Patent Application
20230416424
The present application claims the priority and benefits of the Chinese Patent Application Nos. CN202011156589.6, CN202011157579.4, CN202011157613.8 and CN202011157626.5, filed on Oct. 26, 2020, which are incorporated herein by reference in their entirety and for all purposes.
The present invention relates to a solid component for the preparation of polyolefin catalysts (also known as carrier), a preparation method therefor and use thereof in the preparation of polyolefin catalysts.
Most of the catalysts used for olefin polymerization are prepared by supporting a titanium halide on an active anhydrous magnesium chloride. In such processes, one method used to prepare the active magnesium chloride is to react anhydrous α-MgCl2 with an alcohol to form an adduct, and then this adduct is used as a carrier to support the titanium halide to prepare a solid component of an olefin polymerization catalyst. The magnesium chloride-alcohol adduct can be prepared by methods such as spray drying, spray cooling, high pressure extrusion, high speed stirring, emulsifier, supergravity rotating bed and the like. For instance, U.S. Pat. Nos. 4,421,674, 4,469,648, WO8707620, WO9311166, U.S. Pat. Nos. 5,100,849, 6,020,279, 4,399,054, EP0395383, U.S. Pat. Nos. 6,127,304, 6,323,152, CN1463990, CN1580136, etc. disclose the preparation of the magnesium chloride-alcohol adducts.
In addition, studies have shown that adding a small amount of an electron donor compound to the preparation system of the binary component carrier comprised of the magnesium chloride-alcohol adduct, leading to the formation of a multi-component carrier with a structure formula of MgCl2·mEtOH·nLB, can improve the polymerization performance of the catalyst. For example, patent CN101050245 teaches the addition of phthalate compounds, CN101544710 teaches the addition of C,C-dihydrocarbyloxy hydrocarbon compounds, CN101550205 teaches the addition of polyether compounds, CN101486776 teaches the addition of polyester compounds, CN101215344 teaches the addition of o-alkoxy benzoate compounds, and CN102796127 teaches the addition of alkoxybenzoyl compounds or hydroxybenzoyl compounds. US2008/0293897 teaches the addition of Lewis base compounds other than water during the preparation of the magnesium chloride-alcohol adduct carrier, thereby increasing the polymerization activity of the final catalyst. The Lewis base compounds can be ethers, esters and compounds having a structure formula of RXm, wherein R is an alkyl group of 1 to 20 carbon atoms, and X has the structure of —NH2, —NHR or —OH.
Active magnesium chloride carriers can also be prepared by using magnesium alkoxides as raw materials. CN1016422B discloses a method for preparing a solid component of Z—N catalyst, which is prepared by reacting a soluble dialkylmagnesium with a transition metal halide in the presence of a transition metal alkoxide, and then precipitating the solid component with a liquid hydrocarbon. The alkoxy group in the magnesium dialkoxide used therein is a linear alkoxy group containing 6 to 12 carbon atoms or a branched alkoxy group containing 5 to 12 carbon atoms in order that a magnesium alkoxide solution soluble in liquid hydrocarbons can be formed. However, such magnesium alkoxides are difficult to be obtained. CN1177868C discloses a method for preparing an olefin polymerization catalyst precursor, which is prepared by reacting a magnesium alkoxide with a titanium alkoxide in the presence of a clipping agent to form a solid complex. The magnesium alkoxide is magnesium diethoxide, and the titanium alkoxide is titanium tetraethoxide. CN101056894A discloses a catalyst for propylene polymerization, which is prepared by reacting a magnesium dialkoxide with a titanium halide compound or a halogenated silane compound and an internal electron donor in the presence of an organic solvent. The magnesium dialkoxide has a general formula of Mg(OR)2, wherein R is a C1-C6 alkyl group, and it is prepared by reacting magnesium metal with an alcohol. CN101190953A discloses a method for preparing a solid component of an olefin polymerization catalyst, comprising reacting a magnesium-containing complex of the general formula of ClMg(OR)·n(ROH) with an electron donor compound and a titanium tetrahalide, respectively, in the presence of an inert hydrocarbon. The magnesium-containing complex is prepared by reacting metal magnesium powder with an alcohol, wherein R in the general formula is a C1-C5 alkyl group and n is 0.1 to 1.0.
