CN114478853A - Solid component for preparing olefin polymerization catalyst, preparation method and application thereof - Google Patents

Solid component for preparing olefin polymerization catalyst, preparation method and application thereof Download PDF

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CN114478853A
CN114478853A CN202011156589.6A CN202011156589A CN114478853A CN 114478853 A CN114478853 A CN 114478853A CN 202011156589 A CN202011156589 A CN 202011156589A CN 114478853 A CN114478853 A CN 114478853A
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hydrogen
solid component
linear
branched alkyl
general formula
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CN114478853B (en
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李威莅
夏先知
周俊领
刘月祥
凌永泰
刘涛
赵瑾
高富堂
任春红
谭扬
陈龙
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to TW110139712A priority patent/TWI810689B/en
Priority to US18/250,551 priority patent/US20230416424A1/en
Priority to EP21885150.9A priority patent/EP4234590A1/en
Priority to PCT/CN2021/126397 priority patent/WO2022089423A1/en
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

The invention discloses a solid component for preparing an olefin polymerization catalyst, and a preparation method and application thereof. The solid component comprises a composition shown as a general formula (I), wherein R1Is C1～C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1‑C5A straight or branched chain alkyl group, wherein hydrogen on the alkyl group is optionally substituted with a halogen atom; x is halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n is 2; 0<z<0.5; LB is amide compound with general formula (II). Wherein R is10Is hydrogen, amino or C1～C5Alkyl of R11、R12May be the same or different and is hydrogen or C1～C5Alkyl group of (1). The solid component prepared by the method has better particle morphology, the catalyst prepared by taking the solid component as a carrier is less broken, and the solid component has better stereospecificity when being used for olefin polymerization, particularly propylene polymerization or copolymerization.
Figure DDA0002742976250000011

