CN111072802A - Olefin polymerization catalyst carrier, preparation method and application thereof - Google Patents
Olefin polymerization catalyst carrier, preparation method and application thereof Download PDFInfo
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- CN111072802A CN111072802A CN201811222176.6A CN201811222176A CN111072802A CN 111072802 A CN111072802 A CN 111072802A CN 201811222176 A CN201811222176 A CN 201811222176A CN 111072802 A CN111072802 A CN 111072802A
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Abstract
The invention relates to the field of olefin polymerization, and discloses an olefin polymerization catalyst carrier, and a preparation method and application thereof. The preparation method of the olefin polymerization catalyst carrier comprises the following steps: (1) mixing and emulsifying magnesium carboxylate, magnesium halide, an alcohol compound and an optional inert liquid medium to obtain an emulsified product; (2) and (3) carrying out contact reaction on the emulsified product and an ethylene oxide compound to obtain a solid-liquid mixture containing the olefin polymerization catalyst carrier. The carrier prepared by the method has good particle shape and basically does not have special-shaped particles, and the carrier can also improve the activity and the stereospecific capacity of the olefin polymerization catalyst in the olefin polymerization reaction and ensure that the olefin polymer has higher bulk density.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to an olefin polymerization catalyst carrier and a preparation method and application thereof.
Background
It is well known that the catalysts currently used for the polymerization of olefins are mainly prepared by supporting titanium halides on magnesium chloride alcoholates. This is because the magnesium chloride alcoholate supported Ziegler-Natta catalysts perform significantly better than other supported catalysts when used in the polymerization of olefins, especially propylene. In addition, spherical catalysts prepared from spherical carriers are more popular in the market. Spherical carriers can be prepared by spray drying, spray cooling, high pressure extrusion, high speed stirring, emulsifier method, and high gravity rotating bed method, for example, WO99/44009 and US4399054 disclose that a magnesium chloride alcoholate system can be emulsified by high speed stirring at high temperature and then quenched to form a spherical alcoholate.
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 spherical carrier for olefin polymerization and a preparation method thereof, wherein the carrier is prepared by reacting a magnesium halide alcoholate with an ethylene oxide compound, and specifically discloses adding the ethylene oxide 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 carrier adhesion and poor carrier forming effect.
Therefore, it is of great interest to develop a new catalyst support for olefin polymerization that overcomes the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to solve the above-mentioned drawbacks of the prior art, the present invention aims to provide a novel olefin polymerization catalyst carrier, and a preparation method and application thereof.
The present inventors have surprisingly found that a carrier having a novel composition can be obtained by adding a magnesium carboxylate compound during the preparation of a carrier for an olefin polymerization catalyst, and that the obtained carrier has a good particle morphology and is substantially free of irregular particles, and that a catalyst prepared from the carrier has a high stereotactic ability when used for olefin polymerization. The present invention has been made based on the above findings.
According to a first aspect of the present invention, there is provided a process for preparing an olefin polymerization catalyst support, the process comprising:
(1) mixing and emulsifying magnesium carboxylate, magnesium halide, an alcohol compound and an optional inert liquid medium to obtain an emulsified product;
(2) contacting and reacting the emulsified product with an ethylene oxide compound to obtain a solid-liquid mixture containing an olefin polymerization catalyst carrier;
the general formula of the magnesium halide is MgXY, X is halogen, Y is halogen and C1-C14Alkyl of (C)1-C14Alkoxy group of (C)6-C14Aryl or C of6-C14An aryloxy group of (a);
the general formula of the alcohol compound is ROH, R is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a);
the structure of the ethylene oxide compound is shown as a formula I:
in the formula I, R1And R2Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a).
According to a second aspect of the present invention, there is provided an olefin polymerization catalyst support obtained by the production process according to the first aspect of the present invention.
According to a third aspect of the present invention, there is provided the use of the olefin polymerisation catalyst support in an olefin polymerisation catalyst.