Patent application CN200910235565 discloses a compound that can be used as an olefin polymerization catalyst carrier and a preparation method thereof. The method comprises heating a magnesium halide, an alcohol compound and an inert dispersion medium to form a magnesium halide-alcohol adduct solution, and then reacting the solution with an oxirane-type compound to form a spherical carrier. Patent application CN2013104913936 teaches the addition of a polymeric dispersion stabilizer in the above-described preparation process of the carrier so that solid particles with good particle morphology and narrow particle size distribution can be obtained without adding an inert dispersion medium, thereby improving the single-pot yield and reducing solvent recovery costs. On this basis, patent applications CN111072804A, CN111072811A, CN107915792A, CN107915793A, CN107915795A, CN109400763A, CN109400778A, and CN111072803A have successively disclosed the addition of metal halides such as zinc halides, chromium halides, manganese halides, iron halides, alkali metal halides in the above-described preparation process of the carrier to improve the particle morphology and polymerization properties of the carrier.
There remains a need for solid components/carriers useful in the preparation of olefin polymerization catalysts that exhibit desirable properties such as good particle morphology.
An object of the present invention is to provide a solid component useful in the preparation of polyolefin catalysts, which solid component can be used as a carrier for the preparation of an olefin polymerization catalyst, especially a propylene polymerization or copolymerization catalyst. The solid component/carrier of the present invention exhibits good particle morphology, e.g., without the problems of carrier particle agglomeration suffered by the prior art. Further, when used for olefin polymerization, especially propylene polymerization or copolymerization, the catalyst prepared with the solid component as a carrier exhibits high polymerization activity and stereospecificity and/or good hydrogen modulation sensitivity.
A further object of the present invention is to provide a method for preparing the solid component useful in the preparation of polyolefin catalysts. The method of the invention is simple in preparation process and has a low energy consumption in the preparation process.
A still further object of the present invention is to provide a polyolefin catalyst component, which comprises a reaction product of the carrier/solid component of the present invention with a titanium compound and an internal electron donor compound.
A still further object of the present invention is to provide a polyolefin catalyst system.
A still further object of the present invention is to provide an olefin polymerization method.
Other features and advantages of the present invention will be described in detail hereinbelow.
In a first aspect, the present invention provides a solid component useful in the preparation of polyolefin catalysts, comprising:
In the present disclosure, the terms “solid component useful in the preparation of polyolefin catalysts” and “carrier useful in the preparation of polyolefin catalysts (or simply “carrier”)” are used interchangeably.
In some embodiments, the carrier of the present invention comprises a composition represented by the general formula (I), the general formula (I′) or the general formula (I″), or have a composition represented by the general formula (I), the general formula (I′) or the general formula (I″):
As those skilled in the art could understand, the above-described general formula (I) represents a composition consisting of the magnesium compound
and LB in the specified molar ratio. Likewise, the general formula (I′) represents a composition consisting of
and LB in the specified molar ratio. Likewise, the general formula (I″) represents a composition consisting of
and LB in the specified molar ratio.
In some embodiments, the carrier of the present invention comprises a composition represented by the general formula (I′″), or have a composition represented by the general formula (I′″):
As those skilled in the art could understand, the above-described general formula (I′″) represents a composition consisting of the magnesium compound
and LB in the specified molar ratio.
In some embodiments of the present disclosure, R1 is a C1-C8 linear or branched alkyl. Preferably, R1 is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl and 2-ethylhexyl.
In some embodiments of the present disclosure, R2 and R3 are each independently hydrogen, a C1-C3 linear or branched alkyl or halogenated C1-C3 linear or branched alkyl. Preferably, R2 and R3 are each independently methyl, ethyl, chloromethyl, chloroethyl, bromomethyl or bromoethyl.
In some embodiments of the present disclosure, R5 and R7 are hydrogen or a C1-C5 linear or branched alkyl, R6 is a C1-C5 linear or branched alkylene. In some embodiments, R5 and R7 are independently hydrogen, methyl, ethyl, isopropyl, n-propyl, tert-butyl or isobutyl. In some embodiments, R6 is methylene, ethylene or propylene.
In some embodiments of the present disclosure, the compound represented by the general formula (II) useful in the present disclosure is one or more selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine and N-methyldiethanolamine.
In some embodiments of the present disclosure, R10 is hydrogen, amino or a C1-C5 linear or branched alkyl, R11 and R12 are hydrogen or a C1-C5 linear or branched alkyl.
In some embodiments of the present disclosure, the amide compound represented by the general formula (II′) useful in the present disclosure is one or more selected from the group consisting of formamide, acetamide, propionamide, N-methylacetamide, N,N-dimethylacetamide and carbonamide.
In the context of this application, the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine.
According to the present invention, the carrier can further comprise a metal component other than magnesium, such as a transition metal component. Preferably, the other metal component is one or both of iron and copper.
According to some embodiments of the present invention, the content of the other metal component in the solid component, on weight basis, is from 0 to 1%.
