CN107915789B

CN107915789B - Olefin polymerization catalyst carrier and preparation method thereof, olefin polymerization catalyst component and olefin polymerization catalyst and application thereof

Info

Publication number: CN107915789B
Application number: CN201610881074.XA
Authority: CN
Inventors: 凌永泰; 夏先知; 刘月祥; 李威莅; 赵瑾; 谭扬; 任春红; 高富堂; 彭人琪; 陈龙; 张天一; 张志会; 万真; 马长友; 段瑞林
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: 2016-10-09
Filing date: 2016-10-09
Publication date: 2021-02-05
Anticipated expiration: 2036-10-09
Also published as: CN107915789A

Abstract

The invention relates to the field of olefin catalysts, in particular to an olefin polymerization catalyst carrier, a preparation method of the olefin polymerization catalyst carrier, a catalyst component for olefin polymerization, the catalyst carrier prepared by the method, application of the catalyst component for olefin polymerization in preparation of a catalyst for olefin polymerization, application of the catalyst in olefin polymerization reaction and an olefin polymerization method. By adopting the technical scheme of the invention, in the preparation process of the olefin polymerization catalyst carrier, the oxirane compound and other epoxy compounds are mixed and then react with the magnesium halide alcoholate, so that the carrier with novel composition can be obtained, and the obtained carrier has good particle shape and basically does not have special-shaped particles. And the catalyst prepared by the carrier has higher activity when being applied to alpha-olefin polymerization, and the bulk density and isotacticity of the polymer obtained by polymerization can be improved.

Description

Olefin polymerization catalyst carrier and preparation method thereof, olefin polymerization catalyst component and olefin polymerization catalyst and application thereof

Technical Field

The invention relates to the field of olefin catalysts, in particular to an olefin polymerization catalyst carrier, a preparation method of the olefin polymerization catalyst carrier, a catalyst component for olefin polymerization, the catalyst carrier prepared by the method, application of the catalyst component for olefin polymerization in preparation of a catalyst for olefin polymerization, application of the catalyst in olefin polymerization reaction and an olefin polymerization method.

Background

It is well known that magnesium chloride supported Ziegler-Natta catalysts perform significantly better than other supported catalysts when used in propylene polymerization. Therefore, catalysts for olefin polymerization are mostly prepared by supporting titanium halides on activated magnesium chloride. At present, the activated magnesium chloride is generallyAnhydrous MgCl₂Reacting with alcohol at high temperature to generate alcohol compound, and removing alcohol. To obtain spherical alcoholate, it can be prepared by spray-drying, spray-cooling, high-pressure extrusion, high-speed stirring, the emulsifier method, the supergravity rotating bed method, and the like. Specifically, for example, WO99/44009 and US4399054 are prepared by high-temperature high-agitation emulsification of magnesium chloride alcoholate system and then quenching and shaping.

One of the common points of the preparation methods of the magnesium chloride spherical alcohol compound is that the high-temperature alcohol compound melt is solidified by low-temperature quenching, the energy consumption is large, the preparation process is complex, a plurality of reactors are required to be jointly prepared, and the particle size distribution of the prepared adduct is wide. In order to solve this problem, CN102040683A proposes a method for preparing a support by reacting a magnesium halide alcoholate with a compound. However, in the methods used in the prior art documents, the magnesium halide alcoholate is melt-dispersed and then the compound is directly added to the system, or the magnesium halide alcoholate is melt-dispersed and then directly added to a reactor containing the compound. Due to the property of the high-viscosity liquid, the experimental conditions are not easy to control, the preparation result of the method is unstable, the carrier adhesion phenomenon is easy to occur, and the defect of poor carrier forming effect is caused. Therefore, other surfactants, such as SPAN 80, SPAN 85, etc., need to be added during the preparation process. The addition of these substances not only increases the cost, but also adversely affects the recovery of by-products and increases the cost of post-recovery treatment.

Disclosure of Invention

The inventors of the present invention have surprisingly found that a novel carrier formed by mixing an oxirane compound with other epoxy compounds and then reacting the mixture with a magnesium halide alcoholate during the preparation of the olefin polymerization catalyst carrier has a very good morphology, is not prone to blocking, and does not increase the cost.

It is a first object of the present invention to overcome the above-mentioned drawbacks of the existing olefin polymerization catalyst supports and to provide a novel olefin polymerization catalyst support.

The second object of the present invention is to provide a method for preparing a carrier for an olefin polymerization catalyst.

It is a third object of the present invention to provide a catalyst component for olefin polymerization.

A fourth object of the present invention is a catalyst support as described above, a catalyst support prepared by a process as described above and the use of a catalyst component for the polymerization of olefins as described above for the preparation of a catalyst for the polymerization of olefins.

It is a fifth object of the present invention to provide a catalyst for olefin polymerization.

It is a sixth object of the present invention to provide the use of the catalyst for olefin polymerization as described above in olefin polymerization reactions.

It is a seventh object of the present invention to provide an olefin polymerization process.