Description

Solid component for preparing olefin polymerization catalyst, preparation method and application thereof
Technical Field
The invention relates to a solid component for preparing an olefin polymerization catalyst, and a preparation method and application thereof.
Technical Field
Catalysts for the polymerization of olefins are mostly prepared by supporting titanium halides on active anhydrous magnesium chloride. Among them, one method for preparing active magnesium chloride is to use anhydrous alpha-MgCl2Reacting with alcohol to form adduct, and then using the adduct as carrier to load titanium halide to prepare the solid component of the olefin polymerization catalyst. The magnesium chloride alcoholate can be prepared by spray drying, spray cooling, high-pressure extrusion, high-speed stirring, emulsifying machine, super-gravity rotating bed and the like. Such as: US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304, US6323152, and,Magnesium chloride alcoholates disclosed in CN1463990, CN1580136 and the like.
Patent CN200910235565 discloses a compound useful as a carrier for olefin polymerization catalysts and a process for preparing the same, wherein magnesium halide, an alcohol compound and an inert dispersion medium are heated to form a magnesium halide alcohol compound solution, and then the solution is reacted with an oxirane compound to form a spherical carrier. In patent CN2013104913936, a polymer dispersion stabilizer is added in the above carrier preparation process, 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 the solvent recovery cost.
However, the particle morphology of the carrier obtained by the above reaction precipitation method is not easily controlled, and some particles are easily bonded to each other, which causes deterioration in the particle morphology and flowability of the carrier, and further improvement in the polymerization performance of the catalyst prepared using the carrier is desired.
Disclosure of Invention
It is a first object of the present invention to provide a solid component for preparing an olefin polymerization catalyst, which can be used as a support for preparing an olefin polymerization catalyst, particularly a propylene polymerization or copolymerization catalyst, to overcome the problem of the prior art in which the particles of the support are adhered to each other. Further, when the catalyst prepared by taking the solid component as a carrier is used for olefin polymerization, particularly propylene polymerization or copolymerization, the catalyst shows higher polymerization activity and stereospecificity.
It is a second object of the present invention to provide a process for preparing a solid component for use in the preparation of an olefin polymerization catalyst.
The third object of the present invention is to provide a solid component prepared by the above preparation method.
It is a fourth object of the present invention to provide an olefin polymerization catalyst component.
It is a fifth object of the present invention to provide an olefin polymerization catalyst system.
It is a sixth object of the present invention to provide an olefin polymerization process.
The invention provides a solid component for preparing an olefin polymerization catalyst, which comprises a composition shown in a general formula (I):
Figure BDA0002742976230000021
in the general formula (I), R1Is C1～C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1～C5Wherein hydrogen on the alkyl group is optionally substituted with halogen; x is halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n is 2; 0<z<0.5; LB is an amide compound shown as a general formula (II),
Figure BDA0002742976230000022
in the general formula (II), R10Is hydrogen, amino or C1～C8Linear or branched alkyl of R11And R12Same or different, is hydrogen or C1～C8Linear or branched alkyl groups of (1).
According to the present invention, the above general formula (I) represents a magnesium compound
Figure BDA0002742976230000023
And an amide compound represented by the general formula (II).
According to some embodiments of the invention, in formula (I), R1Is C1～C8Linear or branched alkyl groups of (1). According to some embodiments, R1Selected 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 embodiments of the invention, R2And R3Each independently is hydrogen, C1-C3Linear or branched alkyl or halogen substituted C1-C3Linear or branched alkyl groups of (1). According to some embodiments, R2And R3Each is independentAnd is methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl.
According to some embodiments of the invention, in formula (II), R10Is hydrogen, amino or C1～C5Linear or branched alkyl of R11And R12Is hydrogen or C1～C5Linear or branched alkyl groups of (1).
According to some embodiments of the invention, the amide compound is selected from one or more of formamide, acetamide, propionamide, N-methylacetamide, N-dimethylacetamide and carbamide.
In the context of the present application, the halogen is selected from chlorine, bromine and iodine, preferably chlorine.
According to the present invention, the solid component may further include other metal components other than magnesium, and preferably, the other metal components are selected from one or both of iron and copper.
According to some embodiments of the invention, the other metal component is present in an amount of 0 to 1% by weight of the solid component.
According to some embodiments of the invention, the solid component is spherical, has an average particle diameter of 10 to 100 microns, preferably 30 to 70 microns, and a particle size distribution of less than 1.2, preferably 0.7 to 0.9.
The invention provides a preparation method of a solid component for preparing an olefin polymerization catalyst, which comprises the following steps:
(a) the general formula is MgX2Magnesium halide and a compound of formula R1Reacting an alcohol compound shown by OH with an amide compound shown by a general formula (II) to form a solution,
Figure BDA0002742976230000031
wherein R is1Is C1～C12Linear or branched alkyl of R10Is hydrogen, amino or C1～C8Linear or branched alkyl of R11And R12Is the same as orDifferent from, is hydrogen or C1～C8X is halogen;
(b) (reacting the solution formed in step (a) with an epoxy compound to form a solid component.
According to some preferred embodiments of the present invention, the epoxy compound is represented by the general formula (III),
Figure BDA0002742976230000032
wherein R is2And R3Identical or different and is hydrogen or C1～C5Wherein hydrogen on the alkyl group is optionally substituted with halogen.
According to some preferred embodiments of the invention, R1Is C1～C8Linear or branched alkyl groups of (1). According to some embodiments, R1Selected 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 invention, R in step (a)1The OH compound may be one alcohol compound or a mixture of alcohol compounds. Specific compounds are as follows: methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, 2-ethyl-1-hexanol. The alcohol compounds can be used alone or in combination.
According to some preferred embodiments of the invention, in formula (II), R10Is hydrogen, amino or C1～C5Linear or branched alkyl of R11And R12Is hydrogen or C1～C5Linear or branched alkyl groups of (1). According to some embodiments of the invention, the amide compound is selected from one or more of formamide, acetamide, propionamide, N-methylacetamide, N-dimethylacetamide and carbamide.
According to some preferred embodiments of the invention, R2And R3Each independently is hydrogen, C1-C3OfAlkyl or halogen substituted C1-C3Linear or branched alkyl groups of (1). Preferably, R2And R3Each independently being methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl.
In the step (a), a metal halide having reducibility may be added in the step (a). The metal halide may be MYaWherein Y is halogen and a is 1 or 2. Specifically, when M is copper, a is 1, and when M is iron, a is 2. Preferred compounds are CuCl and FeCl2。
According to some preferred embodiments of the invention, the preparation of the solution in step (a) is carried out at a temperature of 30-160 ℃, preferably 40-120 ℃. According to an embodiment of the invention, R1The OH compound is added in an amount of 3 to 30 moles, preferably 4 to 25 moles, per mole of magnesium. According to an embodiment of the present invention, the compound represented by the general formula (II) is added in a molar ratio to the magnesium halide added of 1: 100-1: 5, preferably 1: 50-1: 5. according to an embodiment of the present invention, the structural formula is MYaThe metal halide of (3) is added in an amount of 0.001 to 0.1 mole, preferably 0.003 to 0.08 mole, per mole of magnesium.
According to some preferred embodiments of the invention, step (a) is carried out in a closed container. According to some preferred embodiments of the present invention, the step (a), during the preparation of the solution, is performed in a non-sequential order.
According to some preferred 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 chosen from liquid aliphatic, aromatic, cycloaliphatic hydrocarbons, silicone oils, or mixtures thereof. According to some preferred embodiments of the invention, the amount of inert dispersion medium added is in combination with R1The ratio (volume ratio) of the added amount of OH is 0 to 5: 1, preferably 0 to 2: 1.
according to some preferred embodiments of the invention, the MgX of step (a)2X is as defined in formula (I), specific compounds are as follows: magnesium dichloride, magnesium dibromide and magnesium diiodide, wherein magnesium dichