CN106608929A - Catalyst components, preparation method and application thereof, catalyst system used for olefin polymerization, application and olefin polymerization method thereof - Google Patents
Catalyst components, preparation method and application thereof, catalyst system used for olefin polymerization, application and olefin polymerization method thereof Download PDFInfo
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Abstract
The invention relates to the field of olefin polymerization and particularly provides catalyst components used for olefin polymerization and a preparation method and application thereof. The preparation method comprises the step that a magnesium halide adduct, a titanium compound and a diether compound are subjected to contact reaction. The preparation of the magnesium halide adduct comprises the steps that (1), water-contained MgX1Y, R1OH and a hydrocarbon-oxyl benzoyl compound are mixed, the obtained mixture is heated, or anhydrous MgX1Y, the R1OH, the hydrocarbon-oxyl benzoyl compound and water are mixed, the obtained mixture is heated, and the liquid magnesium halide adduct is obtained; and (2) in the presence of an inert liquid medium, the liquid magnesium halide adduct penetrates through a structural unit with holes to a liquid cooling medium under the pressure effect, and is quenched for forming and dried. The invention provides a catalyst system used for the olefin polymerization and an application and olefin polymerization method thereof. The prepared catalyst components synthesized by an adduct carrier has improved hydrogen modulation sensitivity when used in the olefin polymerization.
Description
Technical field
The present invention relates to a kind of preparation method of the catalytic component for olefinic polymerization, and catalytic component and its application in the catalyst system for olefinic polymerization is prepared for olefinic polymerization obtained by the method；With the catalyst system for olefinic polymerization and its application in olefinic polyreaction；With a kind of olefine polymerizing process of the catalyst system for olefinic polymerization using the present invention.
Technical background
By it is titanium compound and electron donor compound loaded in magnesium halide in active preparing what Ziegler-Natta catalyst was well known from.Wherein, described magnesium halide in active Jing is frequently with magnesium halide and the adduct of alcohol, spheric catalyst is obtained after reacting with halogenated titanium and electron donor compound as carrier, the spheric catalyst is when being polymerized for alkene (particularly propylene), with higher polymerization activity and stereotaxises ability, resulting polymers also have preferable particle shape and higher apparent density.
Published magnesium halide alcohol adducts are the alcohol adduct of magnesium chloride mostly, 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 be by sprays drying, spray cooling, high pressure extrusion, high-speed stirred or the method such as high-gravity rotating bed preparation.Such as：Chlorination magnesium alcoholate disclosed in US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304, US6323152 and CN1289542C.
US4421674 and CN1765940A disclose the spray drying method that one kind prepares carrier for olefin polymerization catalyst (less than 14%, apparent density 0.32g/ml, the particle diameter of carrier are less than 20 microns to carrier alcohol content).It is preheated to after 90-100 DEG C by the ethanol solution (about 100-300g/L) by magnesium chloride and is sprayed in the vaporizer of flow of warm nitrogen gas, after the most of alcohol of removing, forms the solid particle of chlorination magnesium alcoholate.The 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.The fused mass of chlorination magnesium alcoholate is formed in nozzle spray to cooling medium chlorination magnesium alcoholate solid particle.Alcohol adduct grain diameter prepared by the method is little, and machine utilization is low, but size adjusts difficult.
CN1330086A and US6686307 disclose the height of chlorination magnesium alcoholate and stir preparation technology.Specifically, the suspension of liquid magnesium chloride alcohol adduct is first prepared in inert media, afterwards by high-speed stirred by liquid chlorination magnesium alcoholate emulsifying, and chlorination magnesium alcoholate granule is formed in being transferred to cooling medium.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 suspension of liquid magnesium chloride alcohol adduct is prepared in inert media, 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, the suspension of liquid magnesium chloride alcohol adduct is prepared in inert media, float forms chlorination magnesium alcoholate granule by the high-gravity rotating bed rear cooling medium that enters of rotation at a high speed.The method prepares, the sphericity poor (abnormity material easily occur) of the large-size particles of preparation difficult compared with the alcohol adduct granule of small particle.
The adduct of above-mentioned preparation is by preparing spheric polypropylene catalyst with titanium compound and internal electron donor compound reaction.The form of adduct of magnesium halides carrier decides the form of catalyst, and which prepares the dispersion technology that key is liquid adduct, it controls the size of adduct diameter of carrier and distribution, or even affects the defect of adduct solid magnesium halide lattice, and then affects 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 begins attempt to 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, polymerization activity is low and hydrogen response is poor when for propylene polymerization for the catalyst formed with the adduct and titanium tetrachloride reaction.
CN103073661A discloses formula for MgCl2(ROH)m(LB)nMagnesium chloride adduct, wherein R be it is unsubstituted or by containing heteroatom group replace C1-C15Alkyl, LB are comprising C2-C20Aliphatic ether, C1-C10The lewis base of aliphatic carboxylic acid Arrcostab, ketone or silane, the value of m is 0.08 to 6 for the value of 0.5 to 2.5, n, and 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, wherein X are chlorine or bromine, and R is C1-C4Alkyl, E is o-alkoxyl benzoate compounds, by the adduct of magnesium halides and halogenated titanium and optional internal electron donor reaction, the catalyst with high stereotaxises ability can be obtained, the catalyst for particularly obtaining still has higher stereotaxises ability when for preparing high melt flow index polypropylene, when the adduct of magnesium halides is prepared, the o-alkoxyl benzoate compounds can derive from the alcoholysis reaction of o-alkoxyl Benzenecarbonyl chloride., in order to avoid there is hydrolysis in the alkoxyl in o-alkoxyl Benzenecarbonyl chloride., the raw material to being used is needed to carry out strict anhydrous process, by weight, the condition of the anhydrous process generally makes the water content of magnesium halide be less than 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, and Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Substituted or unsubstituted aryl, C1-C14Straight or branched alkoxyl and C6-C14Substituted or unsubstituted aryloxy group in one kind, R is C1-C20Alkyl, r is more than 1 integer, E is hydroxybenzoic acids or hydroxy benzoic acid esters compound, m is 1-5, n is 0.001-0.5, when for propylene polymerization, the hydrogen response of catalyst has obtained further improvement to the catalyst that the adduct of magnesium halides is prepared with halogenated titanium and optional internal electron donor reaction.