In the preparation method provided by the invention, the collision probability among unformed particles can be reduced and the adhesion among carrier particles can be reduced by adding the magnesium carboxylate, so that the prepared carrier particles have good shapes and basically have no special-shaped particles; meanwhile, compared with the single use of magnesium carboxylate, the compounding of the magnesium carboxylate and magnesium halide does not cause the phenomenon of wall sticking of a reaction kettle, and is beneficial to industrial continuous production. In addition, the olefin polymerization catalyst carrier prepared by the invention can also improve the activity and the stereospecific capacity of the olefin polymerization catalyst in the olefin polymerization reaction, and ensure that the olefin polymer has higher bulk density.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an optical microscope photograph of the morphology of the olefin polymerization catalyst support prepared in example 1;
FIG. 2 is an optical microscope photograph showing the morphology of the olefin polymerization catalyst support prepared in comparative example 1.
Detailed Description
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 a process for preparing an olefin polymerization catalyst support, the process comprising:
(1) mixing and emulsifying magnesium carboxylate, magnesium halide, an alcohol compound and an optional inert liquid medium to obtain an emulsified product;
(2) and (3) carrying out contact reaction on the emulsified product and an ethylene oxide compound to obtain a solid-liquid mixture containing the olefin polymerization catalyst carrier.
In the invention, the magnesium halide has a general formula of MgXY, wherein X is halogen, Y is halogen and C1-C14Alkyl of (C)1-C14Alkoxy group of (C)6-C14Aryl or C of6-C14An aryloxy group of (1).
Preferably, in the general formula MgXY, X is chlorine or bromine, Y is chlorine, bromine or C1-C5Alkyl of (C)1-C5Alkoxy group of (C)6-C10Aryl or C of6-C10An aryloxy group of (1).
In the present invention, C1-C5The alkyl group of (b) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group or a neopentyl group. C1-C5The alkoxy group of (a) may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy. C6-C10The aryl group of (A) may be, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, an m-ethylphenyl groupP-ethylphenyl or naphthyl. C6-C10The aryloxy group of (a) may be, for example, a phenoxy group or a naphthoxy group.
Further preferably, the magnesium halide is at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride. From the viewpoint of availability of raw materials, it is more preferable that the magnesium halide is selected from magnesium chloride.
In the invention, the alcohol compound has a general formula of ROH, wherein R is C1-C8Alkyl or C3-C8Cycloalkyl of (3), preferably C1-C8Alkyl group of (1).
In the present invention, C1-C8The alkyl group of (b) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group or an isooctyl group.
More preferably, the alcohol compound is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
In the present invention, the alcohol compound may be used in an amount of 4 to 30mol, preferably 6 to 15mol, based on 1mol of the magnesium halide.
In the invention, the structure of the ethylene oxide compound is shown as formula I:
in the formula I, R1And R2Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a). Preferably, R1And R2Each independently is hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a).
More preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
In the present invention, the ethylene oxide compound may be used in an amount of 1 to 10mol, preferably 2 to 6mol, based on 1mol of the magnesium halide.
In the present invention, the magnesium carboxylate may be any anhydrous and/or crystal water-containing magnesium carboxylate. Wherein the anhydrous magnesium carboxylate can be represented by the general formula Mg (OCOR)3)2，R3Represents hydrogen or alkyl, typically hydrogen or C1-C6 alkyl. Specific examples of the magnesium carboxylate include, but are not limited to, at least one of magnesium formate, magnesium acetate, magnesium propionate, and magnesium butyrate. Preferably, the magnesium carboxylate is magnesium acetate. Compared with the single use of the magnesium carboxylate, the compound use of the magnesium carboxylate and the magnesium halide can further avoid the phenomenon of wall sticking of a reaction kettle, thereby promoting the continuous production of the carrier in industry.
In the present invention, the magnesium formate may be used in an amount of 0.001 to 0.5mol, preferably 0.008 to 0.4mol, based on 1mol of the magnesium halide.
In the present invention, the inert liquid medium may be any of 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 at least one 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.
In the present invention, the inert liquid medium may be used in an amount of 0 to 10L, preferably 0 to 5L, based on 1mol of the magnesium halide.
According to the present invention, in step (1), the mixing and emulsification of the magnesium carboxylate, the magnesium halide, the alcohol compound, and optionally the inert liquid medium is not particularly limited and may be selected with reference to the prior art. The emulsification is usually carried out under heating and optionally with the addition of an emulsifier.