According to some embodiments of the present invention, the carrier is spherical. As used herein, the term “spherical” means that the carrier has a sphere-like particle morphology, without requiring the carrier to have a perfectly spherical morphology.
In some embodiments, the carrier has an average particle size of from 10 to 100 microns, preferably from 30 to 70 microns, and a particle size distribution of less than 1.2, preferably from 0.7 to 0.9.
In a second aspect, the present invention provides a method for preparing the carrier for polyolefin catalysts, comprising the steps of:
wherein X is a halogen; R1 is a C1-C12 linear or branched alkyl; R5 and R7, which are the same or different, are hydrogen or an unsubstituted or hydroxyl-substituted C1-C8 linear or branched alkyl; R6 is a C1-C8 linear or branched alkylene; R10 is hydrogen, amino or a C1-C8 linear or branched alkyl; and R11 and R12, which are the same or different, are hydrogen or a C1-C8 linear or branched alkyl;
Here, the expression “directly generate spherical solid particles” has the following meanings:
In a sub-aspect of this aspect, the method comprises the steps of:
wherein R1 is a C1-C12 linear or branched alkyl, R5 and R7, which are the same or different, are hydrogen or an unsubstituted or hydroxyl-substituted C1-C8 linear or branched alkyl; R6 is a C1-C8 linear or branched alkylene, X and Y are a halogen, and c=1 or 2, preferably 1;
In another sub-aspect of this aspect, the method comprises the steps of:
wherein R1 is a C1-C12 linear or branched alkyl, R10 is hydrogen, amino or a C1-C8 linear or branched alkyl, R11 and R12, which are the same or different, are hydrogen or a C1-C8 linear or branched alkyl, and X is a halogen;
In some embodiments of this aspect, R1 is a C1-C8 linear or branched alkyl, preferably a C1-C6 linear or branched alkyl. According to some specific embodiments, R1 is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl and 2-ethylhexyl. According to some preferred embodiments of the present invention, the R1OH compound used in step (a) may be one or more of the alcohol compounds. Specific examples of the alcohol include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, 2-ethyl-1-hexanol.
In some embodiments of this aspect, R5 and R7 are hydrogen or a C1-C5 linear or branched alkyl, and R6 is a C1-C5 linear or branched alkylene. In some embodiments, R5 and R7 are hydrogen or methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl or the like. In some embodiments, R6 is methylene, ethylene, propylene or the like. According to some embodiments of the present invention, the compound represented by the general formula (II) is one or more selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine and N-methyldiethanolamine.
In some embodiments of this aspect, R10 is hydrogen, amino or a C1-C8 linear or branched alkyl, and R11 and R12 are hydrogen or a C1-C5 linear or branched alkyl. According to some embodiments of the present invention, the amide compound is one or more selected from the group consisting of formamide, acetamide, propionamide, N-methylacetamide, N,N-dimethylacetamide and carbonamide.
In some embodiments of this aspect, the epoxy compound is preferably represented by general formula (III),
wherein R2 and R3 are the same or different, and are hydrogen or an unsubstituted or halogenated C1-C5 linear or branched alkyl. Preferably, R2 and R3 are each independently hydrogen, a C1-C3 linear or branched alkyl or a halogenated C1-C3 linear or branched alkyl. Preferably, R2 and R3 are each independently methyl, ethyl, chloromethyl, chloroethyl, bromomethyl or bromoethyl.
In some embodiments of this aspect, in step (a), a polymeric dispersion stabilizer is added during the preparation of the solution, and its weight average molecular weight is greater than 1000, preferably greater than 3000.
In some embodiments of this aspect, the magnesium halide of the general formula MgX2 used in step (a) is one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide.
In some embodiments of this aspect, a metal halide, preferably a reductive metal halide, may be added in said step (a). For example, the metal halide can be selected from those having the structural formula MYa, wherein M is a transition metal, Y is a halogen, and a is 1 or 2. In some specific embodiments, M is copper, and a=1. In other specific embodiments, M is iron, and a=2. Preferred metal halides are CuCl and FeCl2.
In some embodiments of this aspect, the metal halide optionally used in step (a) is one or more selected from the group consisting of ferrous chloride, ferrous bromide, ferrous iodide, and hydrates thereof such as ferrous chloride tetrahydrate, preferably ferrous chloride and its hydrates.
In some embodiments of this aspect, the metal halide optionally used in step (a) is a copper halide, preferably a cuprous halide, most preferably cuprous chloride. It has been found that when the cuprous halide is used in the above preparation method, the cuprous halide is insoluble (or slightly soluble) in the reaction system so that the mixture formed in step (a) is a suspension. Surprisingly, the particle size of the final carrier particles can be significantly affected by the amount of the metal halide added within a certain range.