CN102796127A discloses a kind of formula for MgXY-mEtOH-n (LB1)-k(LB2)-p(LB3) adduct of magnesium halides, wherein X be chlorine or bromine, Y be chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Substituted 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 one kind in the alcohol of ethanol, m is 1-5, n is 0.005-2, k is 0.0005-0.3, p is 0.0005-0.3, the catalyst that the adduct and halogenated titanium and optional internal electron donor reaction are further prepared can be adjusted to obtain between ability and stereotaxises ability in hydrogen and preferably be balanced, but, the polymerization activity of the catalyst needs further to improve.
At present, the adduct of magnesium halides as mentioned above containing other electron donors in addition to alcohol and water, is typically also to be prepared by high-speed stirred, spray cooling or the method such as high-gravity rotating bed.
The introducing of electron donor in adduct of magnesium halides can improve the olefinic polymerization performance of catalyst, and different adduct preparation methoies also has the olefinic polymerization performance for improving the catalyst that thus adduct is further prepared to a certain extent.As EP395083 prepares the magnesium chloride adduct of low ethanol content using the method that alcohol content higher adduct is carried out partial dealcoholation successively, the catalyst further prepared by the adduct has good morphological stability, have in olefin polymerization and avoid or limit molecule being formed, to reduce the advantage that problem is brought to polymerization equipment operation.
It is well known that the catalyst with diether compound as internal electron donor is when for olefinic polymerization, resulting polymers have narrow molecular weight distribution and high stereospecificity, are particularly suitable for the production of fibre resin.It is found by the applicant that, during with diether compound as internal electron donor, the catalyst further prepared by the adduct for adopting the adduct melt containing electron donor to prepare through the manufacturing process of the construction unit to cooling medium with hole under pressure, when for olefinic polymerization, catalyst shows further improvement to the sensitivity of hydrogen, and the preparation technology of adduct is simple to operate, adduct particles size is controllable, this has very big industrial application value.
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, it is characterized by using by the new method of the construction unit with hole to cooling medium prepared by adduct melt adduct of magnesium halides under pressure, then making adduct of magnesium halides contact with titanium compound and diether compound；And the catalytic component by the method preparation and catalyst system and its application.When the caltalyst formed by catalytic component prepared according to the methods of the invention ties up to the catalyst as olefinic polymerization, the hydrogen response for further improving is shown.
As stated in the Background Art, the preparation method of adduct of magnesium halides ball type carrier includes 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 in the noble gases of preheating is dried to spherical magnesium chloride support；
However, the present inventor has found under study for action, using spray drying method in carrier preparation process, a large amount of ethanol, nitrogen, energy are expended, and the carrier granular form for finally giving is not good；
Adduct carrier prepared by simultaneous spray drying method has following impact to catalyst：Due to the outlet temperature of spray-dried instrument it is higher, cause the ball type carrier alcohol content for obtaining relatively low, especially the alcohol on spherical carrier particle surface is very few, during follow-up load titanium, active component with carrier useful effect and can not be combined on the surface, make active ingredient content in catalyst low and then affect the polymerization activity of 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 of small particle is obtained, and alcohol content is too high in the carrier for preparing；
The adduct carrier that simultaneously prepared by spray cooling has following impact to catalyst：In ball type carrier, as mean diameter is larger, and alcohol content is higher, when adduct is reacted with titanium-containing compound, as reaction is excessively fierce, often crushes carrier, causes the fine powder content of final polymer to increase.
(3) high pressure extrusion cooling method：With the less oil refining of viscosity, paraffin, white oil etc. as reaction medium, temperature of reaction system rise to 120-130 DEG C and maintain a period of time after, be filled with high pure nitrogen into reactor, make reacting kettle inner pressure reach 10-15 atmospheric pressure；Afterwards, the mixture of chlorination magnesium alcoholate melt and reaction medium is discharged in cooling medium by a discharge duct；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 not good enough, so that the final catalyst granules form for preparing is not good enough, the particle shape of polymer is not ideal enough, and the bulk density of polymer is not high.
(4) high-speed mixing method：Anhydrous magnesium chloride and alcohol are added in the inert liquid medium immiscible with which by a certain percentage, are heated under agitation, is made EtOH/MgCl2Form adduct melt and disperse in media as well, emulsifying then to be carried out in high speed agitator, and is transferred in the medium of low temperature, by MgCl2-ol adduct rapid condensation cured globulate MgCl wherein2Carrier；
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 in the inert liquid medium immiscible with which by a certain percentage, are heated under agitation, is made EtOH/MgCl2Form adduct melt and disperse in media as well, it is then transferred to high-gravity rotating bed, static distribution device through being arranged at rotor center is equably sprayed on the inner edge of the filler that adjustment is rotating, material be adjusted rotate filler shearing, dispersion after, magnesium chloride/alcohol adducts melt is scattered in inert media in the form of fine drop；
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) carrier when, diameter of carrier wider distribution；During steady production, generally use blending agent (generally white oil and silicone oil mixing) normally to produce, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, keep the ratio of the two, 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 adduct carrier technique processed, but this technology is the drawbacks of have aforementioned, needs perspective study and exploitation.