The conditions of the emulsification may include: the temperature is 80-120 ℃, and the preferred temperature is 80-100 ℃; the time is 0.5 to 5 hours, preferably 0.5 to 3 hours.
The emulsifier may be selected with reference to the prior art, and may be selected, for example, from at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol, polyacrylic acid, polyacrylate, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone-vinyl acetate copolymer, alkylphenylpolyoxyethylene ether and polyalkyl methacrylate, preferably polyvinylpyrrolidone and/or polyvinylpyrrolidone-vinyl acetate copolymer. The amount of the surfactant used is preferably 1 to 20g based on 1mol of magnesium halide in the presence of the emulsifier.
Alternatively, a liquid mixture obtainable by mixing the magnesium carboxylate, the magnesium halide, the alcohol compound, and optionally an inert liquid medium is emulsified under low or high shear conditions. 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, in the step (2), the conditions for the contact reaction of the emulsified product with the ethylene oxide compound 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 include: the temperature can be 50-120 ℃, preferably 80-100 ℃; the time may be 20 to 60 minutes, preferably 20 to 50 minutes.
According to a preferred embodiment, the emulsification and the contact reaction are carried out at the same temperature.
According to the present invention, in order to obtain the olefin polymerization catalyst with high purity, the method may further comprise: (3) and carrying out solid-liquid separation on the solid-liquid mixture, and then washing and drying the obtained solid product.
The solid-liquid separation can be any of the existing methods capable of realizing solid-phase and liquid-phase separation, such as suction filtration, filter pressing or centrifugal separation. Preferably, the solid-liquid separation adopts a filter pressing 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 a method known to those skilled in the art, and the obtained solid phase product may be usually washed with 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. In addition, the drying may be performed under normal pressure or reduced pressure.
According to a second aspect of the present invention, there is provided an olefin polymerization catalyst support obtained by the production method according to the first aspect of the present invention. The olefin polymerization catalyst carrier prepared by the method is a spherical carrier. As shown in FIG. 1, the olefin polymerization catalyst carrier prepared by the method of the present invention has regular particle morphology, smooth surface, concentrated particle size and substantially no presence of irregular particles.
According to one embodiment, the olefin polymerization catalyst support may have an average particle diameter of 10 to 100 μm and a particle size distribution of less than 1.2. Preferably, the olefin polymerization catalyst support has an average particle diameter of 40 to 60 μm and a particle size distribution of 0.6 to 0.8.
In the present invention, the average particle diameter of the olefin polymerization catalyst support is referred to as a median particle diameter D50, and the particle size distribution is referred to as (D90-D10)/D50, and the particle diameter can be measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern instruments Ltd.).
According to the invention, the olefin polymerization catalyst support may also contain water, which originates from traces of water carried by the synthesis raw materials and the reaction medium.
According to a third aspect of the present invention there is provided the use of an olefin catalyst support according to the second aspect of the present invention in an olefin polymerisation catalyst.
According to the application of the invention, the olefin polymerization catalyst comprises a main catalyst, an optional cocatalyst and an optional external electron donor compound, wherein the main catalyst is a reaction product of the olefin polymerization catalyst carrier, a titanium compound and the optional internal electron donor compound. The content of the olefin polymerization catalyst carrier in the olefin polymerization catalyst, and other components and contents thereof may be selected with reference to the field of existing olefin polymerization catalysts, and the present invention is not particularly limited thereto.
According to the application of the invention, in the main catalyst, the titanium compound can be one or more of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride and ethoxy titanium trichloride. The internal electron donor compound can be one or more of monobasic or polybasic aliphatic carboxylic acid ester, monobasic or polybasic aromatic carboxylic acid ester, dihydric alcohol ester and dihydric ether.
According to the present invention, the preparation method of the main catalyst may be selected with reference to the prior art, and the present invention is not particularly limited thereto. Generally, the reaction conditions in the preparation process may include: the reaction temperature is 80-130 ℃ and the reaction time is 0.5-10 hours. The titanium compound may be used in an amount of 5 to 60mol, preferably 9 to 30mol, based on 1mol of the magnesium element in the olefin polymerization catalyst support; the amount of the internal electron donor compound may be 0 to 1mol, preferably 0.07 to 1mol, and more preferably 0.1 to 0.2 mol.
