CN107915792B - Olefin polymerization catalyst carrier and preparation method thereof, olefin polymerization catalyst component and olefin polymerization catalyst and application thereof - Google Patents

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

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CN107915792B
CN107915792B CN201610880733.8A CN201610880733A CN107915792B CN 107915792 B CN107915792 B CN 107915792B CN 201610880733 A CN201610880733 A CN 201610880733A CN 107915792 B CN107915792 B CN 107915792B
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olefin polymerization
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夏先知
凌永泰
刘月祥
李威莅
高富堂
赵瑾
谭扬
彭人琪
任春红
陈龙
张天一
张志会
万真
马长友
段瑞林
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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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.

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 alcoholate supported Ziegler-Natta catalysts perform significantly better than other supported catalysts when used in olefin (especially propylene) polymerization. Therefore, the catalysts currently used for olefin polymerization are mostly prepared by supporting titanium halide on magnesium chloride alcoholate. To obtain spherical carriers, they can be prepared by spray drying, spray cooling, high pressure extrusion, high speed stirring, emulsifying machine method and supergravity rotating bed method, etc., as disclosed in WO99/44009 and US4399054, etc., where the spherical alcoholate can be formed by emulsifying the magnesium chloride alcoholate system by high speed stirring at high temperature followed by quenching.
However, when the catalyst prepared from the above-disclosed magnesium chloride alcoholate is used for olefin polymerization, the breakage of polymer particles is easily caused during the polymerization, resulting in a large amount of fine polymer powder. In order to overcome this drawback, attempts have been made to introduce the electron donor compound into the preparation of the magnesium chloride alcoholate support in advance, for example: CN1169840C and CN1286863C introduce internal electron donor phthalate compounds known in the industry into the synthesis of magnesium chloride alcoholate carriers, so as to obtain "magnesium chloride-alcohol-phthalate" spherical carriers, and then the carriers are reacted with titanium tetrachloride to form catalysts. However, the complex spherical carrier is easily sticky during the preparation process, and is difficult to form spherical particles with proper particle size.
In addition, the magnesium chloride alcoholate is prepared by adopting low-temperature quenching and solidifying high-temperature alcoholate melt, not only has large energy consumption, complex preparation process and combined preparation of a plurality of reactors, but also has wider particle size distribution of the prepared alcoholate. In order to solve the problem, CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an oxirane compound, and specifically discloses adding the oxirane compound after melting and dispersing the magnesium halide alcoholate; or the magnesium halide alcoholate is directly added into a reactor containing the ethylene oxide compound after being melted and dispersed. However, the catalyst carrier prepared by the method has the defects of unstable preparation process, easy formation of a large amount of special-shaped particles, carrier adhesion caused by the carrier and poor carrier forming effect, so that the catalyst prepared by the carrier has low activity, the bulk density of the polymer obtained by catalysis is low, and the content of the ethylene structural unit is low when the catalyst is used for copolymerization.
Disclosure of Invention
The present inventors have unexpectedly found that the use of a chromium halide-containing compound in the preparation of the olefin polymerization catalyst support enables to obtain a support having a novel composition and having a good morphology of the support particles and substantially no presence of irregular particles. The catalyst prepared by the carrier has higher activity when being applied to olefin polymerization or copolymerization, and can also improve the content of ethylene structural units in the polymer when being applied to copolymerization.
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),
Figure BDA0001127027990000031
wherein, in the formula (I), R1Is a linear or branched alkyl group of C1-C14; r2，R3And R4The alkyl groups are the same or different and are each independently hydrogen, linear or branched alkyl groups of C1-C5 or linear or branched haloalkyl groups of C1-C5; x is halogen; y is halogen; m is 0.1-1.9, n is 0.1-1.9, m + n is 2; 0<i<3，0≤j<3，0<k<3，i+j+k＝3，0<q≤0.5。
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 chromium halide, magnesium halide, a compound with a general formula of ROH and an optional inert liquid medium to obtain a liquid mixture;
(2) emulsifying the liquid mixture obtained in the step (1), and contacting and reacting the emulsified product with an ethylene oxide compound;
in the general formula ROH, R is C1-C14 alkyl; the structure of the ethylene oxide compound is shown as the formula (II):
Figure BDA0001127027990000032
wherein R is5And R6Each independently hydrogen, C1-C5 linear or branched alkyl, or C1-C5 linear or branched haloalkyl.