The present inventor is proposed in the presence of inert liquid medium first, by liquid halide magnesium adduct under pressure through the construction unit with hole and the manufacturing process of liquid cooling medium contact preparation adduct solid particle, simple to operate, repetition stability is strong, the size and size distribution of adduct of magnesium halides can stably be controlled, the defect of existing adduct carrier technology of preparing is overcome, and the olefin polymerization catalysis further prepared by the adduct for obtaining have the high advantage of hydrogen response.
Specifically, according to the first aspect of the invention, 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 diether compound are carried out into haptoreaction, the preparation process of the adduct of magnesium halides includes：(1) by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and the mixture for obtaining is heated, 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, and the amount of oxyl benzoyl based compound is 0.001-0.32 mole, aqueous MgX1In Y, the amount of water is 0.011-0.081 mole；Or
By anhydrous MgX1Y and R1The mixing of OH, oxyl benzoyl based compound and water, and the mixture for obtaining is heated, 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, and the amount of oxyl 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-C14Straight or branched alkoxyl and C6-C14Aryloxy group in one kind, R1For C1-C12Straight or branched alkyl, C3-C10Cycloalkyl and C7-C10Aralkyl in one kind,
The oxyl benzoyl based compound shown in formula I,
In Formulas I, X2For the one kind in halogen atom,
R2、R3、R4And R5Respectively hydrogen, halogen, nitro, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind, or, R2、R3、R4And R5In two or more be 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 shaped and is dried to liquid cooling medium chilling through the construction unit with hole under pressure, obtain Spherical magnesium halide adduct granule.
According to the second aspect of the invention, the invention provides the catalytic component for olefinic polymerization prepared according to preparation method of the present invention.
According to the third aspect of the present invention, the invention provides a kind of application of catalytic component in the catalyst system for olefinic polymerization is prepared.
According to the fourth aspect of the present invention, the invention provides a kind of catalyst system for olefinic polymerization, the catalyst system contains：I () catalytic component, the catalytic component are 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.
According to the fifth aspect of the present invention, the invention provides caltalyst of the present invention ties up to the application in olefinic polyreaction.
According to the sixth aspect of the invention, the invention provides a kind of olefine polymerizing process, the method is included under olefin polymerization conditions, one or more alkene is 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 inert media production of mixing, can also be using such as individually white oil or the silicone oil production of single medium, it is clear that using Single Medium for the production of adduct carrier undoubtedly improves the repetition stability of its production；And higee technology is during steady production, generally use blending agent (the usually blending agent of white oil and silicone oil) production, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, keep the ratio of the two, this increased difficulty for the repetition stability for maintaining the production of adduct carrier.
Second, compared to aforementioned existing adduct carrier technology of preparing, the equipment of the technology of the present invention is simple, and energy consumption and material consumption are low.
3rd, by key elements such as the mesh number of adjusting hole, the number of plies of construction unit and pressure, it is easier to 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, the catalytic component for producing compared to existing technology, when for olefinic polymerization, with the hydrogen response for improving, this lays a good foundation for the acrylic resin of exploitation high added value.
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, is used to explain the present invention, but is not construed as limiting the invention together with detailed description below.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
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that specific embodiment described herein is merely to illustrate and explains the present invention, the present invention is not limited to.
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 diether compound are carried out into haptoreaction, the preparation process of the adduct of magnesium halides includes：
(1) by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and the mixture for obtaining is heated, obtain the adduct of magnesium halides of liquid；Or
By anhydrous MgX1Y and R1The mixing of OH, oxyl benzoyl based compound and water, and the mixture for obtaining is heated, obtain the adduct of magnesium halides of liquid；
(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is shaped and is dried to liquid cooling medium chilling through the construction unit with hole under pressure, obtain Spherical magnesium halide adduct granule.
The method according to the invention, the MgX1In Y, X1For chlorine or bromine, Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Aryl, C1-C14Straight or branched alkoxyl and C6-C14Aryloxy group in one kind；Preferably, 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 the mixture of two or more magnesium-containing compounds.Specifically, in adduct preparation method of the present invention, MgX1The instantiation of Y can include but is not limited to one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.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-C10Cycloalkyl and C7-C10Aralkyl in one kind；Preferably, R1For C1-C6Straight or branched alkyl；It is highly preferred that R1For 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：Methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, 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,
In Formulas I, X2For the one kind in halogen atom, preferably chlorine；
R2、R3、R4And R5Respectively hydrogen, halogen, nitro, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind, or, R2、R3、R4And R5In two or more be mutually bonded, to form ring,
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；
R6With R1Differ, be C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind；
Preferably, R6For C1-C6Straight or branched alkyl, C3-C6Cycloalkyl, C6-C10Aryl and C7-C10Aralkyl 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 are 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- methoxyl group -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 chlorides、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 chlorides、2- methoxyl group -4- isoamyl benzene formyl chlorides、2- methoxyl group -4- cyclopenta Benzenecarbonyl chloride .s、2- ethoxy benzoyl chlorides and 2- n-butoxy Benzenecarbonyl chloride .s.