According to the use of the present invention, in the olefin polymerization catalyst, the cocatalyst may be an alkylaluminum compound. The alkyl aluminum compound may be, for example, one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, monoisobutylaluminum dichloride, n-butylaluminum dichloride and n-hexylaluminum dichloride. The external electron donor compound may be one or more of carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organic silicon compound, and is preferably an organic silicon compound. Examples of the organosilicon compound may be, but are not limited to: methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane.
In the olefin polymerization catalyst, the molar ratio of the aluminum alkyl compound, calculated as aluminum, to the procatalyst, calculated as titanium, may be from 1 to 2000:1, preferably from 20 to 500: 1. The molar ratio of the external electron donor compound to the alkylaluminum compound may be 0.005-0.5:1, preferably 0.01-0.4: 1.
According to the application of the invention, the olefin polymerization catalyst carrier is introduced into the olefin polymerization catalyst, so that the catalytic activity and the stereospecific capacity of the olefin polymerization catalyst in olefin polymerization reaction can be improved, and olefin polymers with higher bulk density can be obtained. In addition, the specific operation and conditions of the olefin polymerization reaction can be selected by referring to the prior art, and the detailed description of the invention is omitted.
The present invention will be described in detail below by way of examples.
In the following 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 Sizer 2000 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 was determined by the method specified in GB/T1636-2008.
The following examples 1 to 3 are illustrative of the olefin polymerization catalyst support of the present invention and the method for preparing the same.
Example 1
Adding 8.0g (0.08mol) of magnesium chloride, 56mL (0.96mol) of ethanol and 2.1g of anhydrous magnesium acetate (0.015mol) into a 0.6L reaction kettle, heating to 80 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epichlorohydrin, reacting for 30 minutes, carrying out filter pressing, washing a filter-pressed product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst carrier Z1.
The olefin polymerization catalyst carrier Z1 had an average particle diameter (D50) of 51 μm and a particle size distribution ((D90-D10)/D50) of 0.8. The particle morphology observed by an optical microscope is as shown in fig. 1, the particle morphology of the olefin polymerization catalyst carrier Z1 is regular, the surface is smooth, the particle morphology is substantially spherical, the particle size distribution is concentrated, and no irregular particles exist basically.
Example 2
Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol and 1g of anhydrous magnesium acetate (0.007mol) into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epichlorohydrin, reacting for 20 minutes, performing pressure filtration, washing the pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst carrier Z2.
The olefin polymerization catalyst carrier Z2 had an average particle diameter (D50) of 48 μm and a particle size distribution ((D90-D10)/D50) of 0.7. As can be seen from the particle morphology observed by an optical microscope, the olefin polymerization catalyst carrier Z2 has the advantages of regular particle morphology, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Example 3
In a 0.6L reaction kettle, adding 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 4.2g (0.029mol) of anhydrous magnesium acetate and 0.1g of polyvinylpyrrolidone (PVP), heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, then adding 12.5mL (0.16mol) of epoxy chloropropane, reacting for 20 minutes, carrying out filter pressing, washing a filter-pressed product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst carrier Z3.
The olefin polymerization catalyst carrier Z3 had an average particle diameter (D50) of 41 μm and a particle size distribution ((D90-D10)/D50) of 0.7. As can be seen from the particle morphology observed by an optical microscope, the olefin polymerization catalyst carrier Z3 has the advantages of regular particle morphology, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particles.
Comparative example 1
Adding 8.0g (0.08mol) of magnesium chloride and 56mL (0.96mol) of ethanol into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epoxy chloropropane, reacting for 30 minutes, carrying out filter pressing, washing a filter-pressed product with hexane for 5 times, and carrying out vacuum drying to obtain the catalyst carrier D-Z1 for olefin polymerization.
The average particle diameter (D50) of the olefin polymerization catalyst carrier D-Z1 was 100. mu.m, and the particle size distribution ((D90-D10)/D50) was 1.6. As shown in FIG. 2, the morphology of the particles observed by an optical microscope showed that a large number of irregular particles were present in the olefin polymerization catalyst support D-Z1, and the surface was rough.