In some embodiments of this aspect, the prepared carrier has an average particle size of from 10 to 100 microns, preferably from 30 to 70 microns.
In some embodiments of this aspect, the prepared carrier has a particle size distribution of less than 1.2, preferably from 0.7 to 0.9.
In some embodiments of this aspect, the preparation of the solution in said step (a) is carried out at a temperature of from 30 to 160° C., preferably from 40 to 120° C. According to some embodiments of the present invention, the amount of the R1OH compound added ranges from 3 to 30 moles, preferably from 4 to 25 moles, relative to one mole of magnesium. According to some embodiments of the present invention, the molar ratio of the compound represented by the general formula (II) or (II′) to the magnesium halide is from 1:200 to 1:10, preferably from 1:200 to 1:2, for example, from 1:100 to 1:5, preferably from 1:50 to 1:50. According to some preferred embodiments of the present invention, step (a) is carried out in a closed vessel. According to some preferred embodiments of the present invention, in step (a), the order of adding the raw materials during the preparation of the solution is not specific.
In some embodiments of this aspect, the amount of the metal halide added ranges from 0.001 to 0.1 moles, preferably from 0.003 to 0.08 moles, relative to one mole of magnesium.
According to some embodiments of the present invention, an inert dispersion medium may or may not be added during the preparation of the solution in step (a). The inert dispersion medium can be one or a mixture of liquid aliphatic, aromatic or cycloaliphatic hydrocarbons and silicone oils. The ratio (by volume) of the amount of the inert dispersion medium added to the amount of the R1OH added is from 0 to 5:1, preferably from 0 to 2:1.
According to some preferred embodiments of the present invention, examples of the MgX2 compound used in step (a) include, but are not limited to, magnesium dichloride, magnesium dibromide, and magnesium diiodide, among which magnesium dichloride is preferred. The MgX2 compounds can be used separately or in combination.
According to some preferred embodiments of the present invention, the trace amount of water in the individual raw materials added in step (a) can participate in the reaction to form the solution.
According to some preferred embodiments of the present invention, specific examples of the epoxy compound used in step (b) include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epoxy chlorobutane, epoxy bromopropane, epoxy bromobutane, etc.
According to some preferred embodiments of the present invention, the reaction temperature in step (b) ranges from 30 to 160° C., preferably from 40 to 120° C.
According to some preferred embodiments of the present invention, the amount of the ethylene oxide-type compound added in step (b) is from 1 to 10 moles, preferably from 2 to 6 moles, relative to one mole of magnesium.
In order to obtain particles with better particle morphology, it is preferred to add at least one polymeric dispersion stabilizer during the preparation of the solution in step (a), with the weight average molecular weight of the polymeric dispersion stabilizer being greater than 1000, preferably greater than 3000, for example up to 2,000,000 or up to 1,000,000. Particularly, the polymeric dispersion stabilizer may be at least one chosen from polyacrylates, styrene-maleic anhydride copolymers, polystyrene sulfonates, naphthalenesulfonic acid-formaldehyde condensation products, condensed alkyl phenyl ether sulfates, condensed alkylphenol polyoxyethylene ether phosphates, oxyalkyl acrylate copolymer-modified polyethyleneimines, poly(1-dodecyl-4-vinylpyridinium bromide)s, poly(vinylbenzyl trimethyl ammonium salt)s, poly(vinyl alcohol)s, polyacrylamides, ethylene oxide-propylene oxide block copolymers, polyvinylpyrrolidones, poly(vinylpyrrolidone-co-vinyl acetate)s, poly(ethylene glycol)s, alkylphenyl polyoxyethylene ethers and poly(alkyl methacrylate)s, preferably at least one of polyvinylpyrrolidones, poly(vinylpyrrolidone-co-vinyl acetate)s and poly(ethylene glycol)s.
According to some preferred embodiments of the present invention, the amount of the polymeric dispersion stabilizer is from 0.1 to 10 percent by weight, preferably from 0.2 to 5 percent by weight, based on the combined amount of the magnesium compound and the R1OH compound.
According to the present invention, the preparation method further comprises step (c) of recovering the resultant solid particles. The recovering of the solids in step (c) refers to the obtaining of solid particles by using solid-liquid separation techniques known in the art, such as filtration, decanting, centrifugal separation and other operations, and also includes washing the obtained spherical carrier particles with a hydrocarbon solvent and drying. The inert hydrocarbon solvent is preferably a straight-chain or branched-chain liquid alkane with a carbon chain length greater than 4 carbons or an aromatic hydrocarbon, such as hexanes, heptanes, octanes, decanes, toluene, and the like.