With the method for the invention it is preferred to by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and the mixture for obtaining is heated, 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, and preferably 2-3.7 mole, more preferably 2.4-3.7 mole, 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；Aqueous MgX1In Y, the amount of water is 0.011-0.081 mole, preferably 0.016-0.053 mole, more preferably 0.021-0.045 mole；Or；
By anhydrous MgX1Y and R1The mixing of OH, oxyl benzoyl based compound and water, and the mixture for obtaining is heated, 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, preferably 2-3.7 mole, more preferably 2.4-3.7 mole；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 is determined using Karl-Fischer method.Can be by controlling MgX1The drying condition of Y and/or by MgX1Y is contacted with the material for having reactivity to water, 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 using anhydrous process is front carried out, will be raw materials used in moisture Control do not affecting in the range of result of the test.Usually, R1The water content of OH is that the water content of oxyl benzoyl based compound is that the water content of inert liquid medium is less than 50ppm (by weight) less than 10ppm (by weight) less than 100ppm (by weight).In control or reduction solid material or liquid material, the method for water content is well known in the art, for example：Liquid material can be distilled and/or be contacted with water absorbing agent (such as molecular sieve), high-purity inert gas, such as High Purity Nitrogen air-flow can be continually fed into in the solid material of heating or liquid material.
Preparation in accordance with the present invention, for by anhydrous MgX1Y and R1OH, the mixture of oxyl benzoyl based compound and water or aqueous MgX1Y、R1The mixture heating of OH and oxyl benzoyl based compound, is not particularly limited with the condition for being reacted and being formed liquid halogenated magnesium adduct, as long as the condition of the heating be enough to the adduct of magnesium halides to form liquid.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, can further optimize the adduct particles size and size distribution of preparation, while the catalytic component further prepared by the adduct for obtaining is when for olefinic polymerization, with the hydrogen response for improving.
The method of the present invention, only liquid halogenated magnesium adduct need to be made through the construction unit with hole under certain pressure effect, without the need for it is complicated it is high-gravity rotating bed under the conditions of and be capable of achieving the purpose of the present invention without using accurate spraying apparatus, as can be seen here, the method of the present invention, existing solid adduct technology of preparing is compared, equipment is simple, and 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 is 10-1800 μm, more preferably 20-800 μm, more preferably 20-200 μm, more preferably 40-80 μm.
The method according to the invention, the construction unit with hole can be various forms, for example, plate with hole, the net with hole etc..For the present invention, it is however preferred to have the net in hole, according to the ready availability consideration of the needs and material of actual production, twine of the most preferred diameters for 0.025-4mm.
The method according to the invention, the material of the construction unit with hole is without particular/special requirement, for example, one or more in metal material, cloth material, plastic material and ceramic material.According to the ready availability of the needs and material of actual production, preferably metal material.
A preferred embodiment of the invention, the construction unit with hole are stratum reticulare.
A preferred embodiment of the invention, the stratum reticulare are metal net layer.
The method according to the invention, the wire netting using multilamellar macropore gauge structure and the small-bore structural metal net using the relatively little of number of plies, it is possible to obtain the suitable adduct solid particle of particle morphology.The metal mesh structure of 1-20 layer aperture gauge structures (if aperture is for 30-50 μm) is preferably adopted when preparing small particle (such as less than 30 μm) adduct carrier, the metal mesh structure of relative large aperture (if aperture is for the 65-200 μm) structure of 1-20 layers is preferably adopted when big particle diameter (such as larger than 60 μm) adduct carrier is prepared.
A preferred embodiment of the invention, the stratum reticulare include 1-20 layers, preferably include 2-8 layers, more preferably 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 particle diameter, the control of particle shape, that is to say, that the method for the present invention can be according to market demand, and the production for being quantified is changed the line of production convenient and easy.
The method according to the invention, the inert liquid medium can be the liquid compound that chemical reaction does not occur with magnesium halide, alcohol, diether compound, and the preferably inert liquid medium is silicone oil and/or inert fluid hydrocarbon solvent；It is highly preferred that the inert liquid medium is C4-C10Alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, one or more in 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 use the inert media production of mixing, can also be worked well using such as individually white oil or the silicone oil production of single medium.It is clear that using Single Medium for the production of adduct carrier undoubtedly increased its repetition stability.During higee technology steady production, generally use blending agent (the usually blending agent of white oil and silicone oil) production, but with the continuous consumption of production process, need to be continuously replenished fresh inert media, keep the ratio of the two, so for the repetition stability for maintaining carrier production, difficulty is increased.
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, relative to 1 mole of 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 the mixture for obtaining is contacted with liquid cooling medium through the construction unit with hole under pressure carry out cooling forming.
Can also using part described inert liquid medium as the adduct of magnesium halides for preparing the liquid reaction medium, so as to obtain the mixed liquor of the adduct of magnesium halides containing liquid, then the mixed liquor is mixed with the inert liquid medium of remainder, then contacting through the construction unit with hole with liquid cooling medium under pressure carries out cooling forming.
Can also be using all reaction medium of the inert liquid medium as the adduct of magnesium halides for preparing the liquid, so as to obtain the mixed liquor of the adduct of magnesium halides containing liquid, then contacting through the construction unit with hole with liquid cooling medium under pressure carries out cooling forming.
When needing, some surfactants, such as fatty glyceride, fatty acid sorbitan, Polysorbate, polyoxyethylene ether or Pluronic F68 are also optionally added in the inert liquid medium.The consumption of the surfactant can be the conventional amount used of this area, for example：Relative to 1 mole of MgX in terms of magnesium1Y, the consumption of the surfactant can be 0.001-1 mole.
The method according to the invention, the liquid cooling medium can be commonly used in the art various chemically interactive liquid medium does not occur with adduct of magnesium halides.For example, the liquid cooling medium can be unreactive hydrocarbons solvent.The instantiation of the liquid 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 is not affecting the moisture Control in liquid cooling medium used in the range of result of the test using anhydrous process is front carried out.Usually, the water content of the liquid cooling medium is controlled to into not higher than 5ppm (by weight).The method for controlling or reducing water content in the liquid cooling medium is well known in the art, for example：Liquid material can be distilled and/or be contacted with water absorbing agent (such as molecular sieve), high-purity inert gas, such as High Purity Nitrogen air-flow can be continually fed into 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 temperature of the liquid cooling 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 has no particular limits, as long as the consumption of the cooling medium be enough to product is cooled down and shaped.Specifically, the cooling medium and the volume ratio of the product are 1-15:1, preferably 2-9:1.