The following application examples 1 to 6 are intended to illustrate the use of the olefin polymerization catalyst support of the present invention for an olefin polymerization catalyst.
Application example 1
(1) Preparation of olefin polymerization catalyst
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was charged, cooled to-20 ℃, 40g of the olefin polymerization catalyst support Z1 prepared in example 1 was charged and stirred at-20 ℃ for 30 minutes, then slowly warmed to 110 ℃, 1.5mL of diisobutyl phthalate was added during the warming, and after maintaining at 110 ℃ for 30 minutes, the liquid was filtered off. Then, titanium tetrachloride was added to wash the mixture for 2 times, and finally, hexane was added to wash the mixture for 3 times, followed by drying to obtain an olefin polymerization catalyst C1.
(2) Propylene polymerization
In a 5L stainless steel autoclave, purging was performed with a nitrogen stream, and then 2mL of a hexane solution of triethylaluminum (concentration of triethylaluminum is 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, and 10mg of an olefin polymerization catalyst C1, 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, then cooling, releasing pressure, discharging and drying to obtain the polypropylene powder. The polypropylene powder has good particle shape and basically has no special shape.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Application example 2
Propylene polymerization was conducted in accordance with the procedure of application example 1 except that said 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The polypropylene powder has good particle shape and basically has no special-shaped material.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Application example 3
(1) Preparation of olefin polymerization catalyst
An olefin polymerization catalyst was prepared by following the procedure of application example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with an equal weight of the olefin polymerization catalyst carrier Z2 prepared in example 2, to thereby obtain an olefin polymerization catalyst C2.
(2) Propylene polymerization
Propylene was polymerized by the method of practical example 1, except that the olefin polymerization catalyst C1 in practical example 1 was replaced with an equal weight of the olefin polymerization catalyst C2, to thereby obtain a polypropylene powder. The polypropylene powder has good particle shape and basically has no special shape.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Application example 4
Propylene polymerization was conducted in accordance with the procedure of application example 3 except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The polypropylene powder has good particle shape and basically has no special-shaped material.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Application example 5
(1) Preparation of olefin polymerization catalyst
An olefin polymerization catalyst was prepared by following the procedure of application example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with an equal weight of the olefin polymerization catalyst carrier Z3 prepared in example 3, to thereby obtain an olefin polymerization catalyst C3.
(2) Propylene polymerization
Propylene was polymerized by the method of practical example 1, except that the olefin polymerization catalyst C1 in practical example 1 was replaced with an equal weight of the olefin polymerization catalyst C3, to thereby obtain a polypropylene powder. The polypropylene powder has good particle shape and basically has no special shape.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Application example 6
Propylene polymerization was conducted in accordance with the procedure of application example 5 except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain a polypropylene powder. The polypropylene powder has good particle shape and basically has no special-shaped material.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Application comparative example 1
(1) Preparation of olefin polymerization catalyst
An olefin polymerization catalyst was prepared by following the procedure of application example 1, except that the olefin polymerization catalyst carrier Z1 was replaced with an equal weight of the olefin polymerization catalyst carrier D-Z1 prepared in comparative example 1, to thereby obtain an olefin polymerization catalyst D-C1.
(2) Propylene polymerization
Propylene was polymerized by the method of practical example 1, except that the olefin polymerization catalyst C1 in practical example 1 was replaced with an equal weight of the olefin polymerization catalyst D-C1, to thereby obtain a polypropylene powder. The polypropylene powder particles are all special-shaped materials and have poor flowability.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
Comparative application example 2
Propylene polymerization was carried out in the same manner as in comparative example 1 except that 6.5L (standard volume) of hydrogen was substituted with the 1.5L (standard volume) of hydrogen to obtain a polypropylene powder. The polypropylene powder particles are all special-shaped materials and have poor flowability.
The activity of the catalyst, the bulk density of the polypropylene powder and the isotactic index are shown in Table 1.