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 optionally 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, the compound containing chromium halide is used in the preparation process of the olefin polymerization catalyst carrier, a carrier with a novel composition can be obtained, the obtained carrier particle has good shape and basically does not have special-shaped particles, the activity of the catalyst prepared from the carrier is higher when the catalyst is applied to the copolymerization of α -olefin and ethylene, the bulk density of the polymer obtained by polymerization can also be improved, and the content of an ethylene structural unit in the obtained polymer is higher when the catalyst is applied to the copolymerization of olefin.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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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),
Figure BDA0001127027990000051
wherein, in the formula (I), R1Is a linear or branched alkyl group of C1-C14; 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.
R2，R3And R4Identical or different, are each independently hydrogen, linear or branched alkyl of C1 to C5 or linear or branched haloalkyl of C1 to C5, preferably R2，R3And R4Identical 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; among them, the haloalkyl group is preferably a chloroalkyl group and/or a bromoalkyl group; preferably, R2，R3And R4Identical or different, each independently of the others is hydrogen, methyl, ethyl,One or more of chloromethyl, chloroethyl, bromomethyl, and bromoethyl.
X is halogen, preferably chlorine or bromine; y is halogen, preferably chlorine or bromine;
wherein m is 0.1-1.9, n is 0.1-1.9, and m + n is 2; 0< i <3, 0< j <3, 0< k <3, i + j + k 3, 0< q < 0.5.
According to a preferred embodiment of the present invention, the olefin polymerization catalyst support may have an average particle diameter of 10 to 100. mu.m, preferably 40 to 60 μm, and a particle size distribution of less than 1.2, preferably 0.6 to 0.8. in this preferred embodiment, the catalyst prepared from the olefin polymerization catalyst support is capable of obtaining an olefin polymer having a higher bulk density.
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 chromium halide, magnesium halide, a compound with a general formula of ROH, and an ethylene oxide compound;
wherein, in the general formula ROH, R is C1-C14 alkyl; the structure of the ethylene oxide compound is shown as the formula (II):
Figure BDA0001127027990000061
wherein R is5And R6Each independently hydrogen, C1-C5 linear or branched alkyl, or C1-C5 linear or branched haloalkyl.
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, for example, the content of chromium halide may be 0.0001 to 1mol, the content of the compound of the general formula ROH may be 4 to 30mol, and the content of the oxirane compound of the formula (II) may be 1 to 10mol, based on 1mol of magnesium halide; preferably, the content of the chromium halide is 0.01 to 0.1mol, the content of the compound of the formula ROH is 6 to 20mol, and the content of the oxirane compound of the formula (II) is 2 to 6mol based on 1mol of the magnesium halide.
According to the invention, the chromium halide can be an anhydrous chromium halide or a chromium halide containing crystal water, preferably the chromium halide is anhydrous or crystal water-containing chromium chloride or anhydrous or crystal water-containing chromium bromide, more preferably anhydrous or crystal water-containing chromium chloride.
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 ethylene oxide 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. Specific examples of the oxirane compound may be, but are not limited to: one or more of ethylene oxide, 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:
(1) mixing and heating chromium halide, magnesium halide, a compound with a general formula of ROH and an optional inert liquid medium to obtain a liquid mixture;
(2) emulsifying the liquid mixture obtained in the step (1), and contacting and reacting the emulsified product with an ethylene oxide compound;
in the general formula ROH, R is C1-C14 alkyl; the structure of the ethylene oxide compound is shown as the formula (II):
Figure BDA0001127027990000081
wherein R is5And R6Each independently hydrogen, C1-C5 linear or branched alkyl, or C1-C5 linear or branched haloalkyl.
The types of chromium halide, magnesium halide, compound with formula ROH, and oxirane compound are described above and will not be described herein again.