In a preferred embodiment, the method for preparing the carrier comprises:
In a more preferred embodiment, the method for preparing the carrier comprises:
In a preferred embodiment, the method for preparing the solid component comprises:
In a preferred embodiment, a metal halide having the structure of MYa is also added in the above-described step (1).
In a more preferred embodiment, the method for preparing the spherical carrier comprises:
In the above-described preferred embodiments, the recovering of the solid particles can be carried out by conventional solid-liquid separation techniques in the art, for example, filtration, decanting, centrifugal separation or the like. Furthermore, step (3) may further comprise washing the obtained spherical carrier particles with an inert hydrocarbon solvent and drying. The inert hydrocarbon solvent is preferably a straight-chain or branched-chain liquid alkane with a carbon chain length greater than 4 carbons or an aromatic hydrocarbon, such as hexanes, heptanes, octanes, decanes, toluene, and the like.
The present invention further provides the solid component prepared by the above-described preparation methods. According to some embodiments of the present invention, the solid component is spherical, and has an average particle size of from 10 to 100 microns, preferably from 30 to 70 microns, and a particle size distribution of less than 1.2, preferably from 0.7 to 0.9.
The present invention further provides a catalyst component for olefin polymerization, which comprises a reaction product of the carrier/solid component as described herein and/or the solid component prepared by the preparation methods as described herein with a titanium compound and an internal electron donor compound. The synthesis of the catalyst component can adopt a known synthesis method, such as the method as described in Chinese patent CN1091748 by directly reacting the spherical magnesium-containing composition particles with a titanium halide; or the method as described in Chinese patent CN201310469927 by reacting the spherical magnesium-containing composition with an alkoxytitanium compound having a structural formula of Ti(OR)4 first to obtain an intermediate product and then reacting the intermediate product with a titanium halide. In the above-described preparation processes of the catalyst, it is usual to optionally add some internal electron donor compounds known in the art according to the needs of practical application.
The present invention further provides a catalyst system for olefin polymerization comprising the catalyst component, an alkylaluminum compound, and optionally an external electron donor compound.
The present invention further provides a method for olefin polymerization, comprising contacting one or more olefins with the catalyst system under olefin polymerization conditions. In an embodiment of the present invention, the olefin is of the general formula of CH2═CHR, wherein R is hydrogen or a C1 to C7 alkyl. Preferably, the olefin is one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
The present invention has some or all of the following advantages: (1) the solid component having the composition set forth in the present invention has an improved particle morphology, thereby reducing particle agglomeration; (2) when used for olefin polymerization, especially propylene polymerization or copolymerization, the catalyst prepared by using the solid component of the present invention as a carrier has a high stereospecificity; (3) the catalyst prepared by using the solid component of the present invention as a carrier has a high strength and less break-up; (4) by adding the reductive metal halide and the electron donor compound with specific structure to the reaction system, it can be realized to adjust the particle size of the carrier without changing the stirring speed, especially to obtain a carrier having a small particle size (<40 μm) without changing the stirring speed; (5) the carrier preparation method is stable.
The following examples are provided to further illustrate the present invention and by no means intend to limit the scope thereof.
In a 1.0 L reaction kettle, 1.6 g of polyvinylpyrrolidone (PVP, having a weight average molecular weight of 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, and 0.015 mol of formamide were successively added, and the temperature was raised to 70° C. under stirring (450 rpm). After 1 hour of constant temperature reaction, 0.6 mol of epichlorohydrin was added, the temperature was maintained for 0.5 hours, and the liquid was then filtered off. The solids were washed 5 times with hexane, and dried in vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the composition of the solid component particles was found to be:
The solid component particles have a particle size distribution of D50=63.5 μm and span=0.67, and the particle morphology is shown in
Preparation method was the same as described for Example 1, except that the amount of the formamide was 0.03 mol and the reaction temperature was 80° C. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the composition of the solid component particles was found to be:
The solid component particles have a particle size distribution of D50=45.2 μm and span=0.65.
Preparation method was the same as described for Example 1, except that the amount of the formamide was 0.005 mol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the composition of the solid component particles was found to be:
The carrier has a particle size distribution of D50=78.5 μm and span=0.67.
Preparation method was the same as described for Example 1, except that 2 mmol of ferrous chloride was additionally added. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the solid component particles had the same main composition as that of Example 1 and contained 0.046 wt % of Fe.
The solid component particles have a particle size distribution of D50=61.4 μm and span=0.69, and the particle morphology is shown in
Preparation method was the same as described for Example 4, except that the amount of the added ferrous chloride was 9 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the solid component particles had the same main composition as that of Example 1 and contained 0.59 wt % of Fe.
