CN
Inventors: 夏先知; 张纪贵; 刘月祥; 高富堂; 李威莅; 彭人琪; 凌永泰; 赵瑾; 任春红; 谭扬; 张天; 张天一; 张志会; 段瑞林; 万真; 马长友
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2015-10-27
Filing date: 2015-10-27
Publication date: 2019-03-22
Anticipated expiration: 2035-10-27
Also published as: CN106608934A

Abstract

The present invention relates to field of olefin polymerisation, specifically provide a kind of catalytic component and its preparation method and application for olefinic polymerization, it include: that adduct of magnesium halides, titanium compound and aromatic carboxylic acid ester compounds are subjected to haptoreaction, the preparation of adduct of magnesium halides includes: (1) by aqueous MgX¹Y and R¹OH and the mixing of oxyl benzoyl based compound, and obtained mixture is heated；Or by anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated；Obtain the adduct of magnesium halides of liquid；(2) in the presence of inert liquid medium, the adduct of magnesium halides of liquid structural unit with hole is passed through under pressure to shape and be dried to liquid cooling medium chilling.The present invention provides the catalyst systems and its application and olefine polymerizing process for olefinic polymerization.The catalytic component of adduct carrier synthesis prepared by the present invention has improved hydrogen response when being used for olefinic polymerization.

Description

Catalytic component and its preparation method and application and caltalyst for olefinic polymerization System and its application and olefine polymerizing process

Technical field

The present invention relates to a kind of preparation methods of catalytic component for olefinic polymerization, and the use obtained by this method Catalytic component in olefinic polymerization and its application in catalyst system of the preparation for olefinic polymerization；Gather with for alkene The catalyst of conjunction and its application in olefin polymerization；With a kind of using the catalyst for olefinic polymerization of the invention Olefine polymerizing process.

Technical background

By titanium compound and electron donor it is compound loaded in magnesium halide in active to prepare Ziegler-Natta catalyst It is well known from.Wherein, the magnesium halide in active passes through the adduct frequently with magnesium halide and alcohol, as load Body obtains spheric catalyst after reacting with halogenated titanium and electron donor compound, the spheric catalyst is (special for alkene Propylene) polymerization when, polymerization activity and stereotaxis ability with higher, resulting polymers also have preferable particle shape With higher apparent density.

Published magnesium halide alcohol adducts are the alcohol adduct of magnesium chloride mostly, generally include magnesium chloride and alcohol binary group Point.Wherein, the adduct of some published magnesium chlorides and alcohol also contains a small amount of water.Such alcohol adduct can be by doing by spraying Dry, misting cooling, high pressure squeeze out, high-speed stirred or the methods of high-gravity rotating bed preparation.Such as: US4421674, US4469648, WO8707620、WO9311166、US5100849、US6020279、US4399054、EP0395383、US6127304、 Chlorination magnesium alcoholate disclosed in US6323152 and CN1289542C.

US4421674 and CN1765940A, which is disclosed, a kind of to be prepared carrier for olefin polymerization catalyst (carrier alcohol content is less than 14%, apparent density 0.32g/ml, the partial size of carrier is less than 20 microns) spray drying process.By the way that the ethyl alcohol of magnesium chloride is molten Liquid (about 100-300g/L) is sprayed in the vaporizer of flow of warm nitrogen gas after being preheated to 90-100 DEG C, is formed after removing most of alcohol The solid particle of chlorination magnesium alcoholate.This method first prepares the ethanol solution of magnesium chloride, and ethanol consumption is big, and energy consumption is higher.

US6020279 discloses a kind of spray cooling for preparing chlorination magnesium alcoholate.By the melting of chlorination magnesium alcoholate Object forms chlorination magnesium alcoholate solid particle into cooling medium by nozzle spray.The alcohol adduct grain diameter of this method preparation Small, machine utilization is low, but particle size adjusts difficulty.

The height that CN1330086A and US6686307 discloses chlorination magnesium alcoholate stirs preparation process.Specifically, first in inertia The suspension of liquid magnesium chloride alcohol adduct is prepared in medium, is later emulsified liquid chlorination magnesium alcoholate by high-speed stirred, and It is transferred to formation chlorination magnesium alcoholate particle in cooling medium.The solid alcohol adduct particle diameter distribution of this method preparation is wider.

CN1463990A discloses a kind of cooling preparation process of emulsification of chlorination magnesium alcoholate.The preparation solution in inert media The suspension of state chlorination magnesium alcoholate, suspended matter enter cooling medium formation chlorination magnesium alcoholate particle after passing through mulser.It should The solid alcohol adduct partial size of method preparation is small, and machine utilization is low, but particle size adjusts difficulty.

CN1267508C discloses a kind of preparation method and application of magnesium halide/alcohol adducts.Specifically, in inert media The suspension of middle preparation liquid magnesium chloride alcohol adduct, suspended matter pass through high-speed rotating high-gravity rotating bed rear into cooling medium Form chlorination magnesium alcoholate particle.This method prepares, the ball of the large-size particles of preparation difficult compared with the alcohol adduct particle of small particle Shape degree is poor (abnormity material easily occur).

The adduct of above-mentioned preparation prepares spheric polypropylene by reacting with titanium compound and internal electron donor compound Catalyst.The form of adduct of magnesium halides carrier decides the form of catalyst, and it prepares point that key is liquid adduct The technology of dissipating, it controls the size and distribution of adduct diameter of carrier, or even affects lacking for adduct solid magnesium halide lattice It falls into, and then affects the polymerization of catalyst.

For the purposes of improving using adduct of magnesium halides as the polymerization of the olefin polymerization catalysis of carrier, researcher is opened Begin to attempt for other electron donor compounds in addition to alcohol and water to be introduced into the adduct preparation process of magnesium halide and alcohol.

CN1169840C and CN1286863C discloses a kind of " magnesium dichloride-alcohol-phthalic acid ester " spherical magnesium chloride and adds Object is closed, still, polymerization activity when for propylene polymerization is low with catalyst that titanium tetrachloride reaction is formed and hydrogen with the adduct Adjust sensibility poor.

It is MgCl that CN103073661A, which discloses general formula,₂(ROH)_m(LB)_nMagnesium chloride adduct, wherein R be it is unsubstituted Or the C replaced containing heteroatom group₁-C₁₅Alkyl, LB are to include C₂-C₂₀Aliphatic ether, C₁-C₁₀Aliphatic carboxylic acid Arrcostab, ketone Or the lewis base of silane, the value that the value of m is 0.5 to 2.5, n is 0.08 to 6, and the adduct, which can be used for preparing, to be had The catalyst of good morphological stability and high polymerization activity.

CN101486722B discloses a kind of such as formula M gX₂-mROH-nE-pH₂Adduct of magnesium halides shown in O, wherein X For chlorine or bromine, R C₁-C₄Alkyl, E be o-alkoxyl benzoate compounds, by the adduct of magnesium halides and halogen Change titanium and optional internal electron donor reaction, can get the catalyst with high stereotaxis ability, the catalysis especially obtained Agent stereotaxis ability still with higher when being used to prepare high melt flow index polypropylene, is preparing the magnesium halide adduction When object, the o-alkoxyl benzoate compounds can derive from the alcoholysis reaction of o-alkoxyl chlorobenzoyl chloride, in order to keep away The alkoxy exempted from o-alkoxyl chlorobenzoyl chloride hydrolyzes, and needs to carry out used raw material stringent anhydrous processing, By weight, the condition of the anhydrous processing, which is generally, makes the water content of magnesium halide lower than 0.2%, the water content of alcohol be lower than 100ppm。

CN102796131A discloses a kind of such as formula M gXY-mR (OH)_rThe adduct of magnesium halides of-nE, wherein X be chlorine or Bromine, Y are chlorine, bromine, C₁-C₁₄Linear or branched alkyl group, C₆-C₁₄Substituted or unsubstituted aryl, C₁-C₁₄Linear chain or branched chain Alkoxy and C₆-C₁₄One of substituted or unsubstituted aryloxy group, R C₁-C₂₀Alkyl, the integer that r is 1 or more, E is Hydroxybenzoic acids or hydroxybenzoic acid esters compound, m 1-5, n 0.001-0.5, the adduct of magnesium halides The catalyst of preparation is reacted with halogenated titanium and optional internal electron donor when for propylene polymerization, the hydrogen response of catalyst Further improvement is obtained.

It is MgXY-mEtOH-n (LB that CN102796127A, which discloses a kind of formula,₁)-k(LB₂)-p(LB₃) magnesium halide adduction Object, wherein X is chlorine or bromine, and Y is chlorine, bromine, C₁-C₁₄Linear or branched alkyl group, C₆-C₁₄Substituted or unsubstituted aryl, C₁- C₁₄Straight or branched alkoxyl and C₆-C₁₄One of substituted or unsubstituted aryloxy group, LB₁、LB₂And LB₃Respectively carboxylic Acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and different from one of alcohol of ethyl alcohol, m 1-5, n 0.005-2, k are 0.0005-0.3, p 0.0005-0.3, the adduct, which is reacted with halogenated titanium and optional internal electron donor, further to be prepared Catalyst can obtain preferable balance, still, the polymerization activity of the catalyst between hydrogen tune ability and stereotaxis ability It needs to be further increased.

The introducing of electron donor can improve the olefinic polymerization performance of catalyst, different adducts in adduct of magnesium halides Preparation method also has the olefinic polymerization performance for improving the catalyst that thus adduct is further prepared to a certain extent.Such as EP395083 uses the magnesium chloride that the higher adduct of alcohol content is successively carried out to the method preparation low ethanol content of partial dealcoholation Adduct has good morphological stability by the catalyst that the adduct is further prepared, has avoid in olefin polymerization Or limitation molecule is formed, to reduce the advantage for bringing problem to polymerization equipment operation.

Currently, the adduct of magnesium halides as described above containing other electron donors in addition to alcohol and water, is typically also to pass through height Speed stirring, misting cooling or the methods of high-gravity rotating bed preparation.It has been found that by being melted using the adduct containing electron donor Adduct prepared by the manufacturing process that body passes through structural unit with hole to cooling medium under pressure is further prepared Catalyst, when being used for olefinic polymerization, catalyst has some improvement to the sensibility of hydrogen tool, and the preparation of adduct Technological operation is simple, adduct particles size is controllable.

Summary of the invention

It is special the purpose of the present invention is to provide a kind of preparation method of novel catalytic component for olefinic polymerization Adduct melt is prepared halogen by the new method of structural unit with hole to cooling medium under pressure to use by sign Change magnesium adduct, contacts adduct of magnesium halides with titanium compound and aromatic carboxylic acid ester compounds；And by the party The catalytic component and catalyst system of method preparation and its application.It is formed by catalytic component prepared according to the methods of the invention Caltalyst when tying up to the catalyst as olefinic polymerization, show the hydrogen response further improved.

As stated in the background art, the preparation method of adduct of magnesium halides ball type carrier includes spray drying process, misting cooling Method, high pressure extrusion methods, high-speed mixing method and high-gravity rotating bed method etc..

(1) spray drying process: with nitrogen by MgCl₂-ol mixed system sprays into hothouse by specially designed nozzle, and Spherical magnesium chloride support is dried in the inert gas of preheating；

However, the present inventor has found under study for action, using spray drying process in carrier preparation process, expend big Ethyl alcohol, nitrogen, energy are measured, and finally obtained carrier granular form is bad；

The adduct carrier of simultaneous spray drying method preparation has following influence to catalyst: due to the outlet of spray-dried instrument Temperature is higher, and the ball type carrier alcohol content caused is lower, and the alcohol on especially spherical carrier particle surface is very few, in subsequent load During titanium, active component cannot with carrier useful effect and combine on the surface, make in catalyst active ingredient content low into And influence the polymerization activity of final catalyst.

(2) spray cooling: spraying into hothouse by specially designed nozzle for magnesium chloride alcohol mixed system with nitrogen, and Condensation forms spherical magnesium chloride support in cooling medium；

However, the process is complex, instrument and equipment is more demanding, is not easy that the ball type carrier of small particle is made, and Alcohol content is excessively high in the carrier of preparation；

The adduct carrier of spray cooling preparation simultaneously has following influence to catalyst: in ball type carrier, due to average Partial size is larger, and alcohol content is higher, excessively fierce due to reacting when adduct is reacted with titanium-containing compound, often makes carrier broken It is broken, cause the fine powder content of final polymer to increase.

(3) high pressure squeezes out cooling method: with the lesser oil refining of viscosity, paraffin, white oil etc. for reaction medium, temperature of reaction system After rising to 120-130 DEG C and maintaining a period of time, it is filled with high pure nitrogen into reaction kettle, reacting kettle inner pressure is made to reach 10-15 Atmospheric pressure；Later, the mixture of chlorination magnesium alcoholate melt and reaction medium is discharged into cooling medium by a discharge duct；It unloads The length of expects pipe is 3-10m, and bore 1-2mm, flow rate of the mixed liquor in pipe is about 4-7m/s；

The technique has the drawback that the high requirements on the equipment, and the form of obtained chlorination magnesium alcoholate particle Not good enough, so that the catalyst granules form finally prepared is not good enough, the particle shape of polymer is not ideal enough, the heap of polymer Product density is not high.

(4) high-speed mixing method: anhydrous magnesium chloride and alcohol are added to the inert fluid immiscible with it by a certain percentage and are situated between It in matter, heats under stiring, makes EtOH/MgCl₂Adduct melt and dispersion are formed in the medium, then in high speed agitator It is emulsified, and is transferred in the medium of low temperature, by MgCl₂-ol adduct wherein rapid condensation cured at spherical MgCl₂It carries Body；

The adduct carrier fractions wider distribution that the technique has the drawback that, and be difficult to prepare small carrier, The activity of the catalyst further prepared is also unsatisfactory.

(5) anhydrous magnesium chloride and alcohol higee technology: are added to the inertia immiscible with it by a certain percentage It in liquid medium, heats under stiring, makes EtOH/MgCl₂It forms adduct melt and dispersion in the medium, is then transferred to super Gravity revolving bed, the inner edge for being equably sprayed at the filler that adjustment is rotating by the static distribution device at the heart in the rotor is arranged On, after material is adjusted the filler shearing of rotation, dispersion, magnesium chloride/alcohol adducts melt is scattered in the form of fine drop In inert media；

The shortcomings that technique: high-gravity rotating bed to carry producing smaller (<30 microns) partial size and greater particle size (>65 micron) When body, diameter of carrier wider distribution；During steady production, generally just using blending agent (generally white oil and silicone oil mix) It can normally produce, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, keep the ratio of the two Example increases difficulty in this way for the repetition stability for maintaining carrier production.

With the gradually development of carrier technique, the technology of Beijing Chemical Research Institute has evolved to high-gravity rotating bed system and adds Object carrier technique is closed, but there are aforementioned drawbacks for this technology, need perspective study and exploitation.

The present inventor is put forward for the first time in the presence of inert liquid medium, and adduct of magnesium halides is acted in pressure Under across structural unit with hole and liquid cooling medium contact preparation adduct solid particle manufacturing process, operation letter List, repetition stability are strong, can steadily control the particle size and size distribution of adduct of magnesium halides, overcome existing adduct The defect of carrier technology of preparing, and the olefin polymerization catalysis that the adduct by obtaining further is prepared has hydrogen response High advantage.

Specifically, according to the first aspect of the invention, the present invention provides a kind of catalyst groups for olefinic polymerization The preparation method divided, this method comprises: adduct of magnesium halides, titanium compound and aromatic carboxylic acid ester compounds are contacted Reaction, the preparation step of the adduct of magnesium halides include: (1) by aqueous MgX¹Y and R¹OH and oxyl benzoyl based compound Mixing, and obtained mixture is heated, the adduct of magnesium halides of liquid is obtained, relative to 1 mole of MgX in terms of magnesium¹Y, R¹OH Amount be 1-5.5 moles, the amount of oxyl benzoyl based compound is 0.001-0.32 moles, aqueous MgX¹The amount of water is in Y 0.011-0.081 moles；Or

By anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated, it obtains To the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1-5.5 moles, oxyl benzoyl The amount of based compound is 0.001-0.32 moles, and the amount of water is 0.011-0.081 moles；

Wherein, X¹For chlorine or bromine, Y is chlorine, bromine, C₁-C₁₄Linear or branched alkyl group, C₆-C₁₄Aryl, C₁-C₁₄It is straight Chain or branched alkoxy and C₆-C₁₄One of aryloxy group, R¹For C₁-C₁₂Linear or branched alkyl group, C₃-C₁₀Naphthenic base And C₇-C₁₀One of aralkyl,

The oxyl benzoyl based compound is shown in formula I,

In Formulas I, X²For one of halogen atom,

R²、R³、R⁴And R⁵Respectively hydrogen, halogen, nitro, C₁-C₂₀Linear or branched alkyl group, C₃-C₂₀Naphthenic base, C₆- C₂₀Aryl and C₇-C₂₀One of aralkyl, alternatively, R²、R³、R⁴And R⁵In two or more be mutually bonded, with Ring is formed,

R⁶With R¹It is not identical, it is C₁-C₂₀Linear or branched alkyl group, C₃-C₂₀Naphthenic base, C₆-C₂₀Aryl and C₇-C₂₀ One of aralkyl；

(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is passed through under pressure has The structural unit in hole is shaped and is dried to liquid cooling medium chilling, obtains Spherical magnesium halide adduct particle.

According to the second aspect of the invention, it is used for the present invention provides preparation method according to the present invention preparation The catalytic component of olefinic polymerization.

According to the third aspect of the present invention, the present invention provides a kind of catalytic components urges in preparation olefinic polymerization Application in agent system.

According to the fourth aspect of the present invention, the present invention provides a kind of catalyst system for olefinic polymerization, this is urged Agent system contains: (i) catalytic component, which is the catalyst group of the present invention for olefinic polymerization Point；

(ii) at least one alkyl aluminum compound；And

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

According to the fifth aspect of the present invention, the present invention provides caltalyst of the present invention, to tie up to olefinic polymerization anti- Application in answering.

According to the sixth aspect of the invention, the present invention provides a kind of olefine polymerizing process, this method is included in alkene Under polymerizing condition, one or more kinds of alkene are contacted with catalyst system of the present invention.

Method of the invention has the advantage that

First, compared to currently advanced higee technology, the inertia of mixing is can be used in technology of the invention Medium production can also use for example individual white oil of single medium or silicone oil to produce, it is therefore apparent that use Single Medium pair The repetition stability of its production is undoubtedly improved in the production of adduct carrier；And higee technology is in steady production process In, it is generally produced using blending agent (the usually blending agent of white oil and silicone oil), but with the continuous consumption of production process, It needs to be continuously replenished fresh inert media, keeps the ratio of the two, this is for maintaining repetition of adduct carrier production to stablize Property, increase difficulty.

Second, compared to aforementioned existing adduct carrier technology of preparing, the equipment of the technology of the present invention is simple, energy consumption and object It consumes low.

Third, by adjusting elements such as the mesh number in hole, the number of plies of structural unit and pressure, be easier to realize to partial size, The control of particle shape, that is to say, that can be according to market needs, the production quantified is changed the line of production convenient and easy.

4th, the catalytic component of the adduct carrier synthesis of technology preparation according to the present invention, compared to existing production Catalytic component, be used for olefinic polymerization when, have improveds hydrogen response, this for exploitation high added value polypropylene tree Rouge is laid a good foundation.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:

Fig. 1 is the schematic diagram according to the mounting means with pore structure unit of one embodiment of the present invention；

Fig. 2 is the schematic diagram according to the mounting means with pore structure unit of one embodiment of the present invention.

Description of symbols

1: adduct of magnesium halides Location Detection of Medium Transportation Pipeline；

2: the unit with pore structure.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

As previously mentioned, the present invention provides a kind of preparation method of catalytic component for olefinic polymerization, this method packet It includes: adduct of magnesium halides, titanium compound and aromatic carboxylic acid ester compounds is subjected to haptoreaction, the adduct of magnesium halides Preparation step include:

(1) by aqueous MgX¹Y and R¹OH and the mixing of oxyl benzoyl based compound, and obtained mixture is heated, it obtains To the adduct of magnesium halides of liquid；Or

By anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated, it obtains To the adduct of magnesium halides of liquid；

According to the method for the present invention, the MgX¹In Y, X¹For chlorine or bromine, Y is chlorine, bromine, C₁-C₁₄Linear chain or branched chain alkane Base, C₆-C₁₄Aryl, C₁-C₁₄Straight or branched alkoxyl and C₆-C₁₄One of aryloxy group；Preferably, Y be chlorine, Bromine, C₁-C₅Linear or branched alkyl group, C₆-C₁₀Aryl, C₁-C₅Straight or branched alkoxyl and C₆-C₁₀Aryloxy group in One kind.

According to the method for the present invention, the MgX¹Y can be a kind of magnesium-containing compound, or two or more to contain magnesium Close the mixture of object.Specifically, in adduct preparation method of the present invention, MgX¹The specific example of Y can include but is not limited to two One or both of magnesium chloride, magnesium dibromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium with On.The angle ready availability from raw material, MgX¹Y is preferably magnesium dichloride.

According to the method for the present invention, the R¹In OH, R¹For C₁-C₁₂Linear or branched alkyl group, C₃-C₁₀Naphthenic base and C₇-C₁₀One of aralkyl；Preferably, R¹For C₁-C₆Linear or branched alkyl group；It is highly preferred that R¹For methyl, ethyl, One of n-propyl, isopropyl, normal-butyl, isobutyl group and n-hexyl.

R¹The specific example of OH can include but is not limited to: methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, N-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, 1,3- propylene glycol and phenyl methanol.

According to the method for the present invention, the oxyl benzoyl based compound is shown in formula I,

In Formulas I, X²For one of halogen atom, preferably chlorine；

Preferably, R²、R³、R⁴And R⁵Respectively hydrogen, C₁-C₈Linear or branched alkyl group, C₃-C₆Naphthenic base, C₆-C₁₀'s Aryl and C₇-C₁₀One of aralkyl；

It is highly preferred that R²、R³、R⁴And R⁵Respectively hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, uncle Butyl, n-pentyl, isopentyl, cyclopenta, just one of base, n-heptyl and tolyl；

Preferably, R⁶For C₁-C₆Linear or branched alkyl group, C₃-C₆Naphthenic base, C₆-C₁₀Aryl and C₇-C₁₀Aralkyl One of base；

It is highly preferred that R⁶For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, just One of base, benzyl and phenethyl.

According to the method for the present invention, the oxyl benzoyl based compound is preferably 4- oxyl benzoyl based compound And/or 2- oxyl benzoyl based compound, more preferably 2- oxyl benzoyl based compound.

The specific example of the oxyl benzoyl based compound can include but is not limited to: 2- methoxy benzoyl chloride, 2- methoxyl group -3- methyl benzoyl chloride, 2- methoxyl group -4- methyl benzoyl chloride, 2- methoxyl group -5- methyl benzoyl chloride, 2- first Oxygroup -3- ethylamino benzonitrile acyl chlorides, 2- methoxyl group -4- ethylamino benzonitrile acyl chlorides, 2- methoxyl group -5- ethylamino benzonitrile acyl chlorides, 2- methoxyl group - 3- n-propylbenzene formyl chloride, 2- methoxyl group -4- n-propylbenzene formyl chloride, 2- methoxyl group -5- n-propylbenzene formyl chloride, 2- methoxy Base -4- diisopropylbenzoyl peroxide chlorine, 2- methoxyl group -4- isobutyl-benzene formyl chloride, 2- methoxyl group -4- tert-butyl benzoyl chloride, 2- first Oxygroup -4- pentylbenzoyl chloride, 2- methoxyl group -4- isoamyl benzene formyl chloride, 2- methoxyl group -4- cyclopenta chlorobenzoyl chloride, 2- second Oxygroup chlorobenzoyl chloride and 2- n-butoxy chlorobenzoyl chloride.

With the method for the invention it is preferred to by aqueous MgX¹Y and R¹OH and the mixing of oxyl benzoyl based compound, and will Obtained mixture heating, obtains the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1- 5.5 moles, preferably 2-3.7 moles, more preferably 2.4-3.7 moles, the amount of oxyl benzoyl based compound are 0.001- 0.32 mole, preferably 0.005-0.17 moles, more preferably 0.015-0.12 moles；Aqueous MgX¹The amount of water is in Y 0.011-0.081 moles, preferably 0.016-0.053 moles, more preferably 0.021-0.045 moles；Or；

By anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated, it obtains To the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1-5.5 moles, preferably 2-3.7 Mole, more preferably 2.4-3.7 moles；The amount of oxyl benzoyl based compound is 0.001-0.32 moles, preferably 0.005-0.17 moles, more preferably 0.015-0.12 moles；The amount of water is 0.011-0.081 moles, preferably 0.016- 0.053 mole, more preferably 0.021-0.045 moles.

In the present invention, by weight, anhydrous MgX¹Water content in Y is lower than 0.2%, and the water content is taken using karr Not method measures.It can be by controlling MgX¹The drying condition of Y and/or by MgX¹Y has the substance of reactivity to contact with to water, So as to adjust MgX¹Water content in Y.The substance for having reactivity to water can be HCl air-flow.

According to the method for the present invention, MgX is removed¹Remaining raw material outside Y is carrying out anhydrous processing using preceding, by original used Moisture in material controls in the range of not influencing test result.Generally, R¹The water content of OH is lower than 100ppm (with weight Meter), the water content of oxyl benzoyl based compound is lower than 10ppm (by weight), and the water content of inert liquid medium is Lower than 50ppm (by weight).Control or the method for reducing water content in solid material or liquid material are many in the art Well known, such as: liquid material can be carried out distilling and/or contacting with water absorbing agent (such as molecular sieve), it can be to heating High-purity inert gas is continually fed into solid material or liquid material, such as High Purity Nitrogen air-flow.

Preparation method according to the present invention, for by anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water Mixture or aqueous MgX¹Y、R¹The mixture of OH and oxyl benzoyl based compound heating, to be reacted and form liquid The condition of adduct of magnesium halides is not particularly limited, as long as the condition of the heating is enough to be formed the adduct of magnesium halides of liquid i.e. It can.Generally, it is 80-140 DEG C that the condition of the heating, which may include: temperature, and the time is 0.5-4 hours.

According to the method for the present invention, the pressure is the relative pressure applied on the basis of atmospheric pressure, and preferably pressure is 0.05-1.0MPa, more preferably 0.1-0.5MPa, further preferably 0.2-0.5MPa.Using the preferred pressure, Neng Goujin The adduct particles particle size and size distribution of one-step optimization preparation, while the catalysis that the adduct by obtaining further is prepared Agent component has improved hydrogen response when being used for olefinic polymerization.

Method of the invention only need to make liquid halogenated magnesium adduct pass through structure with hole under the effect of certain pressure Unit, it is of the invention without can be realized under the conditions of complicated high-gravity rotating bed and without using accurate spraying apparatus Purpose, it can be seen that, method of the invention, compared to existing solid adduct technology of preparing, equipment is simple, operation is simple, Energy consumption and material consumption are low.

With the method for the invention it is preferred to the aperture in the hole be 10-1800 μm, more preferably 20-800 μm, further Preferably 20-200 μm, particularly preferably 40-80 μm.

According to the method for the present invention, the structural unit with hole can be various forms, plate for example, with hole, Net with hole etc..For the present invention, it is however preferred to have the net in hole is examined according to the needs of actual production and the ready availability of material Consider, most preferred diameters are the twine of 0.025-4mm.

According to the method for the present invention, the material of the structural unit with hole is without particular/special requirement, for example, metal material, One of fabric material, plastic material and ceramic material are a variety of.It is excellent according to the ready availability of the needs of actual production and material It is selected as metal material.

A preferred embodiment of the invention, the structural unit with hole are stratum reticulare.

A preferred embodiment of the invention, the stratum reticulare are metal net layer.

According to the method for the present invention, using the metal mesh of multilayer macropore gauge structure and using the small-bore of the relatively little of number of plies Structural metal net can obtain the comparable adduct solid particle of particle morphology.Prepare small particle (such as less than 30 μm) adduct The metal mesh structure that 1-20 layers of aperture gauge structure (such as aperture is 30-50 μm) is preferably used when carrier is preparing big partial size (as greatly In 60 μm) adduct carrier when preferably use the metal mesh knots of 1-20 layers of opposite large aperture (such as aperture is 65-200 μm) structure Structure.

A preferred embodiment of the invention, the stratum reticulare include 1-20 layers, preferably include 2-8 layers, more preferably It is 3-5 layers；Every thickness degree is respectively 0.01-0.35mm, preferably 0.05-0.25mm, more preferably 0.09-0.1mm.

Method of the invention, it is easy to accomplish to grain by adjusting elements such as the mesh number in hole, the number of plies of structural unit and pressure The control of diameter, particle shape, that is to say, that method of the invention can be according to market needs, the production quantified, change the line of production convenient easy Row.

According to the method for the present invention, the inert liquid medium can for not with magnesium halide, alcohol, aromatic carboxylic acid esters chemical combination The liquid compound that object chemically reacts, the preferably described inert liquid medium are silicone oil and/or inert fluid hydrocarbon solvent；It is more excellent Selection of land, the inert liquid medium are C₄-C₁₀Alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon One of oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil are a variety of；The further preferably described inert fluid is situated between Matter is methyl-silicone oil or white oil/methyl-silicone oil mixture.

Method of the invention, compared to currently advanced higee technology, technology of the invention can be used mixed The inert media of conjunction produces, and for example individual white oil of single medium or silicone oil can also be used to produce, worked well.It is aobvious and easy See, its repetition stability is undoubtedly increased for the production of adduct carrier using Single Medium.Higee technology is steady Determine in production process, is generally produced using blending agent (the usually blending agent of white oil and silicone oil), but with production process Continuous consumption, need to be continuously replenished fresh inert media, the ratio both kept, the in this way weight for maintaining carrier production Multiple stability, increases difficulty.

In the present invention, the dosage of the inert liquid medium can be according to MgX¹The specific dosage of Y selects.Generally, Relative to 1 mole of MgX in terms of magnesium¹Y, the dosage of inert liquid medium are 0.2-13L；Preferably, relative to 1 mole in terms of magnesium MgX¹Y, the dosage of inert liquid medium are 0.6-6.5L.

Method according to the invention it is possible to the adduct of magnesium halides of the liquid be mixed with inert liquid medium, and will Obtained mixture passes through structural unit with hole under pressure and contacts progress cooling forming with liquid cooling medium.

Can also using the part inert liquid medium as the reaction medium for the adduct of magnesium halides for preparing the liquid, To obtain the mixed liquor of the adduct of magnesium halides containing liquid, then by the inert liquid medium of the mixed liquor and remainder Then mixing passes through structural unit with hole under pressure and contacts progress cooling forming with liquid cooling medium.

Can also using all inert liquid mediums as the reaction medium for the adduct of magnesium halides for preparing the liquid, To obtaining the mixed liquor of the adduct of magnesium halides containing liquid, then pass through under pressure structural unit with hole with Liquid cooling medium contact carries out cooling forming.

When needing, some surfactants, such as fatty acid glycerine are also optionally added into the inert liquid medium Ester, fatty acid sorbitan, polysorbate, polyoxyethylene ether or Pluronic F68.The surfactant Dosage can be the conventional amount used of this field, such as: relative to 1 mole of MgX in terms of magnesium¹Y, the dosage of the surfactant It can be 0.001-1 moles.

According to the method for the present invention, the liquid cooling medium can for it is commonly used in the art it is various not with magnesium halide adduction Chemically interactive liquid medium occurs for object.For example, the liquid cooling medium can be unreactive hydrocarbons solvent.The liquid is cold But the specific example of medium can include but is not limited to: pentane, n-hexane, normal heptane, gasoline or petrol ether.

In the present invention, the liquid cooling medium is carrying out anhydrous processing using preceding, by liquid cooling medium used In moisture control in the range of not influencing test result.Generally, it is by the water content control of the liquid cooling medium Not higher than 5ppm (by weight).The method for controlling or reducing water content in the liquid cooling medium is many institutes in the art Known, such as: liquid material can be carried out distilling and/or contacting with water absorbing agent (such as molecular sieve), it can be to the liquid of heating High-purity inert gas is continually fed into body material, such as High Purity Nitrogen air-flow.

The temperature of the liquid cooling medium, which is subject to, can make the product cooling and shape.Generally, the liquid The temperature of cooling medium can be -50 DEG C to 0 DEG C, preferably -40 DEG C to -20 DEG C.Do not have for the dosage of the cooling medium Special limitation, as long as the dosage of the cooling medium is enough product is cooling and shapes.Specifically, the cooling medium Volume ratio with the product is 1-15:1, preferably 2-9:1.

Adduct of magnesium halides particle obtained from shaping through chilling can be washed and be dried.This field skill can be used Method well known to art personnel washs obtained adduct of magnesium halides, for example, can using inertia hydrocarbon system solvent (such as: just Pentane, n-hexane, normal heptane, petroleum ether and gasoline) obtained adduct of magnesium halides is washed.The temperature of the drying can Think not higher than 35 DEG C, preferably 25-30 DEG C；The time of the drying can be 0.5-3 hours, preferably 1-2h.The drying It can be carried out under conditions of normal pressure or reduction pressure.

It is not being bound by any particular theory, with MgX¹Y is MgCl₂, R¹OH is ethyl alcohol, and oxyl benzoyl compound is For 2- methoxy benzoyl chloride, the following reaction mechanism mechanism of reaction is undergone according to the method that above two adduct prepares embodiment, from And obtain adduct of magnesium halides of the invention.

Adduct support preparation method of the invention is simple and easy, such as the unit with pore structure can be installed In adduct of magnesium halides Location Detection of Medium Transportation Pipeline or it is mounted on adduct of magnesium halides Location Detection of Medium Transportation Pipeline and liquid cooling medium Between storage tank.Specifically, as shown in Figure 1, the unit 2 with pore structure is mounted on adduct of magnesium halides material delivery pipe In line 1, adduct of magnesium halides passes through the unit with pore structure before contacting with cooling medium；Alternatively, as shown in Fig. 2, will The unit 2 with pore structure is mounted on adduct of magnesium halides Location Detection of Medium Transportation Pipeline 1 and liquid cooling medium storage tank (in figure not Show) between, adduct of magnesium halides passes through the unit with pore structure before contacting with cooling medium.

The adduct of magnesium halides diameter of carrier size and particle diameter distribution of technology preparation of the invention are easy to control, and use institute State the catalytic component that adduct carrier further synthesizes, the catalytic component produced compared with prior art, poly- for alkene When conjunction, improved hydrogen response is shown, this lays a good foundation for developing the acrylic resin of high added value.

According to a preferred embodiment of the present invention, this method comprises: it is adduct of magnesium halides is anti-with titanium compound It answers, and is added within one or more periods before and after, during the adduct of magnesium halides is reacted with titanium compound The aromatic carboxylic acid ester compounds carry out the haptoreaction.

Specifically, the adduct of magnesium halides and titanium compound react can according to mode same as the prior art into Row, for example, the adduct of magnesium halides can be suspended in the mixed liquor of cold titanium compound or titanium compound and atent solvent In (temperature of the mixture of the titanium compound or titanium compound and atent solvent can be -40 DEG C to 0 DEG C, preferably -25 DEG C To -15 DEG C), obtained mixture is then heated to 40-130 DEG C, is preferably heated to 80-130 DEG C, and tie up at the temperature disclosed above It holds 0.5-2 hours, is then separated by solid-liquid separation and collects solid；Then, obtained solid is suspended in titanium compound, and will Obtained mixture is heated to 60-130 DEG C, is preferably heated to 80-130 DEG C, and maintenance 0.5-2 hours at the temperature disclosed above, so After be separated by solid-liquid separation and collected solid, the operation can carry out it is one or many, preferably carry out 2-4 times；Finally, molten with inertia The solid that agent is washed, the atent solvent are preferably aliphatic hydrocarbon or aromatic hydrocarbons, such as: n-hexane, normal heptane, normal octane, just Decane and toluene.

In the preparation method of the catalytic component for olefinic polymerization, the aromatic carboxylic acid ester compounds are in institute It states in one or more periods in front of and after, during adduct of magnesium halides is reacted with titanium compound and is added, preferably exist Adduct of magnesium halides particle is added while reaction with titanium compound.

In the present invention, the aromatic carboxylic acid esters are preferably polynary aromatic carboxylic acid esters, more preferably phthalic acid alkane Base ester, further preferably alkyl are C₂-C₈Alkyl phthalates.

Specifically, in the present invention, the example of the polynary aromatic carboxylic acid esters can be but be not limited to: phthalic acid two Ethyl ester, diisopropyl phthalate, diisobutyl phthalate, n-butyl phthalate, phthalic acid two are different Monooctyl ester, di-n-octyl phthalate, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids di-n-butyl, triethyl trimellitate, inclined benzene three Sour tri-n-butyl, three triethylenetetraminehexaacetic acid ester of biphenyl, connection benzenetricarboxylic acid tri-n-butyl, in four N-butyl of pyromellitic acid tetra-ethyl ester and pyromellitic acid It is one or more.

In a specific embodiment of the present invention, use diisobutyl phthalate, n-butyl phthalate as Aromatic carboxylic acid esters internal electron donor exemplary illustration advantage of the invention.

Generally, the preparation method of the catalytic component according to the present invention for olefinic polymerization, the titanium compound can Think three halogenated titaniums and general formula Ti (OR⁷)_4-qX² _qShown in one or more of titanium compound, in the general formula, R⁷It can be with For C₁-C₁₀Alkyl, X²It can be halogen, m can be the integer of 0-4.Preferably, the titanium compound is titanium tetrachloride, four Titanium bromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, three titanium butoxide of a chlorine, dichloro dibutoxy titanium, one fourth of trichlorine One or both of oxygroup titanium, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine and titanium trichloride with On.It is highly preferred that the titanium compound is titanium tetrachloride.

According to the present invention, the dosage of the adduct of magnesium halides, the dosage of titanium compound and aromatic carboxylic acid esters chemical combination The dosage of object can make appropriate choice according to the composition of the expected catalytic component for olefinic polymerization.For example, described The molar ratio of titanium compound, aromatic carboxylic acid ester compounds and the adduct of magnesium halides can be 5-100:0.01-0.5:1； Preferably 20-80:0.05-0.35:1, the titanium compound is in terms of titanium elements, and the adduct of magnesium halides is in terms of magnesium elements.This In invention, the amount of titanium compound is the total amount for including the titanium compound used in preparation catalytic component process of the present invention.

As previously mentioned, the present invention also provides the urging for olefinic polymerization that one kind is prepared according to the method described in the present invention Agent component.

Catalytic component according to the present invention for olefinic polymerization, due to having used adduct of magnesium halides according to the present invention The adduct of magnesium halides containing other electron donors in addition to alcohol and water of preparation method preparation, shows when being used for olefin polymerization The hydrogen response improved out.

Catalyst according to the invention component is suitable for being used to preparing olefin polymerization catalyst system.

As previously mentioned, invention further provides a kind of catalyst system for olefinic polymerization, the catalyst system Contain:

(i) catalytic component, the catalytic component are the catalytic component of the present invention for olefinic polymerization；

(ii) at least one alkyl aluminum compound；And

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

Detailed description has been carried out above for the composition and preparation method of the catalytic component, no longer superfluous herein It states.

The alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art.For example, the alkyl calorize Closing object can be alkylaluminium sesquichloride and general formula AlR⁸R⁹R¹⁰One or more of shown compound, the general formula In, R⁸、R⁹And R¹⁰It respectively can be chlorine and C₁-C₈One of alkyl, and R⁸、R⁹And R¹⁰At least one of be C₁-C₈'s Alkyl.Preferably, the alkyl aluminum compound is triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, three just Octyl aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, one ethyl of dichloro Aluminium, one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro, one n-hexyl aluminium of dichloro and Al₂Et₃Cl₃One or more of, Wherein, Et is ethyl.

Catalyst system according to the present invention for olefinic polymerization, the alkyl aluminum compound in terms of aluminium and urging in terms of titanium The molar ratio of agent component can be 1-2000:1, preferably 20-700:1.

In the case where the polymerization of organic vertical structure of alkene especially alpha-olefin (such as propylene or 1- butylene), according to the present invention The catalyst system for olefinic polymerization can also be comprising same or different being given with the compound for being used as internal electron donor Electron compound is as external donor compound.

The external donor compound can be various external donor compounds commonly used in the art, such as: it is described External donor compound can be one in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound Kind is two or more.Preferably, the external electron donor is general formula R¹¹ _xR¹² _ySi(OR¹³)_zShown in organo-silicon compound, this is logical In formula, R¹¹、R¹²And R¹³Respectively C₁-C₁₈Alkyl or contain heteroatomic C₁-C₁₈Alkyl；X and y is respectively the whole of 0-2 Number, z are the integer of 1-3, and x+y+z=4.It is highly preferred that general formula R¹¹ _xR¹² _ySi(OR¹³)_zIn, R¹¹And R¹²At least one of Selected from C₃-C₁₀With or without heteroatomic branched alkyl, C₃-C₁₀With or without heteroatomic substituted or unsubstituted cycloalkanes Base and C₆-C₁₀One of substituted or unsubstituted aryl, R¹³For C₁-C₁₀Alkyl, preferably methyl；X is 1, y 1, z It is 2；Alternatively, R¹²For C₃-C₁₀Branched alkyl or C₃-C₁₀Naphthenic base, and R¹³For methyl, x 0, y 1, z 3.

In the present invention, the example of the organo-silicon compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, Diisopropyl dimethoxy silane, normal-butyl cyclohexyl dimethoxysilane, second, isobutyl dimethoxy silane, diphenyl diformazan Oxysilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- tert-butyl two Methoxy silane, (the fluoro- 2- propyl of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilane, (the fluoro- 2- propyl of 1,1,1- tri-) - Methyl dimethoxysilane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and tertiary hexyl trimethoxysilane.

Generally, relative to 1 mole of alkyl aluminum compound in terms of aluminium, the dosage of the external donor compound can be with It is 0.005-0.5 moles；Preferably, relative to 1 mole of alkyl aluminum compound in terms of aluminium, the external donor compound Dosage is 0.01-0.4 moles.

Catalyst system according to the present invention for olefinic polymerization, preferably with one of above-mentioned electron donor compound Or it is two or more as external electron donor.

According to the present invention, described to be used for olefinic polymerization when the catalyst system for olefinic polymerization is used for olefinic polymerization Catalytic component, alkyl aluminum and optional external electron donor can be separately added into polymer reactor, be added after can also mixing In polymer reactor, prepolymerization method commonly understood in the industry, which can also be used, to be added in polymer reactor after alkene pre-polymerization.

As previously mentioned, the present invention provides the caltalyst of the present invention for olefinic polymerization, to tie up to olefinic polymerization anti- Application in answering.

The present invention also provides a kind of olefine polymerizing process, this method is included under olefin polymerization conditions, by one kind or two Kind or more alkene contacted with catalyst system provided by the invention.

Of the invention thes improvement is that using a kind of adduct prepared by new adduct technology of preparing and then makes The standby catalytic component and its catalyst system for olefinic polymerization.Olefine polymerizing process of the invention is for olefinic polymerization item Part and used alkene are not particularly limited.

Generally, olefine polymerizing process according to the present invention, the alkene can be general formula CH₂=CHR¹⁴Shown in alkene Hydrocarbon, wherein R¹⁴It can be hydrogen, C₁-C₁₂Linear or branched alkyl group and C₆-C₁₂One of aryl.Alkene according to the present invention Polymerized hydrocarbon method, when necessary, the alkene can also contain a small amount of alkadienes.Olefine polymerizing process according to the present invention, institute Stating alkene is preferably propylene or propylene and CH₂=CHR¹⁴Shown in alkene, wherein R¹⁴For hydrogen and C₁-C₆Linear chain or branched chain One of alkyl.

Olefine polymerizing process according to the present invention, the polymerization can carry out according to conventional methods in the art.For example, institute Stating polymerization can be bulk polymerization, gas-phase polymerization, slurry polymerization or liquid-phase bulk-gas phase polymerization mix.Alkene according to the present invention Polymerized hydrocarbon method, the olefin polymerization conditions can be the normal condition of this field, for example, polymerization temperature can be 0-150 DEG C, Preferably 60-90 DEG C；Polymerization pressure can be normal pressure or pressurization.

Following example is used to illustrate the present invention, is not for limiting the scope of the invention.

Test method:

1, it melt index: at 230 DEG C of temperature and the pressure of 2.16kg, is measured according to ASTM D1238-99.

2, polymer isotacticity: using the measurement of heptane extraction process (heptane boiling extracting 6 hours): two grams of dry polymer Sample is placed in extractor after being extracted 6 hours with boiling heptane, and residue is dry to the resulting polymer weight (g) of constant weight Ratio with 2 is isotacticity.

3, particle diameter distribution is tested: average grain diameter and size distribution the Masters Sizer of adduct of magnesium halides particle 2000 (being manufactured by Malvern Instruments Ltd) particle size analyzer determinations.

Prepare embodiment 1

In the reaction kettle of 1000mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd, with Poidometer, water content (are commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, with weight lower than 50ppm), 300mL methyl-silicone oil Meter, water content be lower than 50ppm), 30g contain 0.44wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), 50mL without Water-ethanol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 1mL 2- methoxy benzoyl chloride (quotient Purchased from TOKYO KASEI KOGYO CO.LTD), it is warming up to 125 DEG C under stiring.After isothermal reaction 3 hours, mixture is existed It is depressed into advance under the pressure of 0.3MPa by being preinstalled with the blowing pipeline that 4 layers of aperture are 75 μm of metal meshes (every thickness degree 0.1mm) It is cooled in -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carries out chilling forming.It is filtered to remove liquid, will The solid arrived is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain ball according to the present invention Shape adduct of magnesium halides S1, characterization result such as table 1.

Prepare embodiment 2

In the reaction kettle of 1000mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd, with Poidometer, water content (are commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, with weight lower than 50ppm), 300mL methyl-silicone oil Meter, water content (are commercially available from north lower than 50ppm), 30g anhydrous magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), 50mL dehydrated alcohol Capital chemical plant, by weight, water content be lower than 100ppm), 1mL 2- methoxy benzoyl chloride (be commercially available from TOKYO KASEI KOGYO CO.LTD) and 0.15g water, it is warming up to 125 DEG C under stiring.After isothermal reaction 3 hours, by mixture 0.3MPa's It is depressed into and pre-cools to -30 by being preinstalled with the blowing pipeline that 4 layers of aperture are 75 μm of metal meshes (every thickness degree 0.1mm) under pressure DEG C 2L hexane (by weight, water content be lower than 5ppm) in, carry out chilling forming.It is filtered to remove liquid, the solid that will be obtained It is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain spherical magnesium halide according to the present invention Adduct S2, characterization result such as table 1.

Prepare embodiment 3

Spherical magnesium halide adduct S3 is prepared according to the method for preparation embodiment 1, unlike, structural unit with hole The metal mesh (every thickness degree 0.09mm) for being 48 μm for 4 layers of aperture, characterization result such as table 1.

Prepare embodiment 4

In the reaction kettle of 1000mL, addition 500mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd, with Poidometer, water content be lower than 50ppm), 30g contain 0.44wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), 50mL dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 1mL 2- methoxybenzene first Acyl chlorides (is commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up to 125 DEG C under stiring.After isothermal reaction 3 hours, it will mix Object is closed under the pressure of 0.2MPa by pre-installing the blowing pipeline pressure that aperture is 75 μm of metal meshes (every thickness degree 0.1mm) that is of five storeys To pre-cooling into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), chilling forming is carried out.It is filtered to remove liquid Obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C by body, to obtain according to this The Spherical magnesium halide adduct S4 of invention, characterization result such as table 1.

Prepare embodiment 5

In the reaction kettle of 1000mL, addition 500mL methyl-silicone oil (it is commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, By weight, water content be lower than 50ppm), 30g contain 0.44wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), 50mL dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 1mL 2- methoxybenzene first Acyl chlorides (is commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up to 125 DEG C under stiring.After isothermal reaction 3 hours, it will mix Object is closed under the pressure of 0.5MPa by pre-installing the blowing pipeline pressure that aperture is 75 μm of metal meshes (every thickness degree 0.1mm) that haves three layers To pre-cooling into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), chilling forming is carried out.It is filtered to remove liquid Obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C by body, to obtain according to this The Spherical magnesium halide adduct S5 of invention, characterization result such as table 1.

Prepare comparative example 1

According to the method preparation of preparation embodiment 1, the difference is that, it is 2400rpm that obtained mixture, which is transferred to revolving speed, It is high-gravity rotating bed in, by it is high-gravity rotating bed enter pre-cool to -30 DEG C of 2L hexane (by weight, water content Lower than 5ppm) in, carry out chilling forming.It is filtered to remove liquid, obtained solid is washed 5 times with the hexane of 300mL, and 30 It is dried in vacuo 1.5 hours at DEG C, so that Spherical magnesium halide adduct DS1 according to the present invention is obtained, characterization result such as table 1.

Prepare comparative example 2

According to the method preparation of preparation embodiment 4, the difference is that, it is 2400rpm that obtained mixture, which is transferred to revolving speed, It is high-gravity rotating bed in, by it is high-gravity rotating bed enter pre-cool to -30 DEG C of 2L hexane (by weight, water content Lower than 5ppm) in, carry out chilling forming.It is filtered to remove liquid, obtained solid is washed 5 times with the hexane of 300mL, and 30 It is dried in vacuo 1.5 hours at DEG C, so that Spherical magnesium halide adduct DS2 according to the present invention is obtained, characterization result such as table 1.

Table 1

Prepare embodiment	D10(μm)	D50(μm)	D90(μm)	Span
					1	29.1	48.8	78.9	1.02
2	28.4	48.4	78.7	1.04
					3	25.5	44.4	69.3	0.99
4	43.0	70.3	118.1	1.07
					5	24.2	35.2	60.5	1.03
Prepare comparative example 1	27.6	48.7	79.7	1.07
					Prepare comparative example 2	30.9	65.7	130.7	1.52

Note: Span=(D₉₀-D₁₀)/D₅₀

Compared to higee technology it can be seen from the result of table 1, the present invention can prepare the adduction of different-grain diameter Object carrier, and narrower particle size distribution, big partial size (D50 > 60 μm) the adduct carrier especially prepared still have relatively narrow granularity Distribution.

Embodiment 1

The embodiment is used to illustrate catalytic component for olefinic polymerization and preparation method thereof and for olefinic polymerization Catalyst system and its application.

(1) preparation of the catalytic component of olefinic polymerization is used for using adduct S1 prepared by preparation embodiment 1:

In the glass reaction bottle of 300mL, under the conditions of nitrogen protection, 10mL hexane, 90mL titanium tetrachloride are sequentially added, it is cold But to -20 DEG C, 8.0g Spherical magnesium halide adduct S1 is added, and stir 30 minutes at -20 DEG C.Then, 110 are to slowly warm up to DEG C, and 1.5mL diisobutyl phthalate is added in temperature-rise period.After isothermal reaction 30 minutes, liquid is filtered out at 110 DEG C Body.80mL titanium tetrachloride is added, is warming up to 120 DEG C, filters out liquid after maintaining 30 minutes at 120 DEG C；Then, 80mL tetra- is added Titanium chloride, and 120 DEG C are warming up to, liquid is filtered out after maintaining 30 minutes at 120 DEG C.Finally with 60 DEG C of hexane to obtained solid Washing 5 times (hexane dosage is 80mL/ times), and it is dried in vacuo obtained solid object, to obtain spherical catalyst components C1.

(2) propylene polymerization:

Under nitrogen protection, the hexane solution that 5mL triethyl aluminum is sequentially added into the stainless steel autoclave of 5L is (dense It spends for the hexane solution (concentration 0.1mmol/mL) and 9mg ball of 0.5mmol/mL), 1mL Cyclohexyl Methyl Dimethoxysilane Shape catalytic component C1.Autoclave is closed, 5.0L (normal volume) hydrogen and 2.3L liquid propene is added.70 DEG C are warming up to, instead It answers 1 hour.Then, cool down, release, discharging, and be dried, to obtain polypropylene.The polymerization activity of catalyst is calculated, is surveyed Standby polyacrylic isotactic index and melt index are customized, the results are shown in Table 2.

Comparative example 1

The catalyst for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, as a result in table 2 In list, the difference is that adduct of magnesium halides is prepared as follows:

In the reaction kettle of 500mL, 150mL white oil is added and (Guangzhou Ming En petrochemical industry Co., Ltd is commercially available from, with weight Meter, water content is lower than magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), the 50mL that 50ppm), 30g contain 0.44wt% moisture Dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 1mL 2- methoxy benzoyl chloride (being commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up to 125 DEG C under stiring.After isothermal reaction 3 hours, by mixture The 300mL methyl-silicone oil that indentation is preheated to 125 DEG C (is commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, and by weight, water contains Amount is lower than 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.Then, by emulsification product nitrogen Indentation was pre-cooled into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carried out chilling forming.It is filtered to remove Obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C by liquid, to obtain spherical shape Adduct of magnesium halides.It the results are shown in Table 2.

Comparative example 2

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, the preparation of the catalytic component of olefinic polymerization is used for using adduct DS1 prepared by preparation comparative example 1, to obtain Spherical catalyst components DC1.It the results are shown in Table 2.

Embodiment 2

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not With the additional amount of diisobutyl phthalate is 1.0ml, to obtain spherical catalyst components C2.It the results are shown in Table 2.

Embodiment 3

The embodiment is used to illustrate catalytic component for olefinic polymerization and preparation method thereof and for olefinic polymerization Catalyst and its application.

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not With internal electron donor is the n-butyl phthalate of 1.5ml, to obtain spherical catalyst components C3.As a result see Table 2.

Comparative example 3

Catalytic component and progress propylene polymerization according to the method preparation of comparative example 1 for olefinic polymerization, institute is not With the internal electron donor used is the n-butyl phthalate of 1.5ml.It the results are shown in Table 2.

Embodiment 4

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, the preparation of the catalytic component of olefinic polymerization is used for using adduct S2 prepared by preparation embodiment 2, to obtain ball Shape catalytic component C4.It the results are shown in Table 2.

Comparative example 4

Catalyst and progress propylene polymerization according to the method preparation of embodiment 4 for olefinic polymerization, it is different It is that adduct of magnesium halides is prepared as follows:

In the reaction kettle of 500mL, 150mL white oil is added and (Guangzhou Ming En petrochemical industry Co., Ltd is commercially available from, with weight Meter, water content (are commercially available from lower than 50ppm), 30g anhydrous magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), 50mL dehydrated alcohol Beijing Chemical Plant, by weight, water content be lower than 100ppm), 1mL 2- methoxy benzoyl chloride (be commercially available from TOKYO KASEI KOGYO CO.LTD) and 0.15g water, it is warming up to 125 DEG C under stiring.After isothermal reaction 3 hours, mixture is pressed into It is preheated to 125 DEG C of 300mL methyl-silicone oil and (is commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, and by weight, water content is low In 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.Then, emulsification product is pressed into nitrogen It pre-cools into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carries out chilling forming.Liquid is filtered to remove, Obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain spherical magnesium halide Adduct.It the results are shown in Table 2.

Embodiment 5

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, the preparation of the catalytic component of olefinic polymerization is used for using adduct S3 prepared by preparation embodiment 3, to obtain ball Shape catalytic component C5.It the results are shown in Table 2.

Embodiment 6

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, the preparation of the catalytic component of olefinic polymerization is used for using adduct S4 prepared by preparation embodiment 4, to obtain ball Shape catalytic component C6.It the results are shown in Table 2.

Comparative example 5

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, the preparation of the catalytic component of olefinic polymerization is used for using adduct DS2 prepared by preparation comparative example 2, to obtain Spherical catalyst components DC2.It the results are shown in Table 2.

Embodiment 7

The catalytic component for olefinic polymerization is prepared according to the method for embodiment 1 and carries out propylene polymerization, and institute is not It is same, the preparation of the catalytic component of olefinic polymerization is used for using adduct S5 prepared by preparation embodiment 5, to obtain ball Shape catalytic component C7.It the results are shown in Table 2.

Table 2

From the results shown in Table 2, catalytic component of the invention shows improved hydrogen when being used for propylene polymerization Sensibility is adjusted, while still maintaining higher isotactic index (boiling n-heptane insoluble matter > 96.0wt%), industry with higher Application value.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. a kind of preparation method of the catalytic component for olefinic polymerization, this method comprises: adduct of magnesium halides, titanizing are closed Object and aromatic carboxylic acid ester compounds carry out haptoreaction, which is characterized in that the preparation step packet of the adduct of magnesium halides It includes:

(1) by aqueous MgX¹Y and R¹OH and the mixing of oxyl benzoyl based compound, and obtained mixture is heated, obtain liquid The adduct of magnesium halides of state；Or

By anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated, obtain liquid The adduct of magnesium halides of state；

Wherein, X¹For chlorine or bromine, Y is chlorine, bromine, C₁-C₁₄Linear or branched alkyl group, C₆-C₁₄Aryl, C₁-C₁₄Straight chain or branch Chain alkoxy and C₆-C₁₄One of aryloxy group, R¹For C₁-C₁₂Linear or branched alkyl group, C₃-C₁₀Naphthenic base and C₇- C₁₀One of aralkyl,

The oxyl benzoyl based compound is shown in formula I,

In Formulas I, X²For one of halogen atom,

R²、R³、R⁴And R⁵Respectively hydrogen, halogen, nitro, C₁-C₂₀Linear or branched alkyl group, C₃-C₂₀Naphthenic base, C₆-C₂₀'s Aryl and C₇-C₂₀One of aralkyl, alternatively, R²、R³、R⁴And R⁵In two or more be mutually bonded, with formed Ring,

R⁶With R¹It is not identical, it is C₁-C₂₀Linear or branched alkyl group, C₃-C₂₀Naphthenic base, C₆-C₂₀Aryl and C₇-C₂₀Virtue One of alkyl；

(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is passed through under pressure with hole Structural unit is shaped and is dried to liquid cooling medium chilling, obtains Spherical magnesium halide adduct particle；

The pressure is 0.05-1.0MPa；

The aperture in the hole is 10-1800 μm；

The structural unit with hole is stratum reticulare, and the stratum reticulare is metal net layer.

2. preparation method according to claim 1, wherein the pressure is 0.1-0.5MPa.

3. preparation method according to claim 1, wherein the aperture in the hole is 20-800 μm.

4. preparation method according to claim 1, wherein the number of plies of the stratum reticulare is 1-20 layers；Every thickness degree is respectively 0.01-0.35mm。

5. preparation method according to claim 1, wherein the number of plies of the stratum reticulare is 2-8 layers；Every thickness degree is respectively 0.05-0.25mm。

6. preparation method according to claim 1, wherein the inert liquid medium is silicone oil and/or inert fluid hydrocarbon Solvent.

7. preparation method according to claim 6, wherein the inert liquid medium is C₄-C₁₀Alkane, kerosene, all One of intellectual circle's oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil are more Kind.

8. preparation method according to claim 6, wherein the inert liquid medium is silicone oil.

9. preparation method according to claim 1, wherein the aromatic carboxylic acid ester compounds are polynary aromatic carboxylic acid Ester.

10. preparation method according to claim 1, wherein the aromatic carboxylic acid ester compounds are phthalic acid alkane Base ester.

11. preparation method according to claim 1, wherein it is C that the aromatic carboxylic acid ester compounds, which are alkyl,₂-C₈'s Alkyl phthalates.

12. preparation method according to claim 1, wherein

Relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1-5.5 moles, and the amount of oxyl benzoyl based compound is 0.001-0.32 moles, aqueous MgX¹The amount of water is 0.011-0.081 moles in Y；Or

Relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1-5.5 moles, and the amount of oxyl benzoyl based compound is 0.001-0.32 moles, the amount of water is 0.011-0.081 moles；

The oxyl benzoyl based compound is 4- oxyl benzoyl based compound and/or 2- oxyl benzoyl system chemical combination Object；

The condition of the heating includes: that temperature is 80-140 DEG C, and the time is 0.5-4 hours.

13. preparation method according to claim 1, wherein the titanium compound, aromatic carboxylic acid ester compounds with it is described The molar ratio of adduct of magnesium halides is 5-100:0.01-0.5:1, and the titanium compound is in terms of titanium elements, the magnesium halide adduction Object is in terms of magnesium elements.

14. preparation method according to claim 13, wherein the titanium compound, aromatic carboxylic acid ester compounds and institute The molar ratio for stating adduct of magnesium halides is 20-80:0.05-0.35:1.

15. the catalytic component for olefinic polymerization that method described in any one of claim 1-14 is prepared.

16. the catalytic component described in claim 15 for olefinic polymerization is preparing answering in olefin polymerization catalyst system With.

17. a kind of catalyst system for olefinic polymerization, the catalyst system contain:

(i) catalytic component, the catalytic component are the catalytic component that olefinic polymerization is used for described in claim 15；

(ii) at least one alkyl aluminum compound；And

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

18. the caltalyst described in claim 17 for olefinic polymerization ties up to the application in olefin polymerization.

19. a kind of olefine polymerizing process, this method are included under olefin polymerization conditions, by one or more kinds of alkene and right It is required that catalyst system described in 17 contacts.