According to the present invention, the amount of the chromium halide, the magnesium halide, the compound of formula ROH, and the oxirane 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 chromium halide is 0.0001 to 1mol, the amount of the compound of formula ROH is 4 to 30mol, and the amount of the oxirane compound of formula (II) is 1 to 10 mol; more preferably, the amount of chromium halide used is 0.01 to 0.1mol, the amount of the compound of the formula ROH used is 6 to 20mol, and the amount of the oxirane compound of the formula (I) used is 2 to 6mol, based on 1mol of 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 chromium halide, 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 chromium halide, compound of formula ROH. Generally, the conditions of heating 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.
According to the present invention, in the case where an inert liquid medium is included in step (1), the amount of the inert liquid medium may be selected according to the amount of magnesium halide, and generally, the amount of the inert liquid medium may be 0.8 to 10L, preferably 2 to 8L, based on 1mol of magnesium halide, and the inert liquid medium may be various liquid media commonly used in the art that do not chemically interact with the reactants and the reaction products.
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 the ethylene oxide in the step (2) may be any of the 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 support as described above and/or the catalyst support for olefin polymerization prepared by the method as described above with a titanium compound and optionally an internal electron donor.
The conditions for the reaction of the olefin polymerization catalyst support, the titanium compound and the optional internal electron donor compound according to the catalyst component of the present invention 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 case that the synthesis raw material of the catalyst component includes an internal electron donor, the weight ratio of the titanium element, the magnesium element and the internal electron donor compound in the catalyst component for olefin polymerization may be 1:5-15:2-15, and preferably 1:6-13: 3-12. In the case where an internal electron donor is not included, the weight ratio of the titanium element to the magnesium element in the catalyst component for olefin polymerization may be 1:5 to 15, preferably 1:6 to 13.
According to the catalyst component of the present invention, the titanium compound mayIn order to prepare various titanium compounds conventionally used in the process of preparing catalysts for olefin polymerization. Typically, the titanium compound is of the formula Ti (OR)a)4-rMrWherein R isaIs 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 optionally 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.
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.
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 the bulk density of the polymer obtained by polymerization is also improved when the catalyst for olefin polymerization according to the present invention is used as a catalyst for olefin polymerization.
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 be one or more of carboxylic acid, acid anhydride, ester, ketone, ether, alcohol, organic phosphorus compound, and organic silicon compound; 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 selected from, for example, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, t-hexyltrimethoxysilaneOne or more of a group consisting of a methyltrimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, a group consisting of (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane 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.
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.
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 CH2CHR (wherein R is hydrogen, C1-C6 alkyl group or C6-C12 aryl group), 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 L td);
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. 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 kettle, adding 8.0g (0.08mol) of magnesium chloride, 56m L (0.96mol) of ethanol and 4.3g (0.016mol) of chromium trichloride hexahydrate, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, dispersing the mixture at low speed (the stirring speed is 400 r/min) for 30 minutes to emulsify, adding 0.48mol (38ml) of epoxy chloropropane into the emulsified product, reacting for half an hour, press-filtering, washing the press-filtered product with hexane for 5 times, and drying in vacuum 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:
Figure BDA0001127027990000151
the olefin polymerization catalyst carrier Z1 had an average particle diameter (D50) of 48 μm and a particle size distribution ((D90-D10)/D50) of 0.7. 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
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
Adding 300m of L white oil, 8.0g (0.08mol) of magnesium chloride, 28m of L (0.48mol) of ethanol and 2.1g (0.008mol) of chromium trichloride hexahydrate into a reaction kettle of 1.6L, heating to 100 ℃ under stirring, reacting at constant temperature for 0.5 hour, stirring the mixture at low speed (the stirring speed is 800 revolutions per minute) for dispersing for 30 minutes to emulsify, adding 12.5m of L (0.16mol) of epoxy chloropropane into the emulsified product, reacting for 20 minutes, performing pressure filtration, washing the pressure-filtered product with hexane for 5 times, and finally performing 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:
Figure BDA0001127027990000152
the olefin polymerization catalyst carrier Z2 had an average particle diameter (D50) of 49 μm and a particle size distribution ((D90-D10)/D50) of 0.8. 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
This preparation example is intended to illustrate the olefin polymerization catalyst support and the preparation method thereof provided by the present invention.
