CN109400778B - Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method - Google Patents
Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method Download PDFInfo
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Abstract
The invention relates to the field of olefin polymerization, and discloses a catalyst component for olefin polymerization and a preparation method thereof, a catalyst for olefin polymerization and an olefin polymerization method, wherein the preparation method comprises the following steps: an olefin polymerization catalyst carrier, a titanium compound and an optional internal electron donor compound are reacted, wherein the olefin polymerization catalyst carrier has a structure shown as a formula (1), and R is1Is C1‑C8Alkyl or C3‑C8Cycloalkyl groups of (a); r2And R3Each independently is hydrogen, C1‑C5Alkyl or C1‑C5A haloalkyl group of (a); r4Is C2‑C12Alkyl or haloalkyl of (a); x' is halogen; y' is halogen; m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0<j<3，0<k<3，j+k＝3，0<q≤0.5。
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst for olefin polymerization containing the catalyst component for olefin polymerization, 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 carrier adhesion and poor carrier forming effect. Therefore, it is necessary to add other surfactants such as stearic acid, span, quats, etc. during the preparation process. The addition of these substances not only increases the cost, but also adversely affects the recovery of by-products and reduces the activity of the catalyst prepared from the obtained support.
Disclosure of Invention
The invention aims to overcome the problems of complex preparation method, low activity and poor particle morphology of the olefin polymerization catalyst in the prior art, and provides a catalyst component for olefin polymerization, a preparation method thereof, a catalyst for olefin polymerization and an olefin polymerization method.
In order to achieve the above objects, the inventors of the present invention have unexpectedly found that when a catalyst support prepared from a raw material containing iron halide is used in an olefin polymerization catalyst, the catalyst can exhibit a good catalytic activity, and the distribution morphology of the powder particles of the polymerized olefin prepared by using the catalyst is good.
In one aspect, the present invention provides a method for preparing a catalyst component for olefin polymerization, wherein the method comprises: the method comprises the following steps of reacting an olefin polymerization catalyst carrier, a titanium compound and an optional internal electron donor compound, wherein the olefin polymerization catalyst carrier has a structure shown as a formula (1):
wherein R is1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); r2And R3Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a); r4Is C2-C12Alkyl or haloalkyl of (a); x' is halogen; y' is halogen; m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0<j<3，0<k<3，j+k＝3，0<q≤0.5。
The second aspect of the present invention provides a catalyst component for olefin polymerization prepared by the preparation method of the present invention.
In a third aspect, the present invention provides a catalyst for olefin polymerization, wherein the catalyst comprises:
(1) the catalyst component for olefin polymerization of the present invention;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
In a fourth aspect, the present invention provides an olefin polymerization process, wherein the olefin polymerization process comprises: olefin polymerization is carried out by contacting one or more olefins with the catalyst component for olefin polymerization of the present application, an aluminum alkyl compound, and optionally an external electron donor compound under olefin polymerization conditions.
The preparation method of the catalyst component for olefin polymerization is simple, the catalyst containing the catalyst component obtained by the preparation method has high catalytic activity, and the polymerized olefin powder prepared by the catalyst has good particle distribution form and high bulk density.
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 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.
In one aspect, the present invention provides a method for preparing a catalyst component for olefin polymerization, wherein the method comprises: the method comprises the following steps of reacting an olefin polymerization catalyst carrier, a titanium compound and an optional internal electron donor compound, wherein the olefin polymerization catalyst carrier has a structure shown as a formula (1):
wherein R is1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); r2And R3Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a); r4Is C2-C12Alkyl or haloalkyl of (a); x' is halogen; y' is halogen; m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0<j<3，0<k<3，j+k＝3，0<q≤0.5。
In the present invention, preferably, R1Is C1-C8Alkyl groups of (a); r2And R3Each independently is hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a); r4Is C2-C8Alkyl or haloalkyl of (a); x' is chlorine or bromine; y' is chlorine or bromine.