The solid component particles have a particle size distribution of D50=47.1 μm and span=0.76.
Preparation method was the same as described for Example 1, except that 5 mmol of cuprous chloride was additionally added. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the solid component particles had the same main composition as that of Example 1 and contained 0.038 wt % of Cu.
The solid component particles have a particle size distribution of D50=53.1 μm and span=0.68.
Preparation method was the same as described for Example 1, except that the 0.015 mol of formamide was replaced with 0.02 mol of N,N-dimethylacetamide. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the main composition of the solid component particles was found to be:
The solid component particles have a particle size distribution of D50=65.1 μm and span=0.65.
Preparation method was the same as described for Example 1, except that the 0.015 mol of formamide was replaced with 0.02 mol of N-methylacetamide. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the main composition of the solid component particles was found to be:
The solid component particles have a particle size distribution of D50=57.8 μm and span=0.67.
Preparation method was the same as described for Example 1, except that the amount of the formamide added was changed to 0.04 mol and the reaction temperature was 60° C. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the composition of the solid component particles was found to be:
The solid component particles have a particle size distribution of D50=43.6 μm and span=0.66.
Preparation method was the same as described for Example 1, except that the 0.015 mol of formamide was replaced with 0.01 mol of carbonamide. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, the composition of the solid component particles was found to be:
The solid component particles have a particle size distribution of D50=65.3 μm and span=0.65.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the solid component particles prepared in Example 1 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 1.
The procedure of Example 11 was repeated, except that the solid component particles used were those prepared in Example 6.
The procedure of Example 10 was repeated, except that the solid component particles used were those prepared in Example 7.
The preparation of spherical carrier was the same as described for Example 1, except that the amide compound of the general formula (II) was not added. The morphology of the solid component particles is shown in
Catalyst preparation and propylene polymerization were performed as described in Example 11, and the polymerization results are shown in Table 1.
It can be seen from the particle size distributions of the above solid components and the results of the accompanying drawings that the present invention improves the particle morphology of the carrier by adding the amide compound represented by the general formula (II) during the preparation of the carrier, and further reduces the particle agglomeration.
It can be seen from the results in Table 1 that the addition of amide compounds during the preparation of the carrier can improve the stereospecificity of the catalyst and has little effect on the polymerization activity of the catalyst.
The picture of the catalyst component of the Example 1 is shown in
In a 1.0 L reaction kettle, 1.6 g of polyvinylpyrrolidone (PVP, having a weight average molecular weight of 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, 2 mmol of ferrous chloride, and 2 mmol of triethanolamine were successively added, and the temperature was raised to 70° C. under stirring (450 rpm). After 1 hour of constant temperature reaction, 0.6 mol of epichlorohydrin was added, the temperature was maintained for 0.5 hours, and the liquid was then filtered off. The solids were washed 5 times with hexane, and dried in vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=71.1 μm and span=0.65, and the particle morphology is shown in
The preparation method was the same as described in Example 14, except that the amount of the ferrous chloride added was 4 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=68.2 μm and span=0.67.
The preparation method was the same as described in Example 14, except that the amount of the ferrous chloride added was 8 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=39.8 μm and span=0.68.
The preparation method was the same as described in Example 14, except that the reaction temperature was 80° C. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=72.2 μm and span=0.65.
The preparation method was the same as described in Example 14, except that the reaction temperature was 60° C.
The carrier has a particle size distribution of D50=38.8 μm and span=0.66.
The preparation method was the same as described in Example 18, except that the amount of the ferrous chloride added was 5 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=35.4 μm and span=0.66.
The preparation method was the same as described in Example 14, except that the amount of ferrous chloride tetrahydrate added was 0.1 g.
The carrier has a particle size distribution of D50=81.6 μm and span=0.59.
The preparation method was the same as described in Example 20, except that the amount of the ethanol added was 2.4 mol.
The carrier has a particle size distribution of D50=73.5 μm and span=0.67.
The preparation method was the same as described in Example 14, except that the 2 mmol of triethanolamine was replaced with 4 mmol of N,N-dimethylethanolamine. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=69.5 μm and span=0.64.
The preparation method was the same as described in Example 16, except that the amount of the triethanolamine added was 0.01 mol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following structure:
The carrier has a particle size distribution of D50=53.2 μm and span=0.68.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 14 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 2.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 15 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 2.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 21 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 2.
Preparation method was the same as described in Example 19, except that the ferrous chloride and the compound of the formula (II) were not added, and that the stirring speed was increased to 1600 rpm. The carrier has a particle size distribution of D50=35.4 μm and span=0.9.