Adding 500m of L white oil, 8.0g (0.08mol) of magnesium chloride, 95m of L (1.63mol) of ethanol and 1.1g (0.004mol) of chromium trichloride hexahydrate into a reaction kettle of 1.6L, heating to 80 ℃ under stirring, reacting at constant temperature for 3 hours, dispersing the mixture for 30 minutes under low-speed stirring (the stirring speed is 600 revolutions per minute) to emulsify, adding 25m of L (0.32mol) of epichlorohydrin into the emulsified product, reacting for 40 minutes, performing pressure filtration, washing the pressure-filtered product for 5 times by using hexane, and finally performing 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 46 μm and a particle size distribution ((D90-D10)/D50) of 0.75. The olefin polymerization catalyst carrier Z3 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 chromium chloride was not added, 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
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 ethanol was replaced with the same parts by weight of octadecanol. Thus, an olefin polymerization catalyst carrier DZ2 was obtained.
The olefin polymerization catalyst carrier DZ2 had an average particle diameter (D50) of 100 μm and a particle size distribution ((D90-D10)/D50) of 1.5. The olefin polymerization catalyst carrier DZ2 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
100m of L parts of titanium tetrachloride was charged into a 300m L glass reaction vessel, cooled to-20 ℃ and 40g of the olefin polymerization catalyst support Z1 obtained in preparation example 1 was added thereto and stirred at-20 ℃ for 30 minutes, after which time a slow temperature rise to 110 ℃ was started and 1.5m L parts of diisobutyl phthalate was added during the temperature rise and the temperature was maintained at 110 ℃ for 30 minutes, after which the liquid was filtered off, and then washed 2 times with titanium tetrachloride and finally 3 times with hexane and dried to obtain an olefin polymerization catalyst C1.
(3) Propylene polymerization
In a 5L stainless steel autoclave, nitrogen flow was used for purging, then 1mmol of triethylaluminum in hexane solution (concentration of triethylaluminum is 0.5mmol/m L), 0.05mmol of methylcyclohexyldimethoxysilane, 10m L of anhydrous hexane, 10mg of 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 flow, the temperature was raised to 70 ℃, and the reaction was carried out at the temperature for 1 hour, cooled, decompressed, discharged and dried to obtain polypropylene powder.
The activity of the catalyst is 43.9KgPP/g Cat, and the bulk density of the polypropylene powder is 0.45g/cm3In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 2
This example serves to illustrate the preparation of the olefins provided by the present invention.
Propylene was polymerized by the method of example 1, except that the reaction was carried out for 1 hour, the temperature was lowered, the pressure was released, then a mixed gas of ethylene and propylene (molar ratio C2/(C3+ C2) ═ 0.042) was introduced, the reaction was continued for 0.5 hour, the temperature was lowered, the pressure was released, and the polypropylene powder was obtained by discharge drying.
The activity of the catalyst is 57.8 KgPP/g.Cat, and the bulk density of the polypropylene powder is 0.46g/cm3In addition, the polypropylene powder has good particle shape, no profile is basically existed, and the percentage of ethylene structural units is 5.2%.
Example 3
This example serves to illustrate the preparation of the olefins provided by the present invention.
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 44.1 KgPP/g.Cat, and the bulk density of the polypropylene powder is 0.46g/cm3In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 4
This example serves to illustrate the preparation of the olefins provided by the present invention.
Propylene was polymerized by following the procedure of example 2 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 58.5 KgPP/g.Cat, and the bulk density of the polypropylene powder is 0.48g/cm3In addition, the polypropylene powder has good particle shape, no profile is basically existed, and the percentage of ethylene structural units is 5.0%.
Example 5
This example serves to illustrate the preparation of the olefins provided by the present invention.
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 42.1 KgPP/g.Cat, and the bulk density of the polypropylene powder is 0.47g/cm3In addition, the polypropylene powder has good particle shape and basically has no 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 polypropylene powder is 0.38g/cm3In addition, the polypropylene powder particles are all special-shaped materials and have poor flowability.
Comparative example 2
This comparative example serves to illustrate the reference preparation of olefins.
Propylene polymerization was carried out according to the method of comparative example 1, except that the reaction was carried out for 1 hour, the temperature was lowered, the pressure was released, then the mixed gas of ethylene and propylene (molar ratio C2/(C3+ C2) ═ 0.042) was introduced, the reaction was continued for 0.5 hour, the temperature was lowered, the pressure was released, and the discharge was dried to obtain polypropylene powder.
The activity of the catalyst is 43.1 kgPP/g-cat, and the bulk density of the polypropylene powder is 0.40g/cm3In addition, the polypropylene powder particles are all special-shaped materials, the flowability is poor, and the ethylene percent is 2.6 percent.
Comparative example 3
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 DZ2 obtained in comparative preparation example 2 to obtain a polypropylene powder.
The activity of the catalyst is 32.5 KgPP/g.Cat, and the bulk density of the polypropylene powder is 0.39g/cm3In addition, the polypropylene powder particles are all special-shaped materials and have poor flowability.
Comparative example 4
This comparative example serves to illustrate the reference preparation of olefins.
Propylene polymerization was conducted in accordance with the method of comparative example 2 except that the olefin polymerization catalyst support Z1 was replaced with the olefin polymerization catalyst support DZ2 obtained in comparative preparation example 2.
The activity of the catalyst is 43.3 kgPP/g-cat, and the bulk density of the polypropylene powder is 0.38g/cm3In addition, the polypropylene powder particles are all special-shaped materials, the flowability is poor, and the ethylene percent is 2.7 percent.
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 of the polymerization product and the content of ethylene structural units in the copolymerization can be improved, and the occurrence of foreign materials is substantially avoided.
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 (32)

1. An olefin polymerization catalyst carrier, which is a magnesium-containing compound shown as a formula (I),
Figure FDA0002360251560000011
wherein, in the formula (I), R1Is a linear or branched alkyl group of C1-C14; r2，R3And R4The alkyl groups are the same or different and are each independently hydrogen, linear or branched alkyl groups of C1-C5 or linear or branched haloalkyl groups of C1-C5; x is halogen; y is halogen; m is 0.1-1.9, n is 0.1-1.9, m + n is 2; 0<i<3，0≤j<3，0<k<3，i+j+k＝3，0<q≤0.5。
2. The catalyst carrier according to claim 1, wherein R1Is a linear or branched alkyl group of C1-C8;
R2，R3and R4The alkyl groups are the same or different and are each independently hydrogen, linear or branched alkyl groups of C1-C3 or linear or branched haloalkyl groups of C1-C3;
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 of claim 2Wherein R is2，R3And R4The same or different, each independently is one or more of hydrogen, methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl.
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 40 to 60 microns and a particle size distribution of 0.6 to 0.8.
7. The catalyst support of claim 1, wherein the raw materials for the synthesis of the catalyst support comprise chromium halides, magnesium halides, compounds of formula ROH, ethylene oxide compounds;
wherein, in the general formula ROH, R is C1-C14 straight chain or branched chain alkyl; the structure of the ethylene oxide compound is shown as the formula (II):
Figure FDA0002360251560000021
wherein R is5And R6Each independently hydrogen, C1-C5 linear or branched alkyl, or C1-C5 linear or branched haloalkyl.
8. The catalyst carrier according to claim 7, wherein the content of the chromium halide is 0.0001 to 1mol, the content of the compound of the general formula ROH is 4 to 30mol, and the content of the oxirane compound represented by the formula (II) is 1 to 10mol, based on 1mol of the magnesium halide.
9. The catalyst carrier according to claim 8, wherein the content of the chromium halide is 0.01 to 0.1mol, the content of the compound of the general formula ROH is 6 to 20mol, and the content of the oxirane compound represented by the formula (II) is 2 to 6mol, based on 1mol of the magnesium halide.
10. The catalyst support according to any one of claims 7 to 9, wherein the chromium halide is chromium chloride or chromium bromide, anhydrous or containing water of crystallization.
