CN106608934A

CN106608934A - Catalyst component used for olefin polymerization and preparation method and application thereof, catalyst system used for olefin polymerization and application thereof, and olefin polymerization method

Info

Publication number: CN106608934A
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: 2017-05-03
Anticipated expiration: 2035-10-27
Also published as: CN106608934B

Abstract

The invention relates to the field of olefin polymerization, and specifically provides a catalyst component used for olefin polymerization and a preparation method and application thereof. The preparation method comprises a step of subjecting a magnesium halide adduct, a titanium compound and an aromatic carboxylate compound to a contact reaction. The magnesium halide adduct is prepared through the following steps: (1) mixing aquo MgX1Y, R1OH and an alkoxy benzoyl compound and heating the obtained mixture so as to obtain a liquid magnesium halide adduct, or mixing anhydrous MgX1Y, R1OH, the alkoxy benzoyl compound and water and heating the obtained mixture so as to obtain the liquid magnesium halide adduct; and (2) allowing the liquid magnesium halide adduct to penetrate through a structural unit with holes to a liquid cooling medium under the action of pressure in the presence of an inert liquid medium, and carrying out quenching formation and drying. The invention provides a catalyst system used for olefin polymerization and application thereof, and an olefin polymerization method. The catalyst component synthesized from an adduct carrier prepared by using the method has improved hydrogen sensitivity when used for olefin polymerization.

Description

Catalytic component for olefinic polymerization and its preparation method and application and the catalyst system for olefinic polymerization and its application And olefine polymerizing process

Technical field

The present invention relates to a kind of preparation method of the catalytic component for olefinic polymerization, and by being used for that the method is obtained The catalytic component of olefinic polymerization and its application in the catalyst system for olefinic polymerization is prepared；It is poly- with for alkene The catalyst of conjunction and its application in olefinic polyreaction；With a kind of catalyst for olefinic polymerization using the present invention Olefine polymerizing process.

Technical background

By titanium compound and electron donor it is compound loaded be existing to prepare Ziegler-Natta catalyst in magnesium halide in active Have well known to technology.Wherein, described magnesium halide in active Jing frequently with magnesium halide and alcohol adduct, as load Spheric catalyst is obtained after body and halogenated titanium and the reaction of electron donor compound, the spheric catalyst is (special for alkene Not propylene) polymerization when, with higher polymerization activity and stereotaxises ability, resulting polymers also have preferable Grain form and higher apparent density.

Published magnesium halide alcohol adducts are mostly the alcohol adducts of magnesium chloride, generally include magnesium chloride and alcohol binary composition. Wherein, some published magnesium chlorides also contain a small amount of water with the adduct of alcohol.Such alcohol adduct can by be spray-dried, It is prepared by spray cooling, high pressure extrusion, high-speed stirred or the method such as high-gravity rotating bed.Such as：US4421674、US4469648、 WO8707620、WO9311166、US5100849、US6020279、US4399054、EP0395383、US6127304、 Chlorination magnesium alcoholate disclosed in US6323152 and CN1289542C.

US4421674 and CN1765940A disclose one kind and prepare carrier for olefin polymerization catalyst (carrier alcohol content is less than 14%, apparent density 0.32g/ml, the particle diameter of carrier is less than 20 microns) spray drying method.By by the second of magnesium chloride Alcoholic solution (about 100-300g/L) is preheated to after 90-100 DEG C and is sprayed in the vaporizer of flow of warm nitrogen gas, after the most of alcohol of removing Form the solid particle of chlorination magnesium alcoholate.The method first prepares the ethanol solution of magnesium chloride, and ethanol consumption is big, energy consumption compared with It is high.

US6020279 discloses a kind of spray cooling for preparing chlorination magnesium alcoholate.By the fused mass of chlorination magnesium alcoholate Chlorination magnesium alcoholate solid particle is formed in nozzle spray to cooling medium.Alcohol adduct grain diameter prepared by the method Little, machine utilization is low, but size adjusts difficult.

CN1330086A and US6686307 disclose the height of chlorination magnesium alcoholate and stir preparation technology.Specifically, first lazy Property medium in prepare liquid magnesium chloride alcohol adduct suspension, afterwards by high-speed stirred by liquid chlorination magnesium alcoholate emulsifying, And it is transferred in cooling medium formation chlorination magnesium alcoholate granule.Solid alcohol adduct particle diameter distribution prepared by the method is wider.

CN1463990A discloses a kind of emulsifying cooling preparation technology of chlorination magnesium alcoholate.The preparation solution in inert media The suspension of state chlorination magnesium alcoholate, float is entered cooling medium after mulser and forms chlorination magnesium alcoholate granule. Solid alcohol adduct particle diameter prepared by the method is little, and machine utilization is low, but size adjusts difficult.

CN1267508C discloses a kind of preparation method and application of magnesium halide/alcohol adducts.Specifically, in inert media The middle suspension for preparing liquid magnesium chloride alcohol adduct, float enters cooling Jie by the high-gravity rotating bed rear of high speed rotation Matter forms chlorination magnesium alcoholate granule.The method prepares, the large-size particles of preparation difficult compared with the alcohol adduct granule of small particle Sphericity poor (easily occur abnormity material).

The adduct of above-mentioned preparation is urged by preparing spheric polypropylene with titanium compound and internal electron donor compound reaction Agent.The form of adduct of magnesium halides carrier decides the form of catalyst, and it is dividing for liquid adduct that it prepares key Scattered technology, it controls the size of adduct diameter of carrier and distribution, or even affects adduct solid magnesium halide lattice Defect, and then affect the polymerization of catalyst.

For the purposes of improving the polymerization of the olefin polymerization catalysis with adduct of magnesium halides as carrier, research worker starts Attempt that other the electron donor compounds in addition to alcohol and water are incorporated in adduct preparation process of the magnesium halide with alcohol.

CN1169840C and CN1286863C disclose a kind of " magnesium dichloride-alcohol-phthalic acid ester " spherical magnesium chloride Adduct, but, the catalyst formed with the adduct and titanium tetrachloride reaction polymerization activity when for propylene polymerization is low And hydrogen response is poor.

CN103073661A discloses formula for MgCl₂(ROH)_m(LB)_nMagnesium chloride adduct, wherein R is not to take C that is generation or being replaced containing heteroatom group₁-C₁₅Alkyl, LB is comprising C₂-C₂₀Aliphatic ether, C₁-C₁₀Aliphatic carboxylic acid The lewis base of Arrcostab, ketone or silane, the value of m is 0.08 to 6 for the value of 0.5 to 2.5, n, the adduct Can be used for preparing the catalyst with 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, its Middle X is chlorine or bromine, and R is C₁-C₄Alkyl, E be o-alkoxyl benzoate compounds, by the magnesium halide Adduct and halogenated titanium and optional internal electron donor reaction, can obtain the catalyst with high stereotaxises ability, especially It is that the catalyst for obtaining still has higher stereotaxises ability when for preparing high melt flow index polypropylene, in system During the standby adduct of magnesium halides, the o-alkoxyl benzoate compounds can derive from o-alkoxyl Benzenecarbonyl chloride. Alcoholysis reaction, in order to avoid the alkoxyl in o-alkoxyl Benzenecarbonyl chloride. is hydrolyzed, needs the raw material to being used to carry out Strict anhydrous process, by weight, the condition of the anhydrous process is generally less than the water content of magnesium halide 0.2%, the water content of alcohol is less than 100ppm.