The olefin polymerization catalyst carrier has good morphology distribution, preferably, the average particle diameter of the olefin polymerization catalyst carrier is preferably 10-100 microns, and the particle size distribution is preferably less than 1.2; further preferably, the olefin polymerization catalyst carrier has an average particle diameter of 40 to 60 μm and a particle size distribution of 0.8 or less; more preferably, the olefin polymerization catalyst support has a particle size distribution of 0.2 to 0.8. In the present invention, the average particle diameter and the particle size distribution of the olefin polymerization catalyst support can be measured using a Master Sizer2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).
In the present invention, the preparation method of the olefin polymerization catalyst support preferably comprises:
(1) mixing iron halide, magnesium halide with formula MgXY, alcohol compound with formula ROH and optional inert liquid medium, and emulsifying;
(2) contacting the emulsified product obtained in the step (1) with an ethylene oxide compound shown in a formula (2) for reaction;
wherein, in the general formula MgXY, X is halogen, Y is halogen or C1-C6Alkyl groups of (a); in the general formula ROH, R is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); in the formula (2), R5And R6Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a).
In the present invention, the amount of the raw material used in the process for preparing the olefin polymerization catalyst carrier may be selected and varied within a wide range, and preferably, the amount of the iron halide is 0.01 to 0.3mol, the amount of the alcohol compound of the formula ROH is 4 to 30mol, and the amount of the oxirane compound represented by the formula (2) is 1 to 10mol, based on 1mol of the magnesium halide of the formula MgXY; more preferably, based on 1mol of magnesium halide with the general formula of MgXY, the using amount of the iron halide is 0.01-0.15mol, the using amount of the compound with the general formula of ROH is 6-20mol, and the using amount of the oxirane compound with the structure shown in the formula (2) is 2-6 mol.
In the present invention, in order to further improve the distribution morphology of the carrier particles and improve the catalytic effect of the catalyst prepared from the carrier, the iron halide is preferably iron trichloride or iron bromide, and is further preferably iron trichloride.
In the present invention, in the magnesium halide of the formula MgXY, X is preferably chlorine or bromine and Y is preferably chlorine, bromine or C1-C5Alkyl group of (1). Said C is1-C5The alkyl group of (2) 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. The magnesium halide of the formula MgXY may be one magnesium halide or a mixture of magnesium halides. Magnesium chloride is preferred from the viewpoint of availability of raw materials.
In the present invention, in the alcohol compound of the formula ROH, R is preferably C1-C8Alkyl group of (1). Said C is1-C8The alkyl group of (A) may be, for example, methyl, ethyl, n-propyl, i-propylPropyl, 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.
In the present invention, in the oxirane compound represented by the formula (2), R5And R6Preferably each independently of the other is hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a). Specific examples of the oxirane compound may be, but are not limited to: one or more of ethylene oxide, propylene oxide, epichlorohydrin and epibromohydrin.
In the present invention, the amount of the inert liquid medium may be selected according to the amount of the magnesium halide having the general formula of MgXY. In general, the inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on 1mol of magnesium halide of the formula MgXY. The inert liquid medium may be any of the various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products. For example: the inert liquid medium may be a silicone oil and/or an inert liquid hydrocarbon solvent. Specifically, the inert liquid medium may be one or more of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil. The inert liquid medium according to the invention is particularly preferably white oil.
In the present invention, the conditions of the emulsification in step (1) are not particularly limited as long as the emulsification conditions are such that the magnesium halide having the general formula MgXY is melted and sufficiently reacted with the iron halide. Preferably, the conditions of the emulsification 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.
In the present invention, the mixture obtained in step (1) may be emulsified by various methods known to those skilled in the art. For example, the mixture may be subjected to low or high shear to emulsify it. 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.
In the present invention, in the step (2), the conditions of the contact reaction preferably 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.
The method for preparing the olefin polymerization catalyst carrier can also comprise the steps of carrying out solid-liquid separation on the product obtained by the contact reaction, 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 the present invention, the titanium compound may be various titanium compounds conventionally used in the process of preparing a catalyst for olefin polymerization. Typically, the titanium is combinedThe compound is of the general formula Ti (OR)a)4-mXmWherein R isaIs C1-C14X is F, Cl or Br, m is an integer from 1 to 4; the titanium compound is preferably one or more of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxytrichloride, titanium triethoxide chloride, titanium diethoxide dichloride and titanium ethoxytrichloride.
In the present invention, the "optional internal electron donor compound" means that the internal electron donor compound may or may not be present. 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. In the present invention, the selection of the specific kinds of the mono-or poly-aliphatic carboxylic acid ester, mono-or poly-aromatic carboxylic acid ester, glycol ester and glycol ether can be selected with reference to the prior art, and the present invention will not be described in detail herein.
In the present invention, the weight ratio of the titanium compound calculated as titanium element, the olefin polymerization catalyst carrier calculated as magnesium element, and the internal electron donor compound may be 1: 5-15: 2-15, preferably 1: 6-13: 3-12.
In the present invention, the conditions for the reaction of the olefin polymerization catalyst support, the titanium compound and the optional internal electron donor compound are not particularly limited, and preferably, the reaction conditions may include: the reaction temperature is 80-130 ℃ and the reaction time is 0.5-10 hours.
The second aspect of the present invention provides a catalyst component for olefin polymerization prepared by the preparation method of the present invention.
In a third aspect, the present invention provides a catalyst for olefin polymerization, wherein the catalyst comprises:
(1) the catalyst component for olefin polymerization of the present invention;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
By "optional external electron donor compound" is meant that the external electron donor compound may or may not be present.
The catalyst contains the catalyst component for olefin polymerization, so that when the catalyst is used for olefin polymerization, the bulk density of a polymer obtained by polymerization is improved, and the morphology of polymer particles is good.
In the present invention, in the catalyst for olefin polymerization, the molar ratio of the alkyl aluminum compound in terms of aluminum to the catalyst component for olefin polymerization in terms of titanium may be 1 to 2000:1, preferably 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.
In the present invention, the alkyl aluminum compound may be various alkyl aluminum compounds commonly used in the art. For example, the alkyl aluminum compound may be 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, isobutylaluminum dichloride, n-butylaluminum dichloride, and n-hexylaluminum dichloride.
In the present invention, the external electron donor compound may be various external electron donor compounds 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 silicon compound; preferably, the external electron donor is of the formula R7 aR8 bSi(OR9)cWherein a and b are each an integer of 0, 1 or 2, c is an integer of 1 to 3, and the sum of a + b + c is 4, R7、R8、R0Each independently is C1-C18Substituted or unsubstituted hydrocarbyl of (a); more preferably, a and b are each 1, c is 2, R7、R8Each independentlyIs C3-C10Substituted or unsubstituted hydrocarbyl of, R9Is C1-C10Substituted or unsubstituted hydrocarbyl. Specifically, examples of the organosilicon compound may be, but are not limited to: cyclohexylmethyldimethoxysilane, 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 a fourth aspect, the present invention provides an olefin polymerization process, wherein the olefin polymerization process comprises: one or more olefins are contacted with the catalyst component for olefin polymerization, an alkyl aluminum compound and an optional external electron donor compound under olefin polymerization conditions to carry out olefin polymerization reaction.
The olefin polymerization method of the invention can prepare polymer with good particle shape and high bulk density by using the catalyst component for olefin polymerization of the invention. The olefin polymerization method of the present invention is not particularly limited with respect to the olefin polymerization conditions and the olefin used.
The olefin may be, 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.
In the present invention, the olefin polymerization may be carried out according to a conventional method in the art. For example, the olefin polymerization may be bulk polymerization, gas phase polymerization, or slurry polymerization. The conditions for the olefin polymerization may be conventional in the art, for example, the polymerization temperature may be from 0 to 150 ℃, preferably from 60 to 90 ℃; the polymerization pressure may be atmospheric pressure or elevated pressure.