11. The catalyst support according to claim 10, wherein the chromium halide is anhydrous or a chromium chloride containing water of crystallization.
12. The catalyst support according to any one of claims 7-9 and 11, wherein the magnesium halide is selected from one or more of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.
13. The catalyst support according to any one of claims 7-9 and 11, wherein in the general formula ROH, R is a linear or branched alkyl group from C1 to C8.
14. The catalyst support according to claim 13, 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.
15. The catalyst carrier according to any one of claims 7 to 9, wherein in the oxirane compound of formula (II), R is5And R6Each independently hydrogen, C1-C3 linear or branched alkyl, or C1-C3 linear or branched haloalkyl.
16. The catalyst support according to claim 15, wherein the oxirane is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
17. A method for preparing an olefin polymerization catalyst support, the method comprising the steps of:
(1) mixing and heating chromium halide, magnesium halide, a compound with a general formula of ROH and an optional inert liquid medium to obtain a liquid mixture;
(2) emulsifying the liquid mixture obtained in the step (1), and contacting and reacting the emulsified product with an ethylene oxide compound;
in the general formula ROH, R is C1-C14 alkyl; the structure of the ethylene oxide compound is shown as the formula (II):
Figure FDA0002360251560000041
wherein R is5And R6Each independently hydrogen, C1-C5 linear or branched alkyl, or C1-C5 linear or branched haloalkyl.
18. The process according to claim 17, wherein the chromium halide is used in an amount of 0.0001 to 1mol, the compound of the formula ROH is used in an amount of 4 to 30mol, and the oxirane compound of the formula (II) is used in an amount of 1 to 10mol, based on 1mol of the magnesium halide.
19. The process according to claim 18, wherein the chromium halide is used in an amount of 0.01 to 0.2mol, the compound of the formula ROH is used in an amount of 6 to 20mol, and the oxirane compound of the formula (II) is used in an amount of 2 to 6mol, based on 1mol of the magnesium halide.
20. The method according to claim 17, 18 or 19, wherein in step (1), the heating is carried out at a temperature of 80-120 ℃ for a time of 0.5-5 hours.
21. The method of claim 20, wherein the heating is at a temperature of 80-100 ℃ for a time of 0.5-3 hours.
22. The process of claim 17, 18 or 19, wherein in step (2), the conditions of the contact reaction comprise a temperature of 50-120 ℃ and a time of 20-60 minutes.
23. The method of claim 22, wherein the conditions of the contact reaction include a temperature of 60-100 ℃ and a time of 20-50 minutes.
24. The process according to claim 17, 18 or 19, wherein the inert liquid medium is used in an amount of 0.8 to 10L based on 1mol of the magnesium halide, and the inert liquid medium is a silicone oil and/or an inert liquid hydrocarbon solvent.
25. The method of claim 24, 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.
26. A catalyst component for the polymerization of olefins comprising the product obtained by reacting a catalyst support according to any of claims 1 to 16 and/or a catalyst support prepared by the process according to any of claims 17 to 25 with a titanium compound and optionally an internal electron donor.
27. The catalyst component according to claim 26, wherein the catalyst component comprises a product obtained by reacting the catalyst carrier according to any one of claims 1 to 16 or the catalyst carrier prepared by the method according to any one of claims 17 to 25 with a titanium compound and an internal electron donor, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor compound is 1:5-15: 2-15.
28. The catalyst component according to claim 27, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor compound is 1:6-13: 3-12.
29. Use of a catalyst support according to any one of claims 1 to 16, or a catalyst support prepared by a process according to any one of claims 17 to 25, or a catalyst component for the polymerisation of olefins according to any one of claims 26 to 28, in the preparation of a catalyst for the polymerisation of olefins.
30. A catalyst for the polymerization of olefins, the catalyst comprising:
(1) a catalyst component for the polymerization of olefins according to anyone of claims 26 to 28;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
31. Use of the catalyst for olefin polymerization according to claim 30 in olefin polymerization reactions.
32. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst for olefin polymerization of claim 30 under olefin polymerization conditions.
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