In one aspect, the invention provides an olefin polymerization catalyst carrier, which is a magnesium-containing compound shown as a formula (I),

wherein, in the formula (I), R1 is C1-C14 straight chain or branched chain alkyl; r2 and R3 are the same or different and are each independently hydrogen, C1-C5 linear or branched alkyl or C1-C5 linear or branched haloalkyl, wherein R2 and R3 are not hydrogen at the same time; x is halogen; y is halogen; m is 0.01-1.99, n is 0.01-1.99, q is 0.01-1.99, m + n + q is 2.

In a second aspect, the present invention provides a process for preparing an olefin polymerization catalyst support, the process comprising the steps of:

(1) mixing and heating magnesium halide, a compound with a general formula of ROH and an optional inert liquid medium to obtain a liquid mixture;

(2) stirring and emulsifying the liquid mixture obtained in the step (1), and contacting and reacting an emulsified product with ethylene oxide and a compound shown in a formula (II);

in the general formula ROH, R is C1-C14 alkyl; in the compound represented by the formula (II):

wherein R is₅And R₆Each independently hydrogen, C1-C5 linear or branched alkyl or C1-C5 linear or branched haloalkyl, wherein R₅And R₆Not hydrogen at the same time.

In a third aspect, the present invention provides a catalyst component for olefin polymerization, which comprises the catalyst carrier as described above or the catalyst carrier prepared by the method as described above, a titanium compound and an internal electron donor.

In a fourth aspect, the present invention provides a catalyst support as described above, a catalyst support prepared by a process as described above and the use of a catalyst component for the polymerisation of olefins as described above in the preparation of a catalyst for the polymerisation of olefins.

In a fifth aspect, the present invention provides a catalyst for olefin polymerization, the catalyst comprising:

(1) a catalyst component for the polymerization of olefins as described above;

(2) an alkyl aluminum compound; and

(3) optionally an external electron donor compound.

In a sixth aspect, the present invention provides the use of a catalyst for the polymerisation of olefins as described above in a polymerisation reaction of olefins.

In a seventh aspect, the present invention provides an olefin polymerization process comprising: under olefin polymerization conditions, one or more olefins are contacted with a catalyst for olefin polymerization as described above.

By adopting the technical scheme of the invention, in the preparation process of the olefin polymerization catalyst carrier, the ethylene oxide compound and other epoxy compounds are mixed and then react with the magnesium halide alcoholate, so that the carrier with a novel composition can be obtained, and the obtained carrier has good particle shape and basically does not have special-shaped particles. And the catalyst prepared by the carrier has higher activity when being applied to alpha-olefin polymerization, and the bulk density and isotacticity of the polymer obtained by polymerization can be improved.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is an optical microscope photograph showing the morphology of an olefin polymerization catalyst support prepared in preparation example 1;

FIG. 2 is an optical microscope photograph showing the morphology of the olefin polymerization catalyst support prepared in preparation example 2;

FIG. 3 is an optical microscope photograph showing the morphology of the olefin polymerization catalyst support prepared in comparative preparation example 1.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided an olefin polymerization catalyst support comprising a magnesium-containing compound represented by formula (I),

wherein, in the formula (I), R₁Is a straight chain of C1-C14Or a branched alkyl group; preferably C1-C8, for example, C1, C2, C3, C4, C5, C6, C7, C8; more preferably, R₁One or more selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl.

R₂And R₃The same or different, are each independently hydrogen, C1-C5 linear or branched alkyl or C1-C5 linear or branched haloalkyl, wherein R₂And R₃Not hydrogen at the same time; preferably, R₂And R₃Identical or different, are each independently hydrogen, linear or branched alkyl of C1 to C3 or linear or branched haloalkyl of C1 to C3, e.g. R₂，R₃And R₄Each independently is hydrogen, C1, C2, C3 linear or branched alkyl or C1, C2, C3 linear or branched haloalkyl, wherein R is₂And R₃Not hydrogen at the same time; among them, the haloalkyl group is preferably a chloroalkyl group and/or a bromoalkyl group; preferably, R₂And R₃Identical or different, each independently selected from the group consisting of hydrogen, methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl, R₂And R₃Not hydrogen at the same time.

X is halogen, preferably chlorine or bromine; y is halogen, preferably chlorine or bromine.

Wherein m is 0.01-1.99, n is 0.01-1.99, q is 0.01-1.99, and m + n + q is 2.

According to a preferred embodiment of the present invention, the olefin polymerization catalyst support may have an average particle diameter of 10 to 100 microns, preferably 20 to 90 microns, and a particle size distribution of less than 1.2, preferably 0.7 to 0.9. In the preferred embodiment, the catalyst prepared from the olefin polymerization catalyst support can give an olefin polymer having a higher bulk density. In the present invention, the average particle diameter and the particle size distribution of the olefin polymerization catalyst support can be measured using a Master Sizer2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).

According to the invention, traces of water originating from the synthesis starting materials and from traces of water carried by the reaction medium may also be carried by the olefin polymerization catalyst support.