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 Sizer2000 particle Sizer (manufactured by Malvern Instruments Ltd.);
2. the apparent morphology of the olefin polymerization catalyst support and the polyolefin powder was observed by an optical microscope commercially available from Nikon as Eclipse E200;
3. the bulk density of the polyolefin powder was determined by the method specified in GB/T1636-2008.
Preparation example 1
Adding 0.08mol of magnesium chloride, 0.96mol of ethanol and 2g of anhydrous ferric chloride (0.012mol) into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 0.48mol (38ml) of epoxy chloropropane, reacting for half an hour, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and performing vacuum drying to obtain the catalyst carrier Z1 for olefin polymerization.
The olefin polymerization catalyst carrier Z1 had an average particle diameter (D50) of 47 microns and a particle size distribution ((D90-D10)/D50) of 0.8. The particle morphology observed by an optical microscope is shown in FIG. 1, and it can be seen from the figure that the particle morphology of the olefin polymerization catalyst carrier Z1 is regular, the surface is smooth, the carrier is basically spherical, the particle size distribution is concentrated, and no irregular (non-spherical) particles exist basically.
By infrared spectroscopy and1the structural formula of the olefin polymerization catalyst carrier Z1 is shown as (R) in the following formula (3) determined by an H-NMR method1Is ethyl, R2Is hydrogen, R3Is chloromethyl, R4Is chloropropane, X 'is chlorine, Y' is chlorine, m ═ 1, n ═ 1, j ═ 2, k ═ 1, q ═ 0.06):
preparation example 2
Adding 300mL of white oil, 0.08mol of magnesium chloride, 0.48mol of ethanol and 1g of (0.006) ferric trichloride into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 0.16mol of epoxy chloropropane, reacting for 20 minutes, performing pressure filtration, washing a 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. The particle morphology observed by an optical microscope is shown in FIG. 2, and it can be seen from the figure that the particle morphology of the olefin polymerization catalyst carrier Z2 is regular, the surface is smooth, the carrier is substantially spherical, the particle size distribution is concentrated, and no irregular particles exist basically.
Preparation example 3
Adding 200mL of white oil, 0.08mol of magnesium chloride, 1.6mol of ethanol and 0.004mol of ferric trichloride into a 0.6L reaction kettle, heating to 80 ℃ under stirring, reacting for 3 hours at constant temperature, adding 0.32mol of epoxy chloropropane, reacting for 50 minutes, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing 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 49 μm and a particle size distribution ((D90-D10)/D50) of 0.7. The particle observed by an optical microscope has the advantages that the particle form of the olefin polymerization catalyst carrier Z3 is regular, the surface is smooth, the particle is basically spherical, the particle size distribution is concentrated, and no special-shaped particles exist basically.
Preparation example 4
An olefin polymerization catalyst support was prepared by following the procedure of preparation example 1, except that the same molar amount of ferric bromide was used instead of ferric trichloride. Thus, a catalyst carrier Z4 for olefin polymerization was obtained.
The olefin polymerization catalyst carrier Z4 had an average particle diameter (D50) of 52 μm and a particle size distribution ((D90-D10)/D50) of 0.8. The particle observed by an optical microscope has the advantages that the particle form of the olefin polymerization catalyst carrier Z4 is regular, the surface is smooth, the particle is basically spherical, the particle size distribution is concentrated, and no special-shaped particles exist basically.
Comparative preparation example 1
An olefin polymerization catalyst support was prepared according to the method of preparation example 1, except that ferric chloride was not used in the preparation process. Thus, a catalyst carrier D-Z1 for olefin polymerization was obtained.
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. The morphology of the particles observed by an optical microscope is shown in FIG. 3, and it can be seen that a large number of irregular particles are present in the catalyst carrier D-Z1 for olefin polymerization, and the surface is rough.
Example 1
(1) Preparation of olefin polymerization catalyst
In a 300mL glass reaction vessel, 100mL of titanium tetrachloride was added, cooled to-20 ℃, and 40 g of the olefin polymerization catalyst support Z1 obtained in preparation example 1 was added thereto and stirred at-20 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 1.5mL of diisobutyl phthalate was added during the temperature raising, and the temperature was maintained at 110 ℃ for 30min, after which the liquid was filtered off. Then, titanium tetrachloride was added and the mixture was washed 2 times, finally 3 times with hexane and dried to obtain an olefin polymerization catalyst component C1.
(3) Propylene polymerization
In a 5L stainless steel autoclave, purging was conducted with a nitrogen stream, and then 1mmol of a hexane solution of triethylaluminum (concentration of triethylaluminum is 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, and 10mg of the olefin polymerization catalyst C1 obtained in step (1), 1.5L (standard volume) of hydrogen, and 2.5L of liquid propylene were introduced into the nitrogen stream. Heating to 70 ℃, reacting for 1 hour at the temperature, cooling, releasing pressure, discharging and drying to obtain the polypropylene powder.
The catalytic activity of the catalyst is 37.1 kgPP/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
A polypropylene powder was prepared by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z2 obtained in preparation example 2 was used in place of Z1, to obtain a polypropylene powder.
The catalytic activity of the catalyst is 36.8 kgPP/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 3
A polypropylene powder was prepared by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z3 obtained in preparation example 3 was used in place of Z1, to obtain a polypropylene powder.
The catalytic activity of the catalyst is 36.5 kgPP/g-cat, and the bulk density of the polypropylene powder is 0.44g/cm3In addition, the polypropylene powder has good particle shape and basically has no profile.
Example 4
A polypropylene powder was prepared by following the procedure of example 1, except that the olefin polymerization catalyst carrier Z4 obtained in preparation example 4 was used in place of Z1, to obtain a polypropylene powder.
The catalytic activity of the catalyst is 35.8 kgPP/g-cat, and the bulk density of the polypropylene powder is 0.43g/cm3In addition, the polypropylene powder has good particle shape and basically has no profile.
Comparative example 1
A polypropylene powder was obtained by following the procedure of example 1, except that the olefin polymerization catalyst carrier D-Z1 obtained in comparative preparation example 1 was used in place of Z1.
The catalytic 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.
As can be seen from the comparison of the results of the above preparation examples, examples and comparative examples, the olefin polymerization catalyst carrier of the present invention has good particle morphology and substantially no irregular particles, and the catalyst prepared from the olefin polymerization catalyst carrier has high catalytic activity when used for olefin polymerization, and the obtained polypropylene powder has good morphology and high bulk density.
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 (27)
1. A process for the preparation of a catalyst component for the polymerization of olefins, characterized in that it comprises: the method comprises the following steps of reacting an olefin polymerization catalyst carrier, a titanium compound and an optional internal electron donor compound, wherein the olefin polymerization catalyst carrier has a structure shown as a formula (1):
wherein R is1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); r2And R3Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a); r4Is C2-C12Alkyl or haloalkyl of (a); x' is halogen; y' is halogen; m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0<j<3，0<k<3，j+k＝3，0<q≤0.5。
2. The method of claim 1, wherein R1Is C1-C8Alkyl groups of (a); r2And R3Each independently is hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a); r4Is C2-C8Alkyl or haloalkyl of (a); x' is chlorine or bromine; y' is chlorine or bromine.
3. The production method according to claim 1 or 2, 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.
4. The production process according to claim 3, wherein the olefin polymerization catalyst carrier has an average particle diameter of 40 to 60 μm and a particle size distribution of 0.8 or less.
5. The production method according to claim 3, wherein the olefin polymerization catalyst support has a particle size distribution of 0.2 to 0.8.
6. The production method according to claim 4, wherein the olefin polymerization catalyst support has a particle size distribution of 0.2 to 0.8.