CN102796131A discloses a kind of such as formula M gXY-mR (OH)_rThe adduct of magnesium halides of-nE, wherein X are Chlorine or bromine, Y is chlorine, bromine, C₁-C₁₄Straight or branched alkyl, C₆-C₁₄Substituted or unsubstituted aryl, C₁-C₁₄ Straight or branched alkoxyl and C₆-C₁₄Substituted or unsubstituted aryloxy group in one kind, R is C₁-C₂₀Alkyl, r For more than 1 integer, E is hydroxybenzoic acids or hydroxy benzoic acid esters compound, and m is 1-5, and n is 0.001-0.5, the catalyst that the adduct of magnesium halides is prepared with halogenated titanium and optional internal electron donor reaction is for third When alkene is polymerized, the hydrogen response of catalyst has obtained further improvement.

CN102796127A discloses a kind of formula for MgXY-mEtOH-n (LB₁)-k(LB₂)-p(LB₃) magnesium halide adduction Thing, wherein X are chlorine or bromine, and Y is chlorine, bromine, C₁-C₁₄Straight or branched alkyl, C₆-C₁₄Replacement or unsubstituted Aryl, C₁-C₁₄Straight or branched alkoxyl and C₆-C₁₄Substituted or unsubstituted aryloxy group in one kind, LB₁、 LB₂And LB₃Respectively carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and different from the alcohol of ethanol Kind, m is 1-5, and n is 0.005-2, and k is 0.0005-0.3, and p is 0.0005-0.3, the adduct and halogenated titanium and times The catalyst that the internal electron donor reaction of choosing is further prepared can be adjusted in hydrogen and obtain between ability and stereotaxises ability preferable Balance, but, the polymerization activity of the catalyst needs further to improve.

The introducing of electron donor in adduct of magnesium halides can improve the olefinic polymerization performance of catalyst, different adduct systems Preparation Method, also has to a certain extent the olefinic polymerization performance for improving the thus catalyst that adduct is further prepared.Such as EP395083 prepares the chlorination of low ethanol content using the method that the higher adduct of alcohol content is carried out successively partial dealcoholation Magnesium adduct, the catalyst further prepared by the adduct has good morphological stability, has in olefin polymerization Avoid or limit molecule to be formed, to reduce the advantage for bringing polymerization equipment operation problem.

At present, it is typically also by a high speed as mentioned above containing the adduct of magnesium halides of other electron donors in addition to alcohol and water It is prepared by stirring, spray cooling or the method such as high-gravity rotating bed.It has been found that by using the adduct containing electron donor The adduct that melt is prepared under pressure through the manufacturing process of the construction unit to cooling medium with hole is further made Standby catalyst, when for olefinic polymerization, catalyst has some improvement to the sensitivity tool of hydrogen, and adduct Preparation technology is simple to operate, adduct particles size is controllable.

The content of the invention

It is an object of the invention to provide a kind of preparation method of the new catalytic component for olefinic polymerization, its feature It is under pressure halogenation to be prepared by the new method of the construction unit with hole to cooling medium using by adduct melt Magnesium adduct, then makes adduct of magnesium halides contact with titanium compound and aromatic carboxylic acid ester compounds；And by the party Catalytic component and catalyst system and its application prepared by method.By catalytic component shape prepared according to the methods of the invention Into caltalyst tie up to the catalyst as olefinic polymerization when, show the hydrogen response of further improvement.

As stated in the Background Art, the preparation method of adduct of magnesium halides ball type carrier include spray drying method, spray cooling, High pressure extrusion methods, high-speed mixing method and high-gravity rotating bed method etc..

(1) spray drying method：With nitrogen by MgCl₂-ol mixed system sprays into hothouse by specially designed nozzle, And it is dried to spherical magnesium chloride support in the noble gases of preheating；

However, the present inventor has found under study for action, using spray drying method in carrier preparation process, expend big Amount ethanol, nitrogen, energy, and the carrier granular form for finally giving is not good；

Adduct carrier prepared by simultaneous spray drying method has following impact on catalyst：Due to the outlet temperature of spray-dried instrument Degree is higher, causes that the ball type carrier alcohol content for obtaining is relatively low, and especially the alcohol on spherical carrier particle surface is very few, follow-up During carrying titanium, active component can not make active ingredient content in catalyst with carrier useful effect and with reference on the surface Polymerization activity that is low and then affecting final catalyst.

(2) spray cooling：Magnesium chloride alcohol mixed system is sprayed into into hothouse by specially designed nozzle with nitrogen, And condensation forms spherical magnesium chloride support in cooling medium；

However, the process is complex, instrument and equipment requirement is higher, is difficult the ball type carrier that small particle is obtained, and Alcohol content is too high in the carrier of preparation；

The adduct carrier that simultaneously prepared by spray cooling has following impact on catalyst：In ball type carrier, due to average grain Footpath is larger, and alcohol content is higher, when adduct and titanium-containing compound react, because reaction is excessively fierce, often makes carrier Broken, causing the fine powder content of final polymer increases.

(3) high pressure extrusion cooling method：With the less oil refining of viscosity, paraffin, white oil etc. as reaction medium, reaction system Temperature rise to 120-130 DEG C and maintain a period of time after, be filled with high pure nitrogen into reactor, reach reacting kettle inner pressure 10-15 atmospheric pressure；Afterwards, the mixture of chlorination magnesium alcoholate melt and reaction medium is discharged into cooling and is situated between by a discharge duct In matter；The length of discharge duct is 3-10m, and bore is 1-2mm, and flow rate of the mixed liquor in pipe is about 4-7m/s；

The technique has as a drawback that：The form of higher to equipment requirements and resulting chlorination magnesium alcoholate granule is owed Good, so that the final catalyst granules form for preparing is not good enough, the particle shape of polymer is not ideal enough, polymer Bulk density is not high.

(4) high-speed mixing method：Anhydrous magnesium chloride and alcohol are added to by a certain percentage into the inert fluid immiscible with it to be situated between In matter, heat under agitation, make EtOH/MgCl₂Form adduct melt and disperse in media as well, then in high-speed stirred Emulsifying is carried out in device, and is transferred in the medium of low temperature, by MgCl₂-ol adduct rapid condensation cured globulate wherein MgCl₂Carrier；

The technique has as a drawback that：The adduct carrier fractions wider distribution for obtaining, and be difficult to prepare small carrier, The activity of the catalyst for further preparing is also unsatisfactory.

(5) higee technology：Anhydrous magnesium chloride and alcohol are added to into by a certain percentage the inertia immiscible with it In liquid medium, heat under agitation, make EtOH/MgCl₂Form adduct melt and disperse in media as well, then to shift To high-gravity rotating bed, through being arranged on the static distribution device at rotor center the filler that adjustment is rotating equably is sprayed at Inner edge on, material be adjusted rotate filler shearing, dispersion after, magnesium chloride/alcohol adducts melt is with the shape of fine drop Formula is scattered in inert media；

The shortcoming of the technique：It is high-gravity rotating bed produce it is less (<30 microns) particle diameter and greater particle size (>65 microns) During carrier, diameter of carrier wider distribution；During steady production, blending agent (generally white oil and silicone oil are generally used Mixing) could normally produce, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, protect The ratio of the two is held, so for the repetition stability for maintaining carrier production, difficulty is increased.

With the progressively development of carrier technique, the technology of Beijing Chemical Research Institute has evolved to high-gravity rotating bed adduction processed Thing carrier technique, but this technology is the drawbacks of have aforementioned, needs perspective study and exploitation.