According to the invention, the raw materials for synthesizing the catalyst carrier comprise magnesium halide, a compound with a general formula of ROH, ethylene oxide and a compound shown as a formula (II);

wherein, in the general formula ROH, R is C1-C14 alkyl; in the compound represented by the formula (II):

According to the present invention, the content of each of the above components used for preparing the olefin polymerization catalyst support may be selected and varied within a wide range, and for example, the content of the compound of the formula ROH may be 4 to 30mol, the content of ethylene oxide may be 0.001 to 2mol, and the content of the compound of the formula (II) may be 1 to 10mol based on 1mol of the magnesium halide; preferably, the ethylene oxide is present in an amount of 0.01 to 1.5 mol, the compound of the formula ROH is present in an amount of 6 to 20mol, and the compound of the formula (II) is present in an amount of 2 to 6mol, based on 1mol of the magnesium halide.

According to the invention, the magnesium halide may be one magnesium halide or a mixture of magnesium halides. Specific examples of magnesium halides may be, but are not limited to: one or more of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride. Magnesium chloride is preferred from the viewpoint of availability of raw materials.

According to the invention, in the general formula ROH, R is preferably a C1-C8 alkyl group. The alkyl group of C1 to C8 may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl. Specific examples of compounds of formula ROH may be, but are not limited to: one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.

According to the invention, in the compound with the structure shown as the formula (II), R₅And R₆Preferably each independently hydrogen, C1-C3 linear or branched alkyl or C1-C3 linear or branched haloalkyl, wherein R₅And R₆Not hydrogen at the same time. Specific examples of the compound represented by the formula (ii) may be, but are not limited to: one or more of propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.

According to a second aspect of the present invention, there is provided a process for preparing an olefin polymerization catalyst support, the process comprising the steps of:

(2) emulsifying the liquid mixture obtained in the step (1), and carrying out contact reaction on the emulsified product, ethylene oxide and a compound shown in a formula (II);

Wherein, the types of the magnesium halide, the compound with the general formula of ROH and the compound shown in the formula (II) are described above and will not be described again.

According to the present invention, the amount of the magnesium halide, the compound of formula ROH, the ethylene oxide, and the compound of formula (II) may be appropriately selected according to the composition of the desired olefin polymerization catalyst carrier, and preferably, based on 1mol of the magnesium halide, the amount of the compound of formula ROH is 4 to 30mol, the amount of the ethylene oxide is 0.001 to 2mol, and the amount of the compound of formula (II) is 1 to 10 mol; more preferably, ethylene oxide is used in an amount of 0.01 to 1.5 mol, the compound of the formula ROH is used in an amount of 6 to 20mol, and the compound of the formula (I) is used in an amount of 2 to 6mol, based on 1mol of the magnesium halide.

According to the invention, traces of water in the above-mentioned reactants may also participate in the reaction for forming the support for the olefin polymerization catalyst.

According to the present invention, in step (1), the conditions for heating the mixture of magnesium halide, compound of formula ROH and optionally inert liquid medium are not particularly limited, as long as the heating conditions are such that the magnesium halide melts and reacts with the compound of formula ROH. Generally, the heating temperature is not lower than 60 ℃, and preferably, the heating conditions include: the temperature can be 80-120 ℃, and the time can be 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the time is 0.5-3 hours.

In the present invention, the "and optional inert liquid medium" means that the inert liquid medium may or may not be present, that is, an inert liquid medium may or may not be required in the step of the present invention.

In the case where an inert medium is included in step (1), the amount of the inert liquid medium may be selected according to the amount of the magnesium halide. In general, the inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on 1mol of magnesium halide. The inert liquid medium may be any of the various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products. For example: the inert liquid medium may be a silicone oil and/or an inert liquid hydrocarbon solvent. Specifically, the inert liquid medium may be one or more of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil. The inert liquid medium according to the invention is particularly preferably white oil.

According to the present invention, in the step (2), the liquid mixture obtained in the step (1) may be emulsified by various methods known to those skilled in the art. For example, the liquid mixture may be emulsified by subjecting it to low or high shear. The low shear agitation rate is typically 400-800 rpm. Such high shear methods are well known to those skilled in the art, such as the high speed stirring method disclosed in CN1151183C (i.e., the solution containing the liquid magnesium halide adduct is stirred at a speed of 2000-5000 rpm). In addition, the liquid mixture may be emulsified by the methods disclosed in the following patents: CN1267508C discloses that the solution containing the liquid magnesium halide adduct is dispersed by rotation in a supergravity bed (the speed of rotation can be 100-3000 rpm); CN1463990A discloses that the solution containing the liquid magnesium halide adduct is output in an emulsifying machine at a speed of 1500-8000 rpm; US6020279 discloses emulsifying a solution containing a liquid magnesium halide adduct by spraying.

According to the present invention, the conditions for the contact reaction of the emulsified product with ethylene oxide and the compound represented by the formula (II) in the step (2) may be various existing conditions capable of forming a carrier for an olefin polymerization catalyst, for example, the conditions for the contact reaction may include a temperature of 50 to 120 ℃ and a time of 20 to 60 minutes; preferably, the temperature is 60-100 ℃ and the time is 20-50 minutes.

According to the present invention, the method may further comprise subjecting the product obtained by the contact reaction to solid-liquid separation, washing the solid-phase product and drying. The solid-liquid separation may be any of various conventional methods for separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation is a pressure filtration method. In the present invention, the conditions for the pressure filtration are not particularly limited, and it is considered that the separation of the solid phase and the liquid phase is sufficiently achieved as much as possible. The washing may be carried out by washing the obtained solid phase product by a method known to those skilled in the art, and for example, the obtained solid phase product may be washed by an inert hydrocarbon solvent (e.g., pentane, hexane, heptane, petroleum ether and gasoline). In the present invention, the drying conditions are not particularly limited, and examples thereof include: the drying temperature can be 20-70 ℃, and the drying time can be 0.5-10 hours. According to the invention, the drying can be carried out under atmospheric or reduced pressure.

In addition, the invention also provides a catalyst carrier for olefin polymerization prepared by the method.

In a third aspect, the present invention also provides a catalyst component for olefin polymerization, which comprises a product obtained by reacting the catalyst carrier as described above and/or the catalyst carrier for olefin polymerization prepared by the method as described above with a titanium compound and an internal electron donor.

According to the catalyst component of the present invention, the conditions for the reaction of the olefin polymerization catalyst support, the titanium compound and the internal electron donor compound are not particularly limited, and preferably, the reaction conditions may include: the reaction temperature is 80-130 ℃ and the reaction time is 0.5-10 hours.

More specifically, the reaction conditions include: the prepared catalyst carrier is contacted with a titanium compound (-30 ℃ to 0 ℃) for 20-60min at the temperature of-30 ℃ to 0 ℃, then the contacted compound is heated to 80-130 ℃, internal electron donor is added in the heating process, and the reaction is carried out for 0.5-10 h to obtain the catalyst component of the invention, and more preferably, the method also comprises the steps of washing the obtained product by using the titanium compound and washing by using an inert solvent after the reaction is finished. Among them, the inert solvent may be an inert solvent conventionally used in the art, for example, toluene, hexane, etc.

According to the catalyst component of the present invention, the internal electron donor compound may be various internal electron donor compounds conventionally used in the process of preparing a catalyst for olefin polymerization, and for example, may be one or more of carboxylic acid ester, alcohol ester, ether, ketone, nitrile, amine and silane, and preferably one or more of mono-or poly-aliphatic carboxylic acid ester, mono-or poly-aromatic carboxylic acid ester, glycol ester and diether.

Preferably, the internal electron donor of the present invention is one or more of diisobutyl phthalate, di-n-butyl phthalate, 1, 3-diamyl phthalate, ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, and particularly preferably one or more of di-n-butyl phthalate, diisobutyl phthalate, diethyl ether, propyl ether, butyl ether, pentyl ether, hexyl ether, Tetrahydrofuran (THF), acetone, butanone, 2-pentanone, methyl isobutyl ketone.

According to the catalyst component of the present invention, in the catalyst component for olefin polymerization, the weight ratio of the titanium compound calculated as titanium element, the carrier calculated as magnesium element and the internal electron donor compound may be 1:5-15:2-15, preferably 1:6-13: 3-12.

According to the catalyst component of the present invention, the titanium compound may be various titanium compounds conventionally used in the process of preparing a catalyst for olefin polymerization. Typically, the titanium compound is of the formula Ti (OR)_a)_4-rM_rWherein R is_aIs aliphatic hydrocarbon group of C1-C14, M is F, Cl or Br, r is an integer of 1-4; the titanium compound is preferably one or more of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxychloride, titanium triethoxide chloride, titanium diethoxide dichloride and titanium ethoxychloride.

The catalyst component according to the present invention can be obtained by reacting the catalyst support as described above with a titanium compound and an internal electron donor in the above amount ratio under the above reaction conditions.

In a fourth aspect, the present invention also provides a catalyst support as described above, a catalyst support prepared by a process as described above and the use of a catalyst component for the polymerisation of olefins as described above in the preparation of a catalyst for the polymerisation of olefins.

Among them, the olefin is preferably propylene.

(1) a catalyst component for the polymerization of olefins as described above;

(2) an alkyl aluminum compound; and

(3) optionally an external electron donor compound.

The composition of the catalyst component for olefin polymerization has been described in detail in the foregoing, and will not be described in detail.

The catalyst for olefin polymerization according to the present invention uses the catalyst component for olefin polymerization according to the present invention, and therefore when the catalyst for olefin polymerization according to the present invention is used as a catalyst for olefin polymerization, the bulk density and isotacticity of the polymer obtained by polymerization are also improved.