Preparation method was the same as described in Example 14, except that the 2 mmol of ferrous chloride was replaced with 3 mmol of ferric chloride. The carrier has a particle size distribution of D50=76.5 μm and span=0.68. It was observed that some of the carrier particles agglomerated to form irregular particles.
Preparation method was the same as described in Example 14, except that the 2 mmol of ferrous chloride was replaced with 6 mmol of ferric chloride. The carrier has a particle size distribution of D50=72.5 μm and span=0.67.
Preparation method was the same as described in Example 14, except that the triethanolamine was not added. The carrier has a particle size distribution of D50=71.0 μm and span=0.67. It was observed that the carrier has a rough surface and a small amount of agglomeration.
It can be seen from the particle size distributions of the above carriers and the results of the accompanying drawings that adding ferrous chloride during the preparation of the carriers according to the present invention can significantly improve the particle morphology of the carrier and reduce particle agglomeration. Also, as the amount of the ferrous chloride added increases, the particle size of the carrier decreases significantly (cf. Examples 14 to 16), and a carrier having a small particle size can be obtained even under low-speed stirring (cf. Example 19). When no ferrous chloride is added, even if the stirring speed is increased to 1600 rpm, the particle size of the carrier is still 35 μm, and the particle size distribution is obviously broadened (cf. Comparative Example 2).
Comparative Examples 3 and 4 show that the effect of adding ferric chloride on adjusting the particle size of the carrier particles is not obvious. Comparative Example 5 shows that only when it is used in combination with the compound of the general formula (II), does the ferrous chloride have obvious improvement effects on the particle morphology of the carrier.
A picture of the catalyst of Example 24 is shown in
It can be seen from the results in Table 2 and
In a 1.0 L reaction kettle, 1.6 g of polyvinylpyrrolidone (PVP, having a weight average molecular weight of 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, and 2 mmol of triethanolamine were successively added, and the temperature was raised to 70° C. under stirring (450 rpm). After 1 hour of constant temperature reaction, 0.6 mol of epichlorohydrin was added, the temperature was maintained for 0.5 hours, and the liquid was then filtered off. The solids were washed 5 times with hexane and dried in vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=59.9 μm and span=0.66, and the particle morphology is shown in
The preparation method was the same as described in Example 27, except that the amount of the triethanolamine added was 4 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=66 μm and span=0.65.
The preparation method was the same as described in Example 27, except that the amount of triethanolamine added was 6 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=86 μm and span=0.73.
The preparation method was the same as described in Example 27, except that the 2 mmol of triethanolamine was replaced with 4 mmol of N,N-dimethylethanolamine. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=58.6 μm and span=0.65.
The preparation method was the same as described in Example 27, except that the 2 mmol of triethanolamine was replaced with 2 mmol of diethanolamine. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=58.6 μm and span=0.65.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 27 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 3.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 30 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 3.
It can be seen from the particle size distributions of the above carriers and the results of the accompanying drawings that adding the compound represented by the general formula (II) during the preparation of the carriers according to the present invention can improve the particle morphology of the carrier so that the particles are of surface smooth and therefore further reduce particle agglomeration.
It can be seen from the results in Table 3 that the addition of the alcohol amine compounds during the preparation of the carrier can improve the hydrogen modulation sensitivity of the catalyst.
In a 1.0 L reaction kettle, 1.6 g of polyvinylpyrrolidone (PVP, having a weight average molecular weight of 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, 3 mmol of cuprous chloride and 2 mmol of triethanolamine were successively added, and the temperature was raised to 70° C. under stirring (with a stirring speed of 450 rpm). After 1 hour of constant temperature reaction, 0.6 mol of epichlorohydrin was added, the temperature was maintained for 0.5 hours, and the liquid was then filtered off. The solids were washed 5 times with hexane, and dried in vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=68.2 μm and span=0.64.
The preparation method was the same as described in Example 34, except that the amount of the cuprous chloride added was 6 mmol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=54.8 μm and span=0.64.
The preparation method was the same as described in Example 34, except that the amount of the cuprous chloride added was 0.01 mol. The carrier has a particle size distribution of D50=45.4 μm and span=0.64.
The preparation method was the same as described in Example 36, except that the reaction temperature was 60° C. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=31 μm and span=0.64.
The preparation method was the same as described in Example 36, except that the amount of the ethanol added was 2.4 mol, and the amount of the cuprous chloride added was 0.01 mol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=36.2 μm and span=0.64.
The preparation method was the same as described in Example 35, except that the amount of the triethanolamine added was 0.01 mol. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=57.8 μm and span=0.7.