The present inventor proposes first in the presence of inert liquid medium, by adduct of magnesium halides under pressure Through the manufacturing process of the construction unit with hole and liquid cooling medium contact preparation adduct solid particle, simple to operate, Repetition stability is strong, can stably control the size and size distribution of adduct of magnesium halides, overcomes existing adduct The defect of carrier technology of preparing, and there is the olefin polymerization catalysis further prepared by the adduct for obtaining hydrogen to adjust sensitivity The high advantage of property.

Specifically, according to the first aspect of the invention, the invention provides a kind of catalytic component for olefinic polymerization Preparation method, the method includes：Adduct of magnesium halides, titanium compound and aromatic carboxylic acid ester compounds are connect Reaction is touched, the preparation process of the adduct of magnesium halides includes：(1) by aqueous MgX¹Y and R¹OH and oxyl benzene first Acyl based compound mix, and by the mixture for obtaining heating, obtain the adduct of magnesium halides of liquid, relative to 1 mole with The MgX of magnesium meter¹Y, R¹The amount of OH is 1-5.5 mole, and the amount of oxyl benzoyl based compound is 0.001-0.32 mole, Aqueous MgX¹The amount of water is 0.011-0.081 mole in Y；Or

By anhydrous MgX¹Y and R¹The mixing of OH, oxyl benzoyl based compound and water, and by the mixture for obtaining heating, The adduct of magnesium halides of liquid is obtained, relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1-5.5 mole, hydrocarbon The amount of epoxide benzoyl based compound is 0.001-0.32 mole, and the amount of water is 0.011-0.081 mole；

Wherein, X¹For chlorine or bromine, Y is chlorine, bromine, C₁-C₁₄Straight or branched alkyl, C₆-C₁₄Aryl, C₁-C₁₄ Straight or branched alkoxyl and C₆-C₁₄Aryloxy group in one kind, R¹For C₁-C₁₂Straight or branched alkyl, C₃-C₁₀ Cycloalkyl and C₇-C₁₀Aralkyl in one kind,

The oxyl benzoyl based compound shown in formula I,

(Formulas I)

In Formulas I, X²For the one kind in halogen atom,

R²、R³、R⁴And R⁵Respectively hydrogen, halogen, nitro, C₁-C₂₀Straight or branched alkyl, C₃-C₂₀Cycloalkanes Base, C₆-C₂₀Aryl and C₇-C₂₀Aralkyl in one kind, or, R²、R³、R⁴And R⁵In two or two More than it is mutually bonded, to form ring,

R⁶With R¹Differ, be C₁-C₂₀Straight or branched alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀Aryl and C₇-C₂₀Aralkyl in one kind；

(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is passed through under pressure and is had The construction unit in hole shapes and is dried to liquid cooling medium chilling, obtains Spherical magnesium halide adduct granule.

According to the second aspect of the invention, the invention provides according to preparation method of the present invention preparation for alkene The catalytic component of polymerized hydrocarbon.

According to the third aspect of the present invention, the invention provides a kind of catalytic component is preparing olefinic polymerization catalysis Application in agent system.

According to the fourth aspect of the present invention, the invention provides a kind of catalyst system for olefinic polymerization, the catalysis Agent system contains：I () catalytic component, the catalytic component is the catalyst group for olefinic polymerization of the present invention 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 invention provides caltalyst of the present invention ties up to olefinic polyreaction In application.

According to the sixth aspect of the invention, the invention provides a kind of olefine polymerizing process, it is poly- that the method is included in alkene Under the conditions of conjunction, one or more alkene are contacted with catalyst system of the present invention.

The method of the present invention has following advantage：

First, compared to currently advanced higee technology, the technology of the present invention can use the inertia of mixing to be situated between Matter is produced, and can also be produced using for example single white oil of single medium or silicone oil, it is therefore apparent that use Single Medium For the repetition stability that the production of adduct carrier undoubtedly improves its production；And higee technology is in steady production During, blending agent (the usually blending agent of white oil and silicone oil) production is generally used, but with production process Constantly consume, need to be continuously replenished fresh inert media, keep the ratio of the two, this is for the carrier life of maintenance adduct The repetition stability of product, increased 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 thing Consumption is low.

3rd, by key elements such as the mesh number of adjusting hole, the number of plies of construction unit and pressure, be easier realize to particle diameter, The control of particle shape, that is to say, that can be according to market demand, the production for being quantified is changed the line of production convenient and easy.

4th, the catalytic component of adduct carrier synthesis prepared by technology according to the present invention compares urging for existing production Agent component, when for olefinic polymerization, with the hydrogen response for improving, this is for the polypropylene of exploitation high added value Resin is laid a good foundation.

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

Description of the drawings

Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, concrete with following 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 of the mounting means with pore structure unit according to one embodiment of the present invention；

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

Description of reference numerals

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

2：Unit with pore structure.

Specific embodiment

The specific embodiment of the present invention is described in detail below.It should be appreciated that concrete reality described herein The mode of applying is merely to illustrate and explains the present invention, is not limited to the present invention.

As it was previously stated, the invention provides a kind of preparation method of the catalytic component for olefinic polymerization, the method includes： Adduct of magnesium halides, titanium compound and aromatic carboxylic acid ester compounds are carried out into haptoreaction, the adduct of magnesium halides Preparation process include：

(1) by aqueous MgX¹Y and R¹OH and oxyl benzoyl based compound mix, and the mixture for obtaining is added Heat, obtains the adduct of magnesium halides of liquid；Or

By anhydrous MgX¹Y and R¹The mixing of OH, oxyl benzoyl based compound and water, and by the mixture for obtaining heating, Obtain the adduct of magnesium halides of liquid；

The method according to the invention, the MgX¹In Y, X¹For chlorine or bromine, Y is chlorine, bromine, C₁-C₁₄Straight chain or Branched alkyl, C₆-C₁₄Aryl, C₁-C₁₄Straight or branched alkoxyl and C₆-C₁₄Aryloxy group in one kind；It is preferred that Ground, Y is chlorine, bromine, C₁-C₅Straight or branched alkyl, C₆-C₁₀Aryl, C₁-C₅Straight or branched alkoxyl And C₆-C₁₀Aryloxy group in one kind.

The method according to the invention, the MgX¹Y can be a kind of magnesium-containing compound, or it is two or more containing magnesium The mixture of compound.Specifically, in adduct preparation method of the present invention, MgX¹The instantiation of Y can include but not The one kind being limited in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium Or it is two or more.From the ready availability angle of raw material, MgX¹Y is preferably magnesium dichloride.

The method according to the invention, the R¹In OH, R¹For C₁-C₁₂Straight or branched alkyl, C₃-C₁₀Cycloalkanes Base and C₇-C₁₀Aralkyl in one kind；Preferably, R¹For C₁-C₆Straight or branched alkyl；It is highly preferred that R¹ For the one kind in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and n-hexyl.

R¹The instantiation of OH can be including but not limited to：It is methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, different Butanol, n-amyl alcohol, isoamyl alcohol, hexanol, n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, 1,3- Propylene Glycol and phenyl methanol.

The method according to the invention, the oxyl benzoyl based compound shown in formula I,

(Formulas I)

In Formulas I, X²For the one kind in halogen atom, preferably chlorine；

Preferably, R²、R³、R⁴And R⁵Respectively hydrogen, C₁-C₈Straight or branched alkyl, C₃-C₆Cycloalkyl, C₆-C₁₀Aryl and C₇-C₁₀Aralkyl in one kind；

It is highly preferred that R²、R³、R⁴And R⁵Respectively hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, Isobutyl group, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, one kind just in base, n-heptyl and tolyl；

Preferably, R⁶For C₁-C₆Straight or branched alkyl, C₃-C₆Cycloalkyl, C₆-C₁₀Aryl and C₇-C₁₀ Aralkyl in one kind；

It is highly preferred that R⁶For methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, One kind just in base, benzyl and phenethyl.

The method according to the invention, the oxyl benzoyl based compound be preferably 4- oxyl benzoyl based compounds and / or 2- oxyl benzoyl based compounds, more preferably 2- oxyls benzoyl based compound.

The instantiation of the oxyl benzoyl based compound can be including but not limited to：2- methoxy benzoyl chlorides, 2- Methoxyl group -3- methyl benzoyl chlorides, 2- methoxyl group -4- methyl benzoyl chlorides, 2- methoxyl group -5- methyl benzoyl chlorides, 2- methoxies Base -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 chlorides, 2- methoxyl group -5- n-propylbenzene formyl chlorides, 2- methoxyl group -4- Diisopropylbenzoyl peroxide chlorine, 2- methoxyl group -4- isobutyl-benzene formyl chlorides, 2- methoxyl group -4- tert-butyl benzoyl chlorides, 2- methoxyl group -4- Pentylbenzoyl chloride, 2- methoxyl group -4- isoamyl benzene formyl chlorides, 2- methoxyl group -4- cyclopenta Benzenecarbonyl chloride .s, 2- ethoxybenzenes Formyl chloride and 2- n-butoxy Benzenecarbonyl chloride .s.

With the method for the invention it is preferred to by aqueous MgX¹Y and R¹OH and oxyl benzoyl based compound mix, And by the mixture for obtaining heating, 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 mole, preferably 2-3.7 mole, more preferably 2.4-3.7 mole, oxyl benzoyl based compound Measure as 0.001-0.32 mole, preferably 0.005-0.17 mole, more preferably 0.015-0.12 mole；Aqueous MgX¹Y The amount of middle water is 0.011-0.081 mole, preferably 0.016-0.053 mole, more preferably 0.021-0.045 mole；Or Person；

By anhydrous MgX¹Y and R¹The mixing of OH, oxyl benzoyl based compound and water, and by the mixture for obtaining heating, The adduct of magnesium halides of liquid is obtained, relative to 1 mole of MgX in terms of magnesium¹Y, R¹The amount of OH is 1-5.5 mole, excellent Elect 2-3.7 mole, more preferably 2.4-3.7 mole as；The amount of oxyl benzoyl based compound is 0.001-0.32 mole, Preferably 0.005-0.17 mole, more preferably 0.015-0.12 mole；The amount of water is 0.011-0.081 mole, preferably 0.016-0.053 mole, more preferably 0.021-0.045 mole.

In the present invention, by weight, anhydrous MgX¹Water content in Y is that, less than 0.2%, the water content adopts karr Take not method to determine.Can be by controlling MgX¹The drying condition of Y and/or by MgX¹Y and the thing for having reactivity to water Matter is contacted, so as to adjust MgX¹Water content in Y.The material for having reactivity to water can be HCl air-flows.

The method according to the invention, except MgX¹Remaining raw material outside Y, will be used using anhydrous process is front carried out Moisture Control in raw material is not being affected in the range of result of the test.Usually, R¹The water content of OH is less than 100ppm (by weight), the water content of oxyl benzoyl based compound is that, less than 10ppm (by weight), inert fluid is situated between The water content of matter is less than 50ppm (by weight).Control or the method for reducing water content in solid material or liquid material It is well known in the art, for example：Can by liquid material distilled and/or with water absorbing agent (such as molecular sieve) Contact, can be continually fed into high-purity inert gas, such as High Purity Nitrogen air-flow in the solid material of heating or liquid material.

Preparation in accordance with the present invention, for by anhydrous MgX¹Y and R¹OH, oxyl benzoyl based compound and water Mixture or aqueous MgX¹Y、R¹The mixture heating of OH and oxyl benzoyl based compound, to be reacted simultaneously The condition for forming liquid halogenated magnesium adduct is not particularly limited, as long as the condition of the heating be enough to form the halogenation of liquid Magnesium adduct.Usually, the condition of the heating can include：Temperature is 80-140 DEG C, and the time is 0.5-4 hours.

The method according to the invention, the pressure is the relative pressure applied on the basis of atmospheric pressure, and preferred pressure is 0.05-1.0MPa, more preferably 0.1-0.5MPa, more preferably 0.2-0.5MPa.Using the preferred pressure, energy Adduct particles size prepared by optimization enough further and size distribution, while further being prepared by the adduct for obtaining Catalytic component for olefinic polymerization when, with improve hydrogen response.

The method of the present invention, only need to make liquid halogenated magnesium adduct through the structure list with hole under certain pressure effect Unit, without the need for it is complicated it is high-gravity rotating bed under the conditions of and without using accurate spraying apparatus be capable of achieving the present invention's Purpose, it can be seen that, the method for the present invention compares existing solid adduct technology of preparing, and equipment is simple, simple to operate Easy, energy consumption and material consumption are low.

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

The method according to the invention, the construction unit with hole can be various forms, for example, the plate with hole, Net with hole etc..For the present invention, it is however preferred to have the net in hole, according to the needs of actual production and being easy to get for material Property consider, most preferred diameters for 0.025-4mm twine.

The method according to the invention, the material of the construction unit with hole without particular/special requirement, for example, metal material, One or more in cloth material, plastic material and ceramic material.According to the ready availability of the needs of actual production and material, Preferably metal material.

A preferred embodiment of the invention, the construction unit with hole is stratum reticulare.

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

The method according to the invention, the wire netting using multilamellar macropore gauge structure is tied with the small-bore using the relatively little of number of plies Structure wire netting, it is possible to obtain the suitable adduct solid particle of particle morphology.Prepare small particle (such as less than 30 μm) adduction The metal mesh structure of 1-20 layer aperture gauge structures (if aperture is for 30-50 μm) is preferably adopted during thing carrier, big grain is being prepared 1-20 layers are preferably adopted to tie with respect to large aperture (if aperture is for 65-200 μm) during footpath (such as larger than 60 μm) adduct carrier The metal mesh structure of structure.

A preferred embodiment of the invention, the stratum reticulare includes 1-20 layers, preferably includes 2-8 layers, more preferably For 3-5 layers；0.01-0.35mm, more preferably preferably 0.05-0.25mm, 0.09-0.1mm are respectively per thickness degree.

The method of the present invention, by key elements such as the mesh number of adjusting hole, the number of plies of construction unit and pressure, easily realizes to grain Footpath, the control of particle shape, that is to say, that the method for the present invention can be according to market demand, the production for being quantified is changed the line of production It is convenient and easy.

The method according to the invention, the inert liquid medium can for not with magnesium halide, alcohol, aromatic carboxylic acid esters chemical combination There is the liquid compound of chemical reaction in thing, the preferably inert liquid medium is silicone oil and/or inert fluid hydrocarbon solvent；More Preferably, the inert liquid medium is C₄-C₁₀Alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl silicon One or more in oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil；Further preferably The inert liquid medium is methyl-silicone oil or white oil/methyl-silicone oil mixture.

The method of the present invention, compared to currently advanced higee technology, the technology of the present invention can be using mixing Inert media production, can also be produced using for example single white oil of single medium or silicone oil, work well.It is aobvious and It is clear to, using Single Medium for the production of adduct carrier undoubtedly increased its repetition stability.High-gravity rotating bed skill During art steady production, generally use blending agent (the usually blending agent of white oil and silicone oil) and produce, but with The continuous consumption of production process, needs to be continuously replenished fresh inert media, the ratio of the two is kept, so for maintenance The repetition stability of carrier production, increased difficulty.

In the present invention, the consumption of the inert liquid medium can be according to MgX¹The concrete consumption of Y is selecting.Usually, Relative to 1 mole of MgX in terms of magnesium¹Y, the consumption of inert liquid medium is 0.2-13L；Preferably, rub relative to 1 You are the MgX in terms of magnesium¹Y, the consumption of inert liquid medium is 0.6-6.5L.

Method according to the invention it is possible to the adduct of magnesium halides of the liquid is mixed with inert liquid medium, and will To mixture contact with liquid cooling medium and carry out cooling forming through the construction unit with hole under pressure.

Can also using the part inert liquid medium as the adduct of magnesium halides for preparing the liquid reaction medium, from And the mixed liquor of the adduct of magnesium halides containing liquid is obtained, then by the mixed liquor and the inert liquid medium of remainder Mixing, then contacting with liquid cooling medium through the construction unit with hole under pressure carries out cooling forming.

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

When needing, also optionally add some surfactants in the inert liquid medium, such as fatty glyceride, Fatty acid sorbitan, Polysorbate, polyoxyethylene ether or Pluronic F68.The surfactant Consumption can be the conventional amount used of this area, for example：Relative to 1 mole of MgX in terms of magnesium¹Y, the surfactant Consumption can be 0.001-1 mole.

The method according to the invention, the liquid cooling medium can be it is commonly used in the art it is various not with adduct of magnesium halides The chemically interactive liquid medium of generation.For example, the liquid cooling medium can be unreactive hydrocarbons solvent.The liquid The instantiation of cooling medium can be including but not limited to：Pentane, normal hexane, normal heptane, gasoline or petrol ether.

In the present invention, the liquid cooling medium using anhydrous process is front carried out, by liquid cooling medium used Moisture Control do not affecting in the range of result of the test.Usually, the water content of the liquid cooling medium is controlled to Not higher than 5ppm (by weight).Control reduces the method for water content in the liquid cooling medium and is in the art It is well known that for example：Liquid material can be distilled and/or be contacted with water absorbing agent (such as molecular sieve), Ke Yixiang High-purity inert gas, such as High Purity Nitrogen air-flow are continually fed in the liquid material of heating.

The temperature of the liquid cooling medium is defined so that the product can be made to cool down and shape.Usually, the liquid is cold But the temperature of medium can be -50 DEG C to 0 DEG C, preferably -40 DEG C to -20 DEG C.For the consumption of the cooling medium is without spy Other restriction, as long as the consumption of the cooling medium be enough to that product is cooled down and shaped.Specifically, the cooling is situated between Matter is 1-15 with the volume ratio of the product:1, preferably 2-9:1.

Adduct of magnesium halides granule obtained from the shaping of Jing chillings can be washed and is dried.Art technology can be adopted Method known to personnel is washed the adduct of magnesium halides for obtaining, for example can be using inertia hydrocarbon system solvent (for example： Pentane, normal hexane, normal heptane, petroleum ether and gasoline) adduct of magnesium halides to obtaining washs.The drying Temperature can be not higher than 35 DEG C, preferably 25-30 DEG C；The time of the drying can be 0.5-3 hours, preferred 1-2h. The drying 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 ethanol, oxyl benzoyl chemical combination Thing is as a example by 2- methoxy benzoyl chlorides, to be gone through according to the following reaction of method experience that above two adduct prepares embodiment Journey, so as to obtain the adduct of magnesium halides of the present invention.

The adduct support preparation method of the present invention is simple, for example, can be arranged on the unit with pore structure Store up in adduct of magnesium halides Location Detection of Medium Transportation Pipeline or installed in adduct of magnesium halides Location Detection of Medium Transportation Pipeline and liquid cooling medium Between tank.Specifically, as shown in figure 1, the unit 2 with pore structure is defeated installed in adduct of magnesium halides material Send in pipeline 1, adduct of magnesium halides passes through the unit with pore structure before contacting with cooling medium；Or, such as Fig. 2 It is shown, the unit 2 with pore structure is arranged on into adduct of magnesium halides Location Detection of Medium Transportation Pipeline 1 and liquid cooling medium Between storage tank (not shown), adduct of magnesium halides passes through the unit with pore structure before contacting with cooling medium.

Adduct of magnesium halides diameter of carrier size and particle diameter distribution prepared by the technology of the present invention is easily controlled, and using described The catalytic component that adduct carrier further synthesizes, the catalytic component for producing compared to existing technology, poly- for alkene During conjunction, the hydrogen response of improvement is shown, this lays a good foundation for the acrylic resin of exploitation high added value.

Preferred embodiment, the method includes one kind of the invention：Adduct of magnesium halides and titanium compound are reacted, And add institute within one or more time periods before and after, during the adduct of magnesium halides and titanium compound reaction Stating aromatic carboxylic acid ester compounds carries out the haptoreaction.

Specifically, the adduct of magnesium halides can enter with the reaction of titanium compound according to mode same as the prior art OK, for example, the adduct of magnesium halides can be suspended in the mixing of cold titanium compound or titanium compound and atent solvent (titanium compound or titanium compound and the temperature of the mixture of atent solvent can be -40 DEG C to 0 DEG C, preferably in liquid - 25 DEG C to -15 DEG C), then the mixture for obtaining is heated to into 40-130 DEG C, 80-130 DEG C is preferably heated to, and above-mentioned At a temperature of maintain 0.5-2 hours, then carry out solid-liquid separation and collect solid；Then, the solid for obtaining is suspended in into titanizing In compound, and the mixture for obtaining is heated to into 60-130 DEG C, is preferably heated to 80-130 DEG C, and tieed up at the temperature disclosed above 0.5-2 hours are held, solid-liquid separation is then carried out and is collected solid, the operation can carry out one or many, preferably carry out 2-4 time；Finally, the solid for obtaining is washed with atent solvent, the atent solvent is preferably aliphatic hydrocarbon or aromatic hydrocarbons, for example： Normal hexane, normal heptane, normal octane, n-decane and toluene.

In the preparation method for the catalytic component of olefinic polymerization, the aromatic carboxylic acid ester compounds are described Add in one or more time periods in before and after, during adduct of magnesium halides and titanium compound reaction, preferably exist Add while adduct of magnesium halides granule reacts with titanium compound.

In the present invention, the aromatic carboxylic acid esters are preferably polynary aromatic carboxylic acid esters, more preferably O-phthalic dialkylaminobenzoic acid Ester, more 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 Di-isooctyl, dinoctyl phthalate, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids di-n-butyl, tri trimellitate second Ester, trimellitic acid tri-n-butyl, the triethylenetetraminehexaacetic acid ester of biphenyl three, connection benzenetricarboxylic acid tri-n-butyl, PMA tetra-ethyl ester and equal benzene One or more in the N-butyl of tetracid four.

In a particular embodiment of the present invention, using diisobutyl phthalate, n-butyl phthalate as virtue The advantage of fragrant race's carboxylate internal electron donor exemplary illustration present invention.

Usually, the preparation method of the catalytic component for olefinic polymerization of the invention, the titanium compound can be with For three halogenated titaniums and formula Ti (OR⁷)_4-qX² _qOne or more in shown titanium compound, in the formula, R⁷Can Think C₁-C₁₀Alkyl, X²Can be halogen, m can be the integer of 0-4.Preferably, the titanium compound is four Titanium chloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, the titanium butoxide of a chlorine three, the fourth of dichloro two Epoxide titanium, the titanium butoxide of trichlorine one, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, the ethanolato-titanium of trichlorine one and trichlorine Change titanium in one or more.It is highly preferred that the titanium compound is titanium tetrachloride.

According to the present invention, the consumption of the adduct of magnesium halides, the consumption of titanium compound and aromatic carboxylic acid ester compounds Consumption appropriate selection can be carried out according to the composition of the expected catalytic component for olefinic polymerization.For example, it is described Titanium compound, aromatic carboxylic acid ester compounds can be 5-100 with the mol ratio of the adduct of magnesium halides:0.01-0.5:1； Preferably 20-80:0.05-0.35:1, in terms of titanium elements, the adduct of magnesium halides is in terms of magnesium elements for the titanium compound. In the present invention, the amount of titanium compound is to be included in the total amount for preparing the titanium compound used during catalytic component of the present invention.

As it was previously stated, a kind of present invention also offers catalysis for olefinic polymerization for preparing according to the method described in the present invention Agent component.

Catalytic component for olefinic polymerization of the invention, due to having used according to adduct of magnesium halides system of the present invention Adduct of magnesium halides containing other electron donors in addition to alcohol and water prepared by Preparation Method, shows when for olefinic polyreaction Go out the hydrogen response of improvement.

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

As it was previously stated, invention further provides a kind of catalyst system for olefinic polymerization, the catalyst system contains Have：

I () catalytic component, the catalytic component is the catalytic component for olefinic polymerization of the present invention；

(ii) at least one alkyl aluminum compound；And

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

The composition and preparation method of the catalytic component has been carried out detailed description above, and here is no longer gone to live in the household of one's in-laws on getting married State.

The alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art.For example, the alkyl aluminum chemical combination Thing can be alkylaluminium sesquichloride and formula AlR⁸R⁹R¹⁰One or more in shown compound, the formula In, R⁸、R⁹And R¹⁰Can be each chlorine and C₁-C₈Alkyl in one kind, and R⁸、R⁹And R¹⁰In at least one It is individual for C₁-C₈Alkyl.Preferably, the alkyl aluminum compound be triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, Tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminum, a chlorine two N-hexyl aluminum, the aluminium ethide of dichloro one, the aluminium isobutyl of dichloro one, the n-butylaluminum of dichloro one, the n-hexyl aluminum of dichloro one and Al₂Et₃Cl₃ In one or more, wherein, Et is ethyl.

Catalyst system for olefinic polymerization of the invention, the alkyl aluminum compound in terms of aluminum and the catalysis in terms of titanium The mol ratio of agent component can be 1-2000:1, preferably 20-700:1.

In the case where the organic vertical structure that alkene is particularly alpha-olefin (such as propylene or 1-butylene) is polymerized, according to the present invention The catalyst system for olefinic polymerization can also include from the compound phase as internal electron donor with or different give Electron compound is used as external donor compound.

The external donor compound can be various external donor compounds commonly used in the art, for example：It is described outer Electron donor compound can be in carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound One or more.Preferably, the external electron donor is general formula R¹¹ _xR¹² _ySi(OR¹³)_zShown organosilicon compound Thing, in the formula, R¹¹、R¹²And R¹³Respectively C₁-C₁₈Alkyl or containing heteroatomic C₁-C₁₈Alkyl；X and Y is respectively the integer of 0-2, z for 1-3 integer, and x+y+z=4.It is highly preferred that general formula R¹¹ _xR¹² _ySi(OR¹³)_z In, R¹¹And R¹²At least one of be selected from C₃-C₁₀With or without heteroatomic branched alkyl, C₃-C₁₀Containing or not Containing heteroatomic substituted or unsubstituted cycloalkyl and C₆-C₁₀Substituted or unsubstituted aryl in one kind, R¹³For C₁-C₁₀Alkyl, preferably methyl；X be 1, y be 1, z be 2；Or, R¹²For C₃-C₁₀Branched alkyl or C₃-C₁₀Cycloalkyl, and R¹³For methyl, x be 0, y be 1, z be 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 Dimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- uncles Butyldimethoxysilane, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilanes, (the fluoro- 2- propyl group of 1,1,1- tri-) - Methyl dimethoxysilane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and tertiary hexyl trimethoxy silane.

Usually, relative to 1 mole of alkyl aluminum compound in terms of aluminum, the consumption of the external donor compound can be with For 0.005-0.5 mole；Preferably, relative to 1 mole of alkyl aluminum compound in terms of aluminum, the external electron donor chemical combination The consumption of thing is 0.01-0.4 mole.

Catalyst system for olefinic polymerization of the invention, preferably with the one kind in above-mentioned electron donor compound or It is two or more as external electron donor.

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

As it was previously stated, the invention provides the caltalyst for olefinic polymerization of the present invention ties up to olefinic polyreaction In application.

Present invention also offers a kind of olefine polymerizing process, the method is included under olefin polymerization conditions, by one or two The catalyst system that above alkene is provided with the present invention is contacted.

Theing improvement is that for the present invention employs a kind of adduct prepared by new adduct technology of preparing and then prepares Catalytic component and its catalyst system for olefinic polymerization.The olefine polymerizing process of the present invention is for olefinic polymerization bar Part and the alkene for being used are not particularly limited.

Usually, olefine polymerizing process of the invention, the alkene can be formula CH₂=CHR¹⁴Shown alkene Hydrocarbon, wherein, R¹⁴Can be hydrogen, C₁-C₁₂Straight or branched alkyl and C₆-C₁₂Aryl in one kind.According to this Bright olefine polymerizing process, if necessary, the alkene can also contain a small amount of alkadienes.Alkene of the invention gathers Conjunction method, the alkene is preferably propylene, or propylene and CH₂=CHR¹⁴Shown alkene, wherein, R¹⁴For hydrogen and C₁-C₆Straight or branched alkyl in one kind.

Olefine polymerizing process of the invention, the polymerization can be carried out according to the conventional method of this area.For example, institute It can be polymerisation in bulk, gas-phase polymerization, slurry polymerization or liquid-phase bulk-gas phase polymerization mix to state polymerization.It is of the invention Olefine polymerizing process, the olefin polymerization conditions can be the normal condition of this area, and for example, polymerization temperature can be 0-150 DEG C, preferably 60-90 DEG C；Polymerization pressure can be normal pressure or pressurization.

The examples below is used for illustrating the present invention, is not for limiting the scope of the present invention.

Method of testing：

1st, melt index：At 230 DEG C of temperature and the pressure of 2.16kg, surveyed according to ASTM D1238-99 It is fixed.

2nd, polymer isotacticity：Determined (heptane boiling extracting 6 hours) using heptane extraction process：Two grams of dry polymerizations Thing sample, is placed in extractor after being extracted 6 hours with boiling heptane, by residue drying to the polymer weight obtained by constant weight Ratio of the amount (g) with 2 is isotacticity.

3rd, particle diameter distribution test：The mean diameter and particle size distribution Masters Sizer 2000 of adduct of magnesium halides granule (being manufactured by Malvern Instruments Ltd) particle size analyzer determination.

Prepare embodiment 1

In the reactor of 1000mL, addition 150mL white oils (commercially available from Guangzhou Ming En petrochemical industries company limited, By weight, water content is less than 50ppm), (commercially available from DOW CORNING, viscosity is 300 centipoise/20 to 300mL methyl-silicone oils DEG C, by weight, water content be less than 50ppm), 30g contain 0.44wt% moisture magnesium chloride it is (prosperous commercially available from Fushun City Yi Taichang), 50mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is less than 100ppm) and 1mL 2- methoxy benzoyl chlorides (commercially available from TOKYO KASEI KOGYO CO.LTD), are warming up under agitation 125 ℃.After isothermal reaction 3 hours, by mixture under the pressure of 0.3MPa by being preinstalled with 4 layers of aperture for 75 μm of metals The blowing pipeline of net (per thickness degree 0.1mm) is depressed into 2L hexanes (by weight, the water content pre-cooled to -30 DEG C Less than 5ppm) in, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed into 5 with the hexane of 300mL It is secondary, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct S1 of the invention, characterize As a result such as table 1.

Prepare embodiment 2

In the reactor of 1000mL, addition 150mL white oils (commercially available from Guangzhou Ming En petrochemical industries company limited, By weight, water content is less than 50ppm), (commercially available from DOW CORNING, viscosity is 300 centipoise/20 to 300mL methyl-silicone oils DEG C, by weight, water content be less than 50ppm), 30g anhydrous magnesium chlorides (commercially available from Xin Yitai factories of Fushun City), 50mL Dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is less than 100ppm), 1mL 2- methoxybenzene first Acyl chlorides (commercially available from TOKYO KASEI KOGYO CO.LTD) and 0.15g water, are warming up under agitation 125 DEG C. After isothermal reaction 3 hours, by mixture under the pressure of 0.3MPa by be preinstalled with 4 layers of aperture for 75 μm of wire nettings it is (every Thickness degree 0.1mm) blowing pipeline be depressed into and pre-cool to -30 DEG C of 2L hexanes (by weight, water content be less than 5ppm) In, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed 5 times with the hexane of 300mL, and 30 It is vacuum dried 1.5 hours at DEG C, so as to obtain Spherical magnesium halide adduct S2 of the invention, characterization result such as table 1.

Prepare embodiment 3

Method according to embodiment 1 is prepared prepares Spherical magnesium halide adduct S3, except for the difference that, the construction unit with hole For the wire netting (per thickness degree 0.09mm) that 4 layers of aperture is 48 μm, characterization result such as table 1.

Prepare embodiment 4

In the reactor of 1000mL, addition 500mL white oils (commercially available from Guangzhou Ming En petrochemical industries company limited, By weight, water content be less than 50ppm), 30g contain the magnesium chloride of 0.44wt% moisture (commercially available from the prosperous suitable titanium in Fushun City Factory), 50mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is less than 100ppm) and 1mL 2- Methoxy benzoyl chloride (commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up under agitation 125 DEG C. After isothermal reaction 3 hours, by mixture under the pressure of 0.2MPa by prepackage be of five storeys aperture for 75 μm of wire nettings it is (every Thickness degree 0.1mm) blowing pipeline be depressed into and pre-cool to -30 DEG C of 2L hexanes (by weight, water content be less than 5ppm) In, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed 5 times with the hexane of 300mL, and 30 It is vacuum dried 1.5 hours at DEG C, so as to obtain Spherical magnesium halide adduct S4 of the invention, characterization result such as table 1.

Prepare embodiment 5

In the reactor of 1000mL, (commercially available from DOW CORNING, viscosity is 300 centipoise/20 to add 500mL methyl-silicone oils DEG C, by weight, water content be less than 50ppm), 30g contain 0.44wt% moisture magnesium chloride it is (prosperous commercially available from Fushun City Yi Taichang), 50mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is less than 100ppm) and 1mL 2- methoxy benzoyl chlorides (commercially available from TOKYO KASEI KOGYO CO.LTD), are warming up under agitation 125 ℃.After isothermal reaction 3 hours, mixture is had three layers into aperture for 75 μm of metals under the pressure of 0.5MPa by prepackage The blowing pipeline of net (per thickness degree 0.1mm) is depressed into 2L hexanes (by weight, the water content pre-cooled to -30 DEG C Less than 5ppm) in, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed into 5 with the hexane of 300mL It is secondary, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct S5 of the invention, characterize As a result such as table 1.

Prepare comparative example 1

Prepared by the method according to embodiment 1 is prepared, except for the difference that, the mixture for obtaining is transferred to into rotating speed for 2400rpm It is high-gravity rotating bed in, by it is high-gravity rotating bed enter pre-cool to -30 DEG C of 2L hexanes (by weight, water Content is less than 5ppm) in, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed with the hexane of 300mL Wash 5 times, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct DS1 of the invention, Characterization result such as table 1.

Prepare comparative example 2

Prepared by the method according to embodiment 4 is prepared, except for the difference that, the mixture for obtaining is transferred to into rotating speed for 2400rpm It is high-gravity rotating bed in, by it is high-gravity rotating bed enter pre-cool to -30 DEG C of 2L hexanes (by weight, water Content is less than 5ppm) in, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed with the hexane of 300mL Wash 5 times, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct DS2 of the invention, 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

Can be seen that by the result of table 1 and compare higee technology, the present invention can prepare the adduction of different-grain diameter Thing carrier, and narrower particle size distribution, the big particle diameter (D50 for particularly preparing>60 μm) adduct carrier, still with narrower Particle size distribution.

Embodiment 1

The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization Agent system and its application.

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

In the glass reaction bottle of 300mL, under nitrogen protective condition, 10mL hexanes, the chlorinations of 90mL tetra- are sequentially added Titanium, is cooled to -20 DEG C, adds 8.0g Spherical magnesium halide adducts S1, and stirs 30 minutes at -20 DEG C.Then, slowly 110 DEG C are warming up to, and 1.5mL diisobutyl phthalates are added in temperature-rise period.In 110 DEG C of isothermal reactions 30 After minute, liquid is filtered.80mL titanium tetrachlorides are added, 120 DEG C are warming up to, is filtered after maintaining 30 minutes at 120 DEG C Liquid；Then, add 80mL titanium tetrachlorides, and be warming up to 120 DEG C, after maintaining 30 minutes at 120 DEG C liquid is filtered Body.5 times (hexane consumption is 80mL/ time) is finally washed to the solid for obtaining with 60 DEG C of hexane, and is vacuum dried gained Solidss, so as to obtain spherical catalyst components C1.

(2) propylene polymerization：

Under nitrogen protection, the hexane solution that 5mL triethyl aluminums are sequentially added in the rustless steel autoclave of 5L is (dense Spend for 0.5mmol/mL), the hexane solution (concentration is 0.1mmol/mL) of 1mL Cyclohexyl Methyl Dimethoxysilanes and 9mg spherical catalyst components C1.Autoclave is closed, 5.0L (normal volume) hydrogen and 2.3L liquid propenes is added. 70 DEG C are warming up to, are reacted 1 hour.Then, lower the temperature, release, discharging, and be dried, so as to obtain polypropylene. The polymerization activity of catalyst is calculated, the polyacrylic isotactic index and melt index for preparing is determined, 2 are the results are shown in Table.

Comparative example 1

Method according to embodiment 1 prepare for olefinic polymerization catalyst and carry out propylene polymerization, as a result in table 2 In list, except that, adduct of magnesium halides is prepared as follows：

In the reactor of 500mL, addition 150mL white oils (commercially available from Guangzhou Ming En petrochemical industries company limited, By weight, water content be less than 50ppm), 30g contain the magnesium chloride of 0.44wt% moisture (commercially available from the prosperous suitable titanium in Fushun City Factory), 50mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is less than 100ppm) and 1mL 2- Methoxy benzoyl chloride (commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up under agitation 125 DEG C. After isothermal reaction 3 hours, the 300mL methyl-silicone oils that mixture press-in is preheated to 125 DEG C (commercially available from DOW CORNING, are glued Spend for 300 centipoise/20 DEG C, by weight, water content is less than 50ppm) in, stir 30 with 1600 revs/min of speed Minute, to carry out emulsifying.Then, the press-in of emulsification product nitrogen is pre-cooled to -30 DEG C of 2L hexanes (with weight Meter, water content is less than 5ppm) in, carry out chilling shaping.Liquid is filtered to remove, by the solid for obtaining with 300mL's Hexane is washed 5 times, and is vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct.The results are shown in Table 2.

Comparative example 2

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the preparation of the catalytic component of olefinic polymerization is used for using the adduct DS1 for preparing the preparation of comparative example 1, so as to To spherical catalyst components DC1.The results are shown in Table 2.

Embodiment 2

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the addition of diisobutyl phthalate is 1.0ml, so as to obtain spherical catalyst components C2.The results are shown in Table 2.

Embodiment 3

The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and urging for olefinic polymerization Agent and its application.

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , internal electron donor is the n-butyl phthalate of 1.5ml, so as to obtain spherical catalyst components C3.As a result It is shown in Table 2.

Comparative example 3

Method according to comparative example 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the internal electron donor for using is the n-butyl phthalate of 1.5ml.The results are shown in Table 2.

Embodiment 4

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the preparation of the catalytic component of olefinic polymerization is used for using the adduct S2 for preparing the preparation of embodiment 2, so as to obtain Spherical catalyst components C4.The results are shown in Table 2.

Comparative example 4

Method according to embodiment 4 prepare for olefinic polymerization catalyst and carry out propylene polymerization, except that, Adduct of magnesium halides is prepared as follows：

In the reactor of 500mL, addition 150mL white oils (commercially available from Guangzhou Ming En petrochemical industries company limited, By weight, water content is less than 50ppm), 30g anhydrous magnesium chlorides (commercially available from Xin Yitai factories of Fushun City), 50mL it is anhydrous Ethanol (commercially available from Beijing Chemical Plant, by weight, water content is less than 100ppm), 1mL 2- methoxy benzoyl chlorides (commercially available from TOKYO KASEI KOGYO CO.LTD) and 0.15g water, are warming up under agitation 125 DEG C.Constant temperature After reaction 3 hours, mixture press-in is preheated to into 125 DEG C of 300mL methyl-silicone oils, and (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is less than 50ppm) in, stirred 30 minutes with 1600 revs/min of speed, To carry out emulsifying.Then, the press-in of emulsification product nitrogen is pre-cooled to -30 DEG C of 2L hexanes (by weight, water Content is less than 5ppm) in, carry out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed with the hexane of 300mL Wash 5 times, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct.The results are shown in Table 2.

Embodiment 5

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the preparation of the catalytic component of olefinic polymerization is used for using the adduct S3 for preparing the preparation of embodiment 3, so as to obtain Spherical catalyst components C5.The results are shown in Table 2.

Embodiment 6

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the preparation of the catalytic component of olefinic polymerization is used for using the adduct S4 for preparing the preparation of embodiment 4, so as to obtain Spherical catalyst components C6.The results are shown in Table 2.

Comparative example 5

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the preparation of the catalytic component of olefinic polymerization is used for using the adduct DS2 for preparing the preparation of comparative example 2, so as to To spherical catalyst components DC2.The results are shown in Table 2.

Embodiment 7

Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, institute is different , the preparation of the catalytic component of olefinic polymerization is used for using the adduct S5 for preparing the preparation of embodiment 5, so as to obtain Spherical catalyst components C7.The results are shown in Table 2.

Table 2

From the results shown in Table 2, catalytic component of the invention shows the hydrogen of improvement when for propylene polymerization Sensitivity is adjusted, while still maintaining higher isotactic index (boiling n-heptane insoluble matter>96.0wt%), with higher work Industry using value.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, can carry out various simple variants to technical scheme, These simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not contradiction In the case of, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention is to various Possible compound mode is no longer separately illustrated.

Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as it is without prejudice to this Bright thought, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of preparation method of the catalytic component for olefinic polymerization, the method includes：By adduct of magnesium halides, Titanium compound and aromatic carboxylic acid ester compounds carry out haptoreaction, it is characterised in that the system of the adduct of magnesium halides Standby step includes：

The oxyl benzoyl based compound shown in formula I,

In Formulas I, X²For the one kind in halogen atom,

2. preparation method according to claim 1, wherein, the pressure is 0.05-1.0MPa, preferably 0.1-0.5MPa。

3. preparation method according to claim 1, wherein, the aperture in the hole is 10-1800 μm, preferably 20-800μm。

4. the preparation method according to any one in claim 1-3, wherein, the construction unit with hole is Stratum reticulare.

5. preparation method according to claim 4, wherein, the stratum reticulare includes 1-20 layers, preferably includes 2-8 Layer；0.01-0.35mm, preferably 0.05-0.25mm are respectively per thickness degree.

6. preparation method according to claim 4, wherein, the stratum reticulare is metal net layer.

7. preparation method according to claim 1, wherein, the inert liquid medium is silicone oil and/or inert liquid Body hydrocarbon solvent；Preferably, the inert liquid medium is C₄-C₁₀Alkane, kerosene, paraffin oil, vaseline oil, white One or more in oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil； It is highly preferred that the inert liquid medium is silicone oil.

8. preparation method according to claim 1, wherein, the aromatic carboxylic acid ester compounds are polynary fragrance Race's carboxylate, preferably alkyl phthalates, more preferably alkyl are C₂-C₈Alkyl phthalates.

9. 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 mole, oxyl benzoyl based compound Amount be 0.001-0.32 mole, aqueous MgX¹The amount of water is 0.011-0.081 mole in Y；Or

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

The oxyl benzoyl based compound is 4- oxyl benzoyl based compounds and/or 2- oxyl benzoyls system Compound；

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

10. preparation method according to claim 1, wherein, the titanium compound, aromatic carboxylic acid ester compounds It is 5-100 with the mol ratio of the adduct of magnesium halides:0.01-0.5:1；Preferably 20-80:0.05-0.35:1, the titanium In terms of titanium elements, the adduct of magnesium halides is in terms of magnesium elements for compound.

The catalytic component for olefinic polymerization that method in 11. claim 1-10 described in any one is prepared.

The catalytic component for olefinic polymerization described in 12. claim 11 is in olefin polymerization catalyst system is prepared Application.

A kind of 13. catalyst systems for olefinic polymerization, the catalyst system contains：

I () catalytic component, the catalytic component is the catalytic component for olefinic polymerization described in claim 11；

(ii) at least one alkyl aluminum compound；And

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

The caltalyst for olefinic polymerization described in 14. claim 13 ties up to the application in olefinic polyreaction.

A kind of 15. olefine polymerizing process, the method is included under olefin polymerization conditions, by one or more alkene with Catalyst system contact described in claim 13.