According to the invention, the aluminum alkyl may be conventionally selected in the art, for example, the aluminum alkyl may have the general formula AlR₁₆R₁₆′R₁₆", wherein R₁₆、R₁₆′、R₁₆"are each independently C1-C8 alkyl, and one or two of the groups may be halogen; specific examples of the C1-C8 alkyl group may include, but are not limited to: methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl and the halogen may be fluorine, chlorine, bromine, iodine. Specifically, the alkylaluminum may be selected from, for example, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, monoisobutylaluminum dichloride, mono-n-butylaluminum dichloride, mono-n-hexylaluminum dichloride, Al (n-C)₆H₁₃)₃、Al(n-C₈H₁₇)₃、AlEt₂One or more of Cl, preferably triethylaluminum and/or triisobutylaluminum.

According to the present invention, the external electron donor may be various external electron donors commonly used in the art, for example, the external electron donor may beOne or more of carboxylic acids, anhydrides, esters, ketones, ethers, alcohols, organophosphorus compounds and organosilicon compounds; preferably, the external electron donor is a compound containing at least one Si-OR bond and having the general formula (R)₁₇)_a(R₁₈)_bSi(OR₁₉)_cWherein R is₁₇、R₁₈And R₁₉Is a C1-C18 hydrocarbyl group, optionally containing heteroatoms, a and b are each independently an integer from 0-2, C is an integer from 1-3, and the sum of a, b, and C is 4. Preferably, R₁₇、R₁₈Is C3-C10 alkyl, cycloalkyl, optionally containing heteroatoms; r₁₉Is C1-C10 alkyl, optionally containing heteroatoms. Specifically, the external electron donor may be, for example, one or more selected from the group consisting of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, t-hexyltrimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyl-dimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.

Further, in general, in the catalyst for olefin polymerization, the molar ratio of the catalyst component for olefin polymerization in terms of titanium element to the amount of aluminum alkyl in terms of aluminum element may be 1: (1-2000), preferably 1: (20-500); the molar ratio of the external electron donor to the aluminum alkyl may be 0.005-0.5:1, preferably 0.01-0.4:1, calculated as aluminum element.

According to the present invention, in the preparation process of the catalyst for olefin polymerization, the alkylaluminum and the optional external electron donor compound may be respectively mixed with the catalyst component for olefin polymerization and then reacted, or the alkylaluminum and the optional external electron donor compound may be mixed in advance and then mixed with the catalyst component for olefin polymerization and reacted.

In a sixth aspect, the present invention also provides the use of a catalyst for olefin polymerization as described above in an olefin polymerization reaction.

According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor may be added into the polymerization reactor separately, or may be added into the polymerization reactor after mixing, or may be added into the polymerization reactor after olefin prepolymerization by a prepolymerization method known in the art.

The improvement of the present invention is that the catalyst component prepared by the specific method of the present invention is adopted, and the specific kinds of olefin, the polymerization reaction method and conditions of olefin can be the same as those of the prior art.

According to the invention, the above-mentioned catalysts are particularly suitable for use with catalysts of the formula CH₂Homo-and copolymerization of olefins of ═ CHR (where R is hydrogen, C1-C6 alkyl or C6-C12 aryl), specifically for example one or more of ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene and styrene, preferably one or more of ethylene, propylene, 1-butene, 2-butene and styrene

According to the present invention, the polymerization of the olefin can be carried out according to the existing methods, specifically, under the protection of inert gas, in a liquid phase monomer or an inert solvent containing a polymeric monomer, or in a gas phase, or by a combined polymerization process in a gas-liquid phase. The polymerization temperature may be generally 0 to 150 ℃ and preferably 60 to 90 ℃. The pressure of the polymerization reaction may be normal pressure or higher; for example, it may be in the range of 0.01 to 10MPa, preferably 0.5 to 5 MPa. The polymerization time is from 0.1 to 5 hours, preferably from 0.5 to 3 hours. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen may be added to the reaction system as a polymer molecular weight regulator to regulate the molecular weight and melt index of the polymer. In addition, the kinds and amounts of the inert gas and the solvent are well known to those skilled in the art during the polymerization of olefins, and will not be described herein.

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

In the examples and comparative examples:

1. the average particle diameter and the particle size distribution of the olefin polymerization catalyst support were measured using a Masters Sizer2000 particle Sizer (manufactured by Malvern Instruments Ltd.);

2. the apparent morphology of the olefin polymerization catalyst support was observed by means of an optical microscope, commercially available from Nikon, under the model Eclipse E200;

3. the bulk density of the polyolefin powder is determined by a method specified in GB/T1636-2008;

4. the method for testing the isotacticity of the polymer comprises the following steps: after a 2 gram sample of the dried polymer was extracted in an extractor with boiling heptane for 6 hours, the residue was dried to constant weight and the isotacticity was calculated by the following formula: isotacticity (%) — mass of polymer after extraction/2 × 100;

5. catalyst activity is the weight of polymer obtained using the catalyst/weight of catalyst.

Preparation example 1

This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.

In a 0.6L reaction vessel, 8.0g (0.08mol) of magnesium chloride and 56mL (0.96mol) of ethanol were added, and the temperature was raised to 90 ℃ with stirring. The reaction was maintained at constant temperature for 2 hours. The mixture was dispersed for 30 minutes with low-speed stirring (stirring rate of 400 rpm) to effect emulsification. And adding 0.48mol of ethylene oxide and 0.01: 1mol of epichlorohydrin into the emulsified product, reacting for half an hour, then carrying out pressure filtration, washing the pressure filtration product with hexane for 5 times, and carrying out vacuum drying to obtain the catalyst carrier Z1 for olefin polymerization.

The obtained catalyst carrier Z1 has the following structural formula by nuclear magnetic resonance and element analysis characterization:

the olefin polymerization catalyst carrier Z1 had an average particle diameter (D50) of 24 μm and a particle size distribution ((D90-D10)/D50) of 0.9. The particle morphology observed with an optical microscope is shown in FIG. 1. As can be seen from the figure, the olefin polymerization catalyst carrier Z1 has a relatively regular particle morphology, a smooth surface, a substantially spherical shape, a relatively concentrated particle size distribution, and substantially no irregular particles.

Preparation example 2

Into a 0.6L reactor, 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, and 28mL (0.48mol) of ethanol were added, and the mixture was heated to 100 ℃ with stirring and reacted at a constant temperature for 1 hour. The mixture was dispersed for 30 minutes with low-speed stirring (stirring rate of 600 rpm) to effect emulsification. And adding 0.45mol of ethylene oxide and 0.05: 1mol of epichlorohydrin into the emulsified product, reacting for 20 minutes, then carrying out pressure filtration, washing the pressure-filtered product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst carrier Z2.

The obtained catalyst carrier Z2 has the following structural formula by nuclear magnetic resonance and element analysis characterization:

the olefin polymerization catalyst carrier Z2 had an average particle diameter (D50) of 30 μm and a particle size distribution ((D90-D10)/D50) of 0.7. The particle morphology observed with an optical microscope is shown in fig. 2. As can be seen from the figure, the olefin polymerization catalyst carrier Z2 has a relatively regular particle morphology, a smooth surface, a substantially spherical shape, a relatively concentrated particle size distribution, and substantially no irregular particles.

Preparation example 3

500mL of white oil, 8.0g (0.08mol) of magnesium chloride, and 95mL (1.63mol) of ethanol were put into a 0.6L reactor, and the temperature was raised to 80 ℃ with stirring to conduct a reaction at a constant temperature for 3 hours. The mixture was dispersed for 30 minutes with low-speed stirring (stirring rate of 800 rpm) to effect emulsification. And adding 0.32mol (the mass ratio of substances is 0.1:1) of ethylene oxide and epichlorohydrin into the emulsified product, reacting for 40 minutes, then carrying out pressure filtration, washing the pressure-filtered product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst carrier Z3.

The structure of the olefin polymerization catalyst carrier Z3 is consistent with the structure of the formula (I) by the nuclear magnetic resonance and the elemental analysis.

The olefin polymerization catalyst carrier Z2 had an average particle diameter (D50) of 47 microns and a particle size distribution ((D90-D10)/D50) of 0.7. The olefin polymerization catalyst carrier Z2 has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.

Comparative preparation example 1

This comparative preparation example is intended to illustrate a reference olefin polymerization catalyst support and a method for preparing the same.

An olefin polymerization catalyst carrier was prepared by following the procedure of example 1, except that epichlorohydrin alone, and not ethylene oxide, was added to the emulsified product, to obtain a catalyst carrier for olefin polymerization DZ 1.

The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ1 was 100. mu.m, and the particle size distribution ((D90-D10)/D50) was 1.6. The particle morphology observed with an optical microscope is shown in fig. 3. As can be seen from the figure, the catalyst carrier for olefin polymerization DZ1 had a large number of irregularly shaped particles and had a rough surface.

Comparative preparation example 2

An olefin polymerization catalyst carrier was prepared by following the procedure of example 1, except that only ethylene oxide was added to the emulsified product, and epichlorohydrin was not added, to obtain a catalyst carrier for olefin polymerization DZ 2.

The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ2 was 110. mu.m, and the particle size distribution ((D90-D10)/D50) was 1.7. The catalyst carrier DZ2 for olefin polymerization had a large number of irregular particles and a rough surface as observed by an optical microscope.

Comparative preparation example 3

An olefin polymerization catalyst carrier was prepared by following the procedure of example 1, except that ethanol was replaced with the same parts by weight of octadecanol. Thus, an olefin polymerization catalyst carrier DZ3 was obtained.

The olefin polymerization catalyst carrier DZ3 had an average particle diameter (D50) of 90 μm and a particle size distribution ((D90-D10)/D50) of 1.5. The olefin polymerization catalyst carrier DZ3 has a large number of irregular particles and a rough surface by optical microscope observation.

Example 1

This example serves to illustrate the preparation of the olefins provided by the present invention.

(1) Preparation of olefin polymerization catalyst

In a 300mL glass reaction vessel, 100mL of titanium tetrachloride was added, cooled to-20 ℃, and 40 g of the olefin polymerization catalyst support Z1 obtained in preparation example 1 was added thereto and stirred at-20 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 1.5mL of diisobutyl phthalate was added during the temperature raising, and the temperature was maintained at 110 ℃ for 30min, after which the liquid was filtered off. Then, titanium tetrachloride was added and the mixture was washed 2 times, finally, 3 times with hexane and dried to obtain an olefin polymerization catalyst C1.

(3) Propylene polymerization

In a 5L stainless steel autoclave, purging was conducted with a nitrogen stream, and then 1mmol of a hexane solution of triethylaluminum (concentration of triethylaluminum is 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, and 10mg of the olefin polymerization catalyst C1 obtained in step (1), 1.5L (standard volume) of hydrogen, and 2.5L of liquid propylene were introduced into the nitrogen stream. Heating to 70 ℃, reacting for 1 hour at the temperature, cooling, releasing pressure, discharging and drying to obtain the polypropylene powder.

The activity of the catalyst is 43.8KgPP/g Cat, and the bulk density of the obtained polypropylene powder is 0.44g/cm³The isotacticity is 98.4%, and in addition, the polypropylene powder has good particle shape and basically has no profile.

Example 2

Propylene was polymerized by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier Z2 obtained in preparation example 2, to obtain a polypropylene powder.

The activity of the catalyst is 44.2 KgPP/g.Cat, and the bulk density of the obtained polypropylene powder is 0.45g/cm³The isotacticity is 98.5%, and in addition, the polypropylene powder has good particle shape and basically has no profile.

Example 3

Propylene was polymerized by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier Z3 obtained in preparation example 3, to obtain a polypropylene powder.

The activity of the catalyst is 44.1 KgPP/g.Cat, and the bulk density of the obtained polypropylene powder is 0.46g/cm³The isotacticity was 98.7%, and in addition, the polypropylene powder had a good particle morphology and was substantially free of profile.

Comparative example 1

This comparative example serves to illustrate the reference preparation of olefins.

Propylene was polymerized by following the procedure of example 1 except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier DZ1 obtained in comparative preparation example 1 to obtain a polypropylene powder.

The activity of the catalyst is 32.2 KgPP/g.Cat, and the bulk density of the obtained polypropylene powder is 0.38g/cm³The isotacticity was 97.8%, in additionThe polypropylene powder particles are all special-shaped materials and have poor flowability.

Comparative example 2

Propylene was polymerized by following the procedure of example 1 except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier DZ2 obtained in comparative preparation example 2 to obtain a polypropylene powder.

The activity of the catalyst is 32.0 KgPP/g.Cat, and the bulk density of the obtained polypropylene powder is 0.36g/cm³The isotacticity was 97.2%, and in addition, the polypropylene powder particles were all irregular and had poor flowability.

Comparative example 3

Propylene was polymerized by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with the olefin polymerization catalyst carrier DZ3 obtained in comparative preparation example 3, to obtain a polypropylene powder.

The activity of the catalyst is 30.5 KgPP/g.Cat, and the bulk density of the obtained polypropylene powder is 0.35g/cm³The isotacticity was 97.3%, and in addition, the polypropylene powder particles were all irregular and had poor flowability.

From the above results, it can be seen that the olefin polymerization catalyst carrier prepared by the method of the present invention has good particle morphology, smooth surface and substantially no occurrence of irregular particles, and when the catalyst prepared by the obtained carrier is used for olefin (especially propylene) polymerization, the activity of the catalyst is high, and the bulk density and isotacticity of the polymerization product can be improved, and the occurrence of foreign materials is substantially avoided. In addition, as can be seen from the comparison between example 1 and comparative example 1, the olefin polymerization catalyst carrier with the novel composition has better morphology, higher bulk density of the polymer, higher activity when the catalyst is applied to alpha-olefin polymerization reaction, higher bulk density and isotacticity of the obtained polymerized olefin, and great industrial application prospect.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. An olefin polymerization catalyst carrier, which is a magnesium-containing compound shown as a formula (I),

wherein, in the formula (I), R₁Is a linear or branched alkyl group of C1-C14; r₂And R₃The same or different, are each independently hydrogen, C1-C5 linear or branched alkyl or C1-C5 linear or branched haloalkyl, wherein R₂And R₃Not hydrogen at the same time; x is halogen; y is halogen; m is 0.01-1.99, n is 0.01-1.99, q is 0.01-1.99, m + n + q is 2;

wherein, the synthetic raw materials of the catalyst carrier comprise magnesium halide, a compound with a general formula of ROH, ethylene oxide and a compound shown as a formula (II);

wherein, in the general formula ROH, R is C1-C14 straight chain or branched chain alkyl; in the compound represented by the formula (II):

wherein R is₅And R₆Each independently hydrogen, C1-C5 linear or branched alkyl or C1-C5 linear or branched haloalkyl, wherein R₅And R₆Not hydrogen at the same time;

wherein, based on 1mol of magnesium halide, the content of the compound with the general formula of ROH is 4-30mol, the content of ethylene oxide is 0.001-2 mol, and the content of the compound shown in the formula (II) is 1-10 mol.

2. The catalyst carrier according to claim 1, wherein R₁Is a linear or branched alkyl group of C1-C8;

R₂and R₃The same or different, are each independently hydrogen, C1-C3 linear or branched alkyl or C1-C3 linear or branched haloalkyl, wherein R₂And R₃Not hydrogen at the same time;

x is chlorine or bromine and Y is chlorine or bromine.

3. The catalyst carrier according to claim 2, wherein R₁One or more selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl.

4. The catalyst carrier according to claim 2, wherein R₂And R₃Identical or different, each independently selected from the group consisting of hydrogen, methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl, wherein R₂And R₃Not hydrogen at the same time.

5. The catalyst carrier according to any one of claims 1 to 4, wherein the catalyst carrier has an average particle diameter of 10 to 100 microns and a particle size distribution of less than 1.2.

6. The catalyst carrier according to claim 5, wherein the catalyst carrier has an average particle diameter of 30 to 70 μm and a particle size distribution of 0.7 to 0.9.

7. The catalyst carrier according to claim 1, wherein the content of ethylene oxide is 0.01 to 1.5 mol, the content of the compound of the formula ROH is 6 to 20mol, and the content of the compound of the formula (II) is 2 to 8mol based on 1mol of the magnesium halide.

8. The catalyst support according to claim 1 or 7, wherein the magnesium halide is selected from one or more of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.

9. The catalyst support according to claim 1 or 7, wherein in the general formula ROH, R is a linear or branched alkyl group of C1-C8.

10. The catalyst support according to claim 9, wherein the compound of formula ROH is selected from one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.

11. The catalyst carrier according to claim 1 or 7, wherein in the compound of formula (II), R is₅And R₆Each independently hydrogen, C1-C3 linear or branched alkyl or C1-C3 linear or branched haloalkyl, wherein R₅And R₆Not hydrogen at the same time.

12. The catalyst support according to claim 11, wherein the compound of formula (II) is selected from one or more of propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.

13. A method for preparing an olefin polymerization catalyst support, the method comprising the steps of:

14. The process according to claim 13, wherein the compound of the formula ROH is used in an amount of 4 to 30mol, the ethylene oxide is contained in an amount of 0.001 to 2mol, and the compound of the formula (II) is used in an amount of 1 to 10mol, based on 1mol of the magnesium halide.

15. The process according to claim 14, wherein the ethylene oxide is present in an amount of 0.01 to 1.5 mol, the compound of the formula ROH is present in an amount of 6 to 20mol, and the compound of the formula (II) is present in an amount of 2 to 8mol, based on 1mol of the magnesium halide.

16. The method according to any one of claims 13 to 15, wherein the heating in step (1) is carried out at a temperature of 80 to 120 ℃ for a time of 0.5 to 5 hours.

17. The method of claim 16, wherein the heating is at a temperature of 80-100 ℃ for a time of 0.5-3 hours.

18. The method according to any one of claims 13 to 15, wherein in step (2), the contact reaction conditions comprise a temperature of 50 to 120 ℃ and a time of 20 to 60 minutes.

19. The method of claim 18, wherein the conditions of the contact reaction include a temperature of 60-100 ℃ and a time of 20-50 minutes.

20. The process according to any one of claims 13 to 15, wherein the inert liquid medium is used in an amount of 0.8 to 10L, based on 1mol of magnesium halide; the inert liquid medium is silicone oil and/or an inert liquid hydrocarbon solvent.

21. The method of claim 20, wherein the inert liquid medium is one or more of kerosene, petrolatum, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil.

22. A catalyst component for olefin polymerization, comprising a product obtained by reacting the catalyst support of any one of claims 1 to 13 and/or the catalyst support prepared by the method of any one of claims 13 to 21 with a titanium compound and an internal electron donor.

23. The catalyst component according to claim 22 in which the weight ratio of the titanium compound, calculated as titanium element, the support and the internal electron donor compound, calculated as magnesium element, is 1:5-15: 2-15.

24. The catalyst component according to claim 23 in which the weight ratio of the titanium compound, calculated as titanium element, the support and the internal electron donor compound, calculated as magnesium element, is 1:6-13: 3-12.

25. Use of a catalyst support according to any one of claims 1 to 12, a catalyst support prepared by a process according to any one of claims 13 to 21 and a catalyst component for the polymerization of olefins according to any one of claims 22 to 24 in the preparation of a catalyst for the polymerization of olefins.

26. A catalyst for the polymerization of olefins, the catalyst comprising:

(1) a catalyst component for the polymerization of olefins according to anyone of claims 22 to 24;

(2) an alkyl aluminum compound; and

(3) optionally an external electron donor compound.

27. Use of the catalyst for olefin polymerization according to claim 26 in olefin polymerization reactions.

28. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst for olefin polymerization of claim 26 under olefin polymerization conditions.