Adduct of magnesium halides granule obtained from the shaping of Jing chillings can be washed and is dried.Can adopt well known to a person skilled in the art the adduct of magnesium halides for obtaining is washed by method, 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 temperature of the drying 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 in normal pressure or under conditions of reducing pressure.
It is not being bound by any particular theory, with MgX1Y is MgCl2, R1OH is ethanol, as a example by oxyl benzoyl compound is 2- methoxy benzoyl chlorides, experiences the following reaction mechanism mechanism of reaction according to the method that above two adduct prepares embodiment, 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, the unit with pore structure can be arranged in adduct of magnesium halides Location Detection of Medium Transportation Pipeline or is arranged between adduct of magnesium halides Location Detection of Medium Transportation Pipeline and liquid cooling medium storage tank.Specifically, as shown in figure 1, the unit 2 with pore structure is arranged in adduct of magnesium halides Location Detection of Medium Transportation Pipeline 1, adduct of magnesium halides passes through the unit with pore structure before contacting with cooling medium；Or, as shown in Figure 2, the unit 2 with pore structure is arranged between adduct of magnesium halides Location Detection of Medium Transportation Pipeline 1 and liquid cooling medium 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 the catalytic component further synthesized using the adduct carrier, the catalytic component for producing compared to existing technology, when for olefinic polymerization, 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 is reacted with titanium compound, and within one or more time periods before and after, during the adduct of magnesium halides with titanium compound reaction adds the diether compound to carry out the haptoreaction.
Specifically, the adduct of magnesium halides can be carried out according to mode same as the prior art with the reaction of titanium compound, for example, the adduct of magnesium halides can be suspended in the mixed liquor of cold titanium compound or titanium compound with 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 -25 DEG C to -15 DEG C), then the mixture for obtaining is heated to into 40-130 DEG C, it is preferably heated to 80-130 DEG C, and 0.5-2 hours are maintained at the temperature disclosed above, then carry out solid-liquid separation and collect solid；Then, the solid for obtaining is suspended in titanium compound, and the mixture for obtaining is heated to into 60-130 DEG C, 80-130 DEG C is preferably heated to, and maintains 0.5-2 hours at the temperature disclosed above, then carried out solid-liquid separation and collect 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 diether compound before and after, during the reaction of the adduct of magnesium halides and titanium compound in one or more time periods in add, preferably add while adduct of magnesium halides granule is reacted with titanium compound.
According to the present invention, the diether compound can be it is commonly used in the art it is various can be used as the diether compound of catalyst component for olefin polymerization internal electron donor compound.For example, the diether compound can be 1, the 3- diether compounds shown in formula II：
In Formula II, RI、RII、RIII、RIV、RVAnd RVIRespectively hydrogen, halogen, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind, RVIIAnd RVIIIRespectively C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind.In the present invention, RI、RII、RIII、RIV、RVAnd RVIIn two or more can be mutually bonded, to form ring.
Preferably, in Formula II：
RI、RII、RVAnd RVIFor hydrogen；
RVIIAnd RVIIIRespectively C1-C4Straight or branched alkyl, more preferably methyl；
RIIIFor methyl, ethyl, n-pro-pyl or isopropyl, RIVFor the one kind in ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, isopentyl, 2- ethylhexyls, cyclopenta, cyclohexyl, methylcyclohexyl, phenyl and benzyl；Or, RIIIFor hydrogen, RIVFor the one kind in ethyl, normal-butyl, sec-butyl, the tert-butyl group, 2- ethylhexyls, cyclohexyl-ethyl, diphenyl methyl, rubigan, 1- naphthyls and 1- decahydro naphthyls；Or, RIIIAnd RIVIt is identical, and for the one kind in ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, neopentyl, phenyl, benzyl, cyclohexyl and cyclopenta；Or, RIIIAnd RIVIt is mutually bonded, to form cyclopentadienyl group, fluorenyl or indenyl.