7. The production method according to claim 1 or 2, wherein the production method of the olefin polymerization catalyst support comprises:
(1) mixing iron halide, magnesium halide with formula MgXY, alcohol compound with formula ROH and optional inert liquid medium, and emulsifying;
(2) contacting the emulsified product obtained in the step (1) with an ethylene oxide compound shown in a formula (2) for reaction;
wherein, in the general formula MgXY, X is halogen, Y is halogen or C1-C6Alkyl groups of (a); in the general formula ROH, R is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); in the formula (2), R5And R6Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a).
8. The process according to claim 7, wherein R is C1-C8Alkyl groups of (a); r5And R6Each independently is hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a); x is chlorine or bromine; y is chlorine, bromine or C1-C5Alkyl group of (1).
9. The process according to claim 7, wherein the iron halide is used in an amount of 0.01 to 0.3mol, the alcohol compound of the formula ROH is used in an amount of 4 to 30mol, and the oxirane compound of the formula (2) is used in an amount of 1 to 10mol, based on 1mol of the magnesium halide of the formula MgXY.
10. The process according to claim 9, wherein the iron halide is used in an amount of 0.01 to 0.15mol, the compound of formula ROH is used in an amount of 6 to 20mol, and the oxirane compound of formula (2) is used in an amount of 2 to 6mol, based on 1mol of magnesium halide of formula MgXY.
11. The process according to claim 8, wherein the iron halide is used in an amount of 0.01 to 0.3mol, the alcohol compound of the formula ROH is used in an amount of 4 to 30mol, and the oxirane compound of the formula (2) is used in an amount of 1 to 10mol, based on 1mol of the magnesium halide of the formula MgXY.
12. The process according to claim 11, wherein the iron halide is used in an amount of 0.01 to 0.15mol, the compound of formula ROH is used in an amount of 6 to 20mol, and the oxirane compound of formula (2) is used in an amount of 2 to 6mol, based on 1mol of magnesium halide of formula MgXY.
13. The method according to claim 7, wherein the iron halide is ferric chloride or ferric bromide.
14. The method of claim 13, wherein the iron halide is ferric chloride.
15. The method according to claim 8, wherein the iron halide is ferric chloride or ferric bromide.
16. The method of claim 15, wherein the iron halide is ferric chloride.
17. The production method according to claim 7, wherein in the step (1), the emulsification conditions include: the temperature is 80-120 ℃ and the time is 0.5-5 hours.
18. The preparation method according to claim 17, wherein in the step (1), the emulsification conditions include: the temperature is 80-100 ℃ and the time is 0.5-3 hours.
19. The production method according to claim 8, wherein in the step (1), the emulsification conditions include: the temperature is 80-120 ℃ and the time is 0.5-5 hours.
20. The preparation method according to claim 19, wherein in the step (1), the emulsification conditions include: the temperature is 80-100 ℃ and the time is 0.5-3 hours.
21. The production method according to claim 7, wherein in the step (2), the conditions of the contact reaction include: the temperature is 80-120 ℃ and the time is 20-60 minutes.
22. The production method according to claim 21, wherein in the step (2), the conditions of the contact reaction include: the temperature is 80-100 ℃ and the time is 20-50 minutes.
23. The production method according to claim 8, wherein in the step (2), the conditions of the contact reaction include: the temperature is 80-120 ℃ and the time is 20-60 minutes.
24. The production method according to claim 23, wherein in the step (2), the conditions of the contact reaction include: the temperature is 80-100 ℃ and the time is 20-50 minutes.
25. A catalyst component for olefin polymerization prepared by the preparation method of any one of claims 1 to 24.
26. A catalyst for the polymerization of olefins, characterized in that the catalyst comprises:
(1) the catalyst component for the polymerization of olefins according to claim 25;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
27. An olefin polymerization process, comprising: olefin polymerization is carried out by contacting one or more olefins with the catalyst component for olefin polymerization of claim 25, an alkylaluminum compound and optionally an external electron donor compound under olefin polymerization conditions.
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