The preparation method was the same as described in Example 34, except that the 2 mmol of triethanolamine was replaced with 4 mmol of N,N-dimethylethanolamine. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=52.8 μm and span=0.64.
The preparation method was the same as described in Example 37, except that the stirring speed was 1200 rpm.
The carrier has a particle size distribution of D50=24.5 μm and span=0.64.
The preparation method was the same as described in Example 34, except that the triethanolamine was not added. Through characterization by nuclear magnetic resonance, elemental analysis and gas chromatography, it was found that the carrier had the following composition:
The carrier has a particle size distribution of D50=60.4 μm and span=0.63.
The preparation method was the same as described in Example 42, except that the amount of the cuprous chloride was 6 mmol, and the triethanolamine was not added.
The carrier has a particle size distribution of D50=57.2 μm and span=0.64.
The preparation method was the same as described in Example 43, except that the amount of the cuprous chloride was 12 mmol, and the triethanolamine was not added.
The carrier has a particle size distribution of D50=35.3 μm and span=0.67.
The preparation method was the same as described in Example 34, except that the cuprous chloride was replaced with copper chloride.
The carrier has a particle size distribution of D50=62.5 μm and span=0.69.
The preparation method was the same as described in Example 45, except that the amount of the copper chloride added was 6 mmol.
The carrier has a particle size distribution of D50=60.2 μm and span=0.68.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 34 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 4.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 40 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 4.
In a 300 mL glass reaction flask with mechanical stirring, under nitrogen atmosphere, 10 g of the carrier prepared in Example 42 were dispersed in 100 mL of hexane, cooled to −10° C., and maintained for 0.5 hr. Then, 2.5 ml of tetraethyl titanate (TET) (corresponding to a molar ratio of TET/Mg=0.2) was added thereto, and the temperature was slowly raised to 60° C. and maintained for 0.5 hr. The liquid was filtered off, and the solids were washed three times with hexane and then dried under vacuum to afford an intermediate product.
Under an inert atmosphere, 100 ml of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to −20° C., and 8 g of the intermediate product prepared above in (1) was added thereto. The temperature was raised to 110° C., and 1.5 ml of diisobutyl phthalate was added during the heating process. The liquid was filtered off, and the solids were washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain a spherical catalyst component.
A liquid phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 ml of triethylaluminum solution in hexane (having a concentration of 0.5 mmol/ml), 1 ml of cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (having a concentration of 0.1 mmol/ml) and 9 mg of the above spherical catalyst component were successively added to the autoclave. The autoclave was closed and an amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70° C., and the reaction was performed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the materials were discharged, and the resultant propylene homopolymer was dried and weighed. The results are shown in Table 4.
It can be seen from the particle size distributions of the above carriers and the results of the accompanying drawings that adding cuprous chloride during the preparation of the carriers according to the present invention can significantly improve the particle morphology of the carrier and reduce particle agglomeration. Also, as the amount of the cuprous chloride added increases, the particle size of the carrier decreases significantly (cf. Examples 34 to 36 and 42 to 44). In particular, when the cuprous chloride is used in combination with the amine compound represented by the general formula (II), the surface of the carrier is smoother, the sphericity of the carrier is better, the adjustment effect on the particle size is more obvious, and a small particle size carrier can be obtained even under low-speed stirring (cf. Example 37). When the stirring speed is increased, the particle size of the carrier can be further reduced to 25 μm and a narrow particle size distribution can be achieved (cf Example 41). When no cuprous chloride is added, even if the stirring speed is increased to 1600 rpm, the particle size of the carrier is still 35 μm, and the particle size distribution is obviously broadened (cf. Comparative Example 2). Examples 45 and 46 show that the effect of adding copper chloride on adjusting the particle size of the carrier particles is not obvious.
It can be seen from the results in Table 4 that the addition of alcohol amine compounds during the preparation of the carrier can improve the hydrogen modulation sensitivity of the catalyst, and has substantially no influence on the polymerization activity of the catalyst.
It should be noted that the foregoing examples are only used to explain the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to typical examples, but it should be understood that the words used therein are descriptive and explanative, rather than limitative. The present invention may be modified within the scope of the claims of the present invention as specified, and may be modified without departing from the scope and spirit of the present invention. Although the invention described herein relates to the specific methods, materials and examples, it is not intended to be limited to the specific examples disclosed therein, but rather, the invention extends to all other methods and applications having the same function.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202011156589.6 | Oct 2020 | CN | national |
| 202011157579.4 | Oct 2020 | CN | national |
| 202011157613.8 | Oct 2020 | CN | national |
| 202011157626.5 | Oct 2020 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/126397 | 10/26/2021 | WO |