According to the present invention, the example of the diether compounds can be including but not limited to：2- (2- ethylhexyls) -1,3- dimethoxy propanes、2- isopropyls -1,3- dimethoxy propanes、2- butyl -1,3- dimethoxy propanes、2- sec-butyls -1,3- dimethoxy propanes、2- cyclohexyl -1,3- dimethoxy propanes、2- phenyl -1,3- dimethoxy propanes、2- (2- phenylethyls) -1,3- dimethoxy propanes、2- (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes、2- (p- chlorphenyl) -1,3- dimethoxy propanes、2- (diphenyl methyl) -1,3- dimethoxy propanes、2,2- dicyclohexyls -1,3- dimethoxy propanes、2,2- bicyclopentyls -1,3- dimethoxy propanes、2,2- diethyl -1,3- dimethoxy propanes、2,2- dipropyl -1,3- dimethoxy propanes、2,2- diisopropyls -1,3- dimethoxy propanes、2,2- dibutyl -1,3- dimethoxy propanes、2- methyl-2-propyls -1,3- dimethoxy propanes、2- methyl -2- benzyls -1,3- dimethoxy propanes、2- methyl -2- ethyls -1,3- dimethoxy propanes、2- methyl -2- isopropyls -1,3- dimethoxy propanes、2- methyl -2- phenyl -1,3- dimethoxy propanes、2- methyl -2- cyclohexyl -1,3- dimethoxy propanes、2,Double (the 2- cyclohexyl-ethyls) -1 of 2-,3- dimethoxy propanes、2- methyl -2- isobutyl groups -1,3- dimethoxy propanes、2- methyl -2- (2- ethylhexyls) -1,3- dimethoxy propanes、2,2- diisobutyls -1,3- dimethoxy propanes、2,2- diphenyl -1,3- dimethoxy propanes、2,2- dibenzyl -1,3- dimethoxy propanes、2,Double (cyclohexyl methyls) -1 of 2-,3- dimethoxy propanes、2- isobutyl group -2- isopropyls -1,3- dimethoxy propanes、2- (1- methyl butyls) -2- isopropyls -1,3- dimethoxy propanes、2- isopropyl -2- isopentyl -1,3- dimethoxy propanes、2- phenyl -2- isopropyls -1,3- dimethoxy propanes、2- phenyl -2- sec-butyls -1,3- dimethoxy propanes、2- benzyl -2- isopropyls -1,3- dimethoxy propanes、2- cyclopenta -2- isopropyls -1,3- dimethoxy propanes、2- cyclopenta -2- sec-butyls 1,3- dimethoxy propanes、2- cyclohexyl -2- isopropyls -1,3- dimethoxy propanes、2- cyclohexyl -2- sec-butyls -1,3- dimethoxy propanes、2- isopropyl -2- sec-butyls -1,3- dimethoxy propanes、2- cyclohexyl -2- cyclohexyl methyls -1,3- dimethoxy propanes，9,9- dimethoxy-methyl fluorenes.
In an embodiment of the present invention, using 2- isopropyl -2- isopentyl -1, advantage of the 3- dimethoxy propanes as the illustrative present invention of diether compound.
CN1020448C, CN100348624C, CN1015062B and CN1121368C disclose above-mentioned diether compound, and related content disclosed in which is all incorporated herein by reference.
Usually, the preparation method of the catalytic component for olefinic polymerization of the invention, the titanium compound can be three halogenated titaniums and formula Ti (OR7)4 - qX2 qOne or more in shown titanium compound, in the formula, R7Can be C1-C10Alkyl, X2Can be halogen, m can be the integer of 0-4.Preferably, the titanium compound be titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, three titanium butoxide of a chlorine, dichloro dibutoxy titanium, one titanium butoxide of trichlorine, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, one ethanolato-titanium of trichlorine and titanous chloride. in one or more.It is highly preferred that the titanium compound is titanium tetrachloride.
According to the present invention, the consumption of the consumption of the adduct of magnesium halides, the consumption of titanium compound and diether compound can carry out appropriate selection according to the composition of the expected catalytic component for olefinic polymerization.For example, the titanium compound, diether compound and the mol ratio of the adduct of magnesium halides can be 5-100:0.01-0.5:1；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 be included in prepare catalytic component of the present invention during the total amount of titanium compound that uses.
As it was previously stated, a kind of present invention also offers catalytic component for olefinic polymerization for preparing according to the method described in the present invention.
Catalytic component for olefinic polymerization of the invention, due to having used the adduct of magnesium halides containing other electron donors in addition to alcohol and water prepared according to adduct of magnesium halides preparation method of the present invention, the hydrogen response of improvement is shown when for olefinic polyreaction, but while still maintains high polymerization activity, high capacity of orientation and narrow molecular weight distribution.
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：
I () catalytic component, the catalytic component are 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, will not be described here.
The alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art.For example, the alkyl aluminum compound can be alkylaluminium sesquichloride and formula AlR8R9R10One or more in shown compound, in the formula, R8、R9And R10Can be each chlorine and C1-C8Alkyl in one kind, and R8、R9And R10At least one of be C1-C8Alkyl.Preferably, the alkyl aluminum compound is 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 di-n-hexyl aluminum, one aluminium ethide of dichloro, one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro, one n-hexyl aluminum of dichloro and Al2Et3Cl3In one or more, wherein, Et is ethyl.
The mol ratio of the catalyst system for olefinic polymerization of the invention, the alkyl aluminum compound counted with aluminum and the catalytic component counted with titanium can be as 1-2000:1, preferably 20-700:1.
In the case where the organic vertical structure of alkene particularly alpha-olefin (such as propylene or 1-butylene) is polymerized, the catalyst system for olefinic polymerization of the invention can also be comprising the electron donor compound same or different from the compound phase as internal electron donor as external donor compound.
The external donor compound can be various external donor compounds commonly used in the art, for example：The external donor compound can be carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound in one or more.Preferably, the external electron donor is general formula R11 xR12 ySi(OR13)zShown organo-silicon compound, in the formula, R11、R12And R13Respectively C1-C18Alkyl or contain heteroatomic C1-C18Alkyl；X and y is respectively the integer of 0-2, integers of the z for 1-3, and x+y+z=4.It is highly preferred that general formula R11 xR12 ySi(OR13)zIn, R11And R12At least one of be selected from C3-C10With or without heteroatomic branched alkyl, C3-C10With or without 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, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- t-butyldimethoxysilanes, (1,1, tri- fluoro- 2- propyl group of 1-) -2- ethyl piperidine base dimethoxysilanes, (1, tri- fluoro- 2- propyl group of 1,1-)-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 0.005-0.5 mole；Preferably, relative to 1 mole of alkyl aluminum compound in terms of aluminum, the consumption of the external donor compound is 0.01-0.4 mole.
Catalyst system for olefinic polymerization of the invention, preferably using one or more in above-mentioned electron donor compound as external electron donor.
According to the present invention, when the catalyst system for olefinic polymerization is used for olefinic polymerization, the catalytic component for olefinic polymerization, alkyl aluminum and optional external electron donor can be separately added in polymer reactor, in polymer reactor being added after mixing also, 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 the application in olefinic polyreaction.