TABLE 1
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 presence of irregular particles. Moreover, when the catalysts prepared from the supports obtained in examples 1 to 3 were used for olefin (particularly propylene) polymerization, the activity and stereospecificity of the catalysts were higher under high and low hydrogen usage conditions, and the prepared polypropylene powders had higher bulk density, as compared to the olefin polymerization catalyst prepared from the olefin polymerization catalyst support of comparative example 1.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A method for preparing an olefin polymerization catalyst support, the method comprising:
(1) mixing and emulsifying magnesium carboxylate, magnesium halide, an alcohol compound and an optional inert liquid medium to obtain an emulsified product;
(2) contacting and reacting the emulsified product with an ethylene oxide compound to obtain a solid-liquid mixture containing an olefin polymerization catalyst carrier;
the general formula of the magnesium halide is MgXY, X is halogen, Y is halogen and C1-C14Alkyl of (C)1-C14Alkoxy group of (C)6-C14Aryl or C of6-C14An aryloxy group of (a);
the general formula of the alcohol compound is ROH, R is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a);
the structure of the ethylene oxide compound is shown as a formula I:
in the formula I, R1And R2Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a).
2. The preparation method according to claim 1, wherein the magnesium carboxylate is used in an amount of 0.001 to 0.5mol, the alcohol compound is used in an amount of 4 to 30mol, the inert liquid medium is used in an amount of 0 to 10L, and the oxirane compound is used in an amount of 1 to 10mol, based on 1mol of the magnesium halide;
preferably, based on 1mol of the magnesium halide, the amount of the magnesium carboxylate is 0.008 to 0.4mol, the amount of the alcohol compound is 6 to 15mol, the amount of the inert liquid medium is 0 to 5L, and the amount of the ethylene oxide compound is 2 to 6 mol.
3. The production method according to claim 1, wherein in the step (1), the emulsification conditions include: the temperature is 80-120 ℃, and the preferred temperature is 80-100 ℃; the time is 0.5 to 5 hours, preferably 0.5 to 3 hours.
4. The production method according to claim 1 or 3, wherein, in step (1), the emulsification is performed in the presence of an emulsifier selected from at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone-vinyl acetate copolymer, alkylphenylpolyoxyethylene ether and polyalkylmethacrylate, preferably polyvinylpyrrolidone and/or polyvinylpyrrolidone-vinyl acetate copolymer;
preferably, the emulsifier is used in an amount of 1 to 20g based on 1mol of the magnesium halide.
5. The production method according to claim 1, wherein in the step (2), the conditions of the contact reaction include: the temperature is 80-120 ℃, and the preferred temperature is 80-100 ℃; the time is 20 to 60 minutes, preferably 20 to 50 minutes.
6. The production method according to any one of claims 1 to 5, wherein the magnesium carboxylate is at least one selected from the group consisting of magnesium formate, magnesium acetate, magnesium propionate and magnesium butyrate, preferably magnesium acetate.
7. The process according to any one of claims 1 to 5, wherein in the formula MgXY, X is chlorine or bromine and Y is chlorine, bromine or C1-C5Alkyl groups of (a);
preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.
8. The process according to any one of claims 1 to 5, wherein R in the formula ROH is C1-C8Alkyl groups of (a);
preferably, the alcohol compound is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
9. The process according to any one of claims 1 to 5, wherein in formula I, R is1And R2Each independently is hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a);
preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
10. The production method according to any one of claims 1 to 5, wherein the inert liquid medium is a silicone oil and/or an inert liquid hydrocarbon solvent;
preferably, the inert liquid medium is at least one 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.
11. The production method according to any one of claims 1 to 5, wherein the method further comprises:
(3) and carrying out solid-liquid separation on the solid-liquid mixture, and then washing and drying the obtained solid product.
12. An olefin polymerization catalyst support obtained by the production method according to any one of claims 1 to 11.
13. The olefin polymerization catalyst support according to claim 12, wherein the olefin polymerization catalyst support has an average particle diameter of 10 to 100 μm and a particle size distribution of less than 1.2;
preferably, the olefin polymerization catalyst support has an average particle diameter of 40 to 60 μm and a particle size distribution of 0.6 to 0.8.
14. Use of the olefin polymerization catalyst support according to claim 12 or 13 in an olefin polymerization catalyst.
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| CN114478864A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Spherical catalyst carrier for olefin polymerization and preparation method and application thereof |
| CN114478860A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst carrier for olefin polymerization, preparation method and application thereof, olefin polymerization catalyst and application thereof |
| CN114478847A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof |
| CN114478862A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
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