Present invention also offers a kind of olefine polymerizing process, the method is included under olefin polymerization conditions, and the catalyst system that one or more alkene are provided with the present invention is contacted.
The present invention's thes improvement is that the catalytic component and its catalyst system for olefinic polymerization for employing a kind of adduct prepared by new adduct technology of preparing and then preparing.The olefine polymerizing process of the present invention is not particularly limited for olefin polymerization conditions and the alkene for being used.
Usually, olefine polymerizing process of the invention, the alkene can be formula CH2=CHR14Shown alkene, wherein, R14Can be hydrogen, C1-C12Straight or branched alkyl and C6-C12Aryl in one kind.Olefine polymerizing process of the invention, if necessary, the alkene can also contain a small amount of alkadienes.Olefine polymerizing process of the invention, the alkene are 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, the polymerization can be polymerisation in bulk, gas-phase polymerization, slurry polymerization or liquid-phase bulk-gas phase polymerization mix.Olefine polymerizing process of the invention, 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, determined according to ASTM D1238-99.
2nd, polymer isotacticity：(heptane boiling extracting 6 hours) is determined using heptane extraction process：The ratio of residue drying to the polymer weight (g) obtained by constant weight and 2, after being extracted 6 hours with boiling heptane in being placed on extractor, is isotacticity by two grams of dry polymer samples.
3rd, particle diameter distribution test：The mean diameter and particle size distribution of adduct of magnesium halides granule Masters Sizer 2000 (being manufactured by Malvern Instruments Ltd) particle size analyzer determination.
4th, the molecular weight distribution of polymer adopts PDI (Mw/Mn)：Determined using Waters companies Waters Alliance GPC2000 chromatograph of gel permeation, 1,2,4- trichloro-benzenes are solvent, and styrene is standard specimen, and temperature is 25 DEG C.
Prepare embodiment 1
In the reactor of 1000mL, 150mL white oils are added (commercially available from Guangzhou Ming En petrochemical industries company limited, by weight, water content is less than 50ppm), 300mL methyl-silicone oils are (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is less than 50ppm), 30g contains the magnesium chloride (commercially available from Xin Yitai factories of Fushun City) of 0.44wt% moisture, 50mL dehydrated alcohol is (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), 125 DEG C are warming up under agitation.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 (per thickness degree 0.1mm) blowing pipeline be depressed into pre-cool to -30 DEG C 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 5 times, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct S1 of the invention, characterization result such as table 1.
Prepare embodiment 2
In the reactor of 1000mL, 150mL white oils are added (commercially available from Guangzhou Ming En petrochemical industries company limited, by weight, water content is less than 50ppm), 300mL methyl-silicone oils are (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is less than 50ppm), 30g anhydrous magnesium chlorides (commercially available from Xin Yitai factories of Fushun City), 50mL dehydrated alcohol is (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, 125 DEG C are warming up under agitation.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 (per thickness degree 0.1mm) blowing pipeline be depressed into pre-cool to -30 DEG C 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 5 times, and be vacuum dried 1.5 hours at 30 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, and except for the difference that, the construction unit with hole is 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, 500mL white oils are added (commercially available from Guangzhou Ming En petrochemical industries company limited, by weight, water content be less than 50ppm), 30g contain the magnesium chloride (commercially available from Xin Yitai factories of Fushun City) of 0.44wt% moisture, 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), 125 DEG C are warming up under agitation.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 (per thickness degree 0.1mm) blowing pipeline be depressed into pre-cool to -30 DEG C 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 5 times, and be vacuum dried 1.5 hours at 30 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, 500mL methyl-silicone oils are added (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content be less than 50ppm), 30g contain the magnesium chloride (commercially available from Xin Yitai factories of Fushun City) of 0.44wt% moisture, 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), 125 DEG C are warming up under agitation.After isothermal reaction 3 hours, by mixture under the pressure of 0.5MPa by prepackage have three layers aperture for 75 μm of wire nettings (per thickness degree 0.1mm) blowing pipeline be depressed into pre-cool to -30 DEG C 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 5 times, and be vacuum dried 1.5 hours at 30 DEG C, so as to obtain Spherical magnesium halide adduct S5 of the invention, characterization result such as table 1.
Prepare comparative example 1
It is prepared by the method according to embodiment 1 is prepared, except for the difference that, by the mixture for obtaining be transferred to 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 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 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
It is prepared by the method according to embodiment 4 is prepared, except for the difference that, by the mixture for obtaining be transferred to 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 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 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 adduct carrier of different-grain diameter, 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 the catalyst system for olefinic polymerization 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, 90mL titanium tetrachlorides are sequentially added, -20 DEG C are cooled to, added 8.0g Spherical magnesium halide adducts S1, and stir 30 minutes at -20 DEG C.Then, 110 DEG C are to slowly warm up to, and 1.2mL 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes is added in temperature-rise period.After 110 DEG C of isothermal reactions 30 minutes, liquid is filtered.80mL titanium tetrachlorides are added, 120 DEG C are warming up to, after maintaining 30 minutes at 120 DEG C, liquid is filtered；Then, 80mL titanium tetrachlorides are added, and is warming up to 120 DEG C, after maintaining 30 minutes at 120 DEG C, filter liquid.5 times (hexane consumption is 80mL/ time) is finally washed with 60 DEG C of hexane to the solid for obtaining, and is vacuum dried gained solidss, so as to obtain spherical catalyst components C1.
(2) propylene polymerization：
Under nitrogen protection, the hexane solution (concentration is 0.5mmol/mL) of 5mL triethyl aluminums, the hexane solution (concentration is 0.1mmol/mL) of 1mL Cyclohexyl Methyl Dimethoxysilanes and 9mg spherical catalyst components C1 are sequentially added in the rustless steel autoclave of 5L.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, polyacrylic isotactic index, melt index and the molecular weight distribution for preparing is determined, be the results are shown in Table 2.
Comparative example 1
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, adduct of magnesium halides is prepared as follows：
In the reactor of 500mL, 150mL white oils are added (commercially available from Guangzhou Ming En petrochemical industries company limited, by weight, water content be less than 50ppm), 30g contain the magnesium chloride (commercially available from Xin Yitai factories of Fushun City) of 0.44wt% moisture, 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), 125 DEG C are warming up under agitation.After isothermal reaction 3 hours, mixture press-in is preheated to 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 into -30 DEG C of 2L hexanes (by weight, water content is less than 5ppm), carries out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed with the hexane of 300mL 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.
Comparative example 2
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, it is used for the preparation of the catalytic component of olefinic polymerization using the adduct DS1 for preparing the preparation of comparative example 1, so as to obtain spherical catalyst components DC1.The results are shown in Table 2.
Embodiment 2
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and the catalyst system for olefinic polymerization and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, 2- isopropyl -2- isopentyl -1, the addition of 3- dimethoxy propanes are 1.6mL, 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 the catalyst system for olefinic polymerization and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, using prepare embodiment 2 prepare carrier S 2 be used for olefinic polymerization catalytic component preparation, so as to obtain spherical catalyst components C3.The results are shown in Table 2.
Comparative example 3
Method according to embodiment 3 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, adduct of magnesium halides is prepared as follows：
In the reactor of 500mL, 150mL white oils are added (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 dehydrated alcohol is (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, be warming up to 125 DEG C under agitation.After isothermal reaction 3 hours, mixture press-in is preheated to 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 into -30 DEG C of 2L hexanes (by weight, water content is less than 5ppm), carries out chilling shaping.Liquid is filtered to remove, the solid for obtaining is washed with the hexane of 300mL 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 4
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and the catalyst system for olefinic polymerization and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, using prepare embodiment 3 prepare adduct S3 be used for olefinic polymerization catalytic component preparation, so as to obtain spherical catalyst components C4.The results are shown in Table 2.
Embodiment 5
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and the catalyst system for olefinic polymerization and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, it is used for the preparation of the catalytic component of olefinic polymerization using the adduct S4 for preparing the preparation of embodiment 4, so as to obtain spherical catalyst components C5.The results are shown in Table 2.
Comparative example 4
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, it is used for the preparation of the catalytic component of olefinic polymerization using the adduct DS2 for preparing the preparation of comparative example 2, so as to obtain spherical catalyst components DC2.The results are shown in Table 2.
Embodiment 6
The embodiment is used for explanation for catalytic component of olefinic polymerization and preparation method thereof and the catalyst system for olefinic polymerization and its application.
Method according to embodiment 1 prepare for olefinic polymerization catalytic component and carry out propylene polymerization, except that, using prepare embodiment 5 prepare adduct S5 be used for olefinic polymerization catalytic component preparation, so as to obtain spherical catalyst components C6.The results are shown in Table 2.
Table 2
From the results shown in Table 2, the method according to the invention prepares catalytic component when for propylene polymerization, is maintaining high isotactic index (boiling n-heptane insoluble matter>97.0wt%), high polymerization activity and while narrow molecular weight distribution, shows the hydrogen response of improvement, and this has higher industrial application value.The high isotactic PP resins of higher melting index are may be implemented in while maintain high Mechanical Properties of Products in the production for fiber material products (such as non-woven fabrics), further reduce the processing temperature of resin；Meanwhile, because of the narrow molecular weight distribution of polymer, be conducive to further reducing the fineness of fibre denier silk, improve the performances such as the anti-permeability of fibre.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the range of the technology design of the present invention; various simple variants can be carried out 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 the case of reconcilable, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as which is without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of preparation method of the catalytic component for olefinic polymerization, the method include：By adduct of magnesium halides,
Titanium compound and diether compound carry out haptoreaction, it is characterised in that the preparation process of the adduct of magnesium halides
Including：
(1) by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, 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 the mixture for obtaining is heated,
Obtain the adduct of magnesium halides of liquid；
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,
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 is shaped and is dried to liquid cooling medium chilling, obtains Spherical magnesium halide adduct granule.
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 methyl-silicone oil or white oil/methyl-silicone oil mixture.
8. preparation method according to claim 1, wherein, the diether compound is 1,3- shown in formula II
Diether compound,
In Formula II, RI、RII、RIII、RIV、RVAnd RVIRespectively hydrogen, halogen, C1-C20Straight or branched alkyl,
C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind, RVIIAnd RVIIIRespectively C1-C20
Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one kind；Alternatively,
RI、RII、RIII、RIV、RVAnd RVIIn two or more be mutually bonded, to form ring.
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 MgX1In Y, the amount of water is 0.011-0.081 mole；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, diether compound with it is described
The mol ratio of adduct of magnesium halides is 5-100:0.01-0.5:1；Preferably 20-80:0.05-0.35:1, the titanium compound
In terms of titanium elements, the adduct of magnesium halides is in terms of magnesium elements.
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 preparing the catalyst for olefinic polymerization
Application in system.
A kind of 13. catalyst systems for olefinic polymerization, the catalyst system contain：
I () catalytic component, the catalytic component are 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 are included under olefin polymerization conditions, by one or more alkene with
Catalyst system contact described in claim 13.
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| CN102796210A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method |
| CN102796127A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN104109081A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for improving quality of glycol product prepared by using synthetic gas |
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| CN102796210A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method |
| CN102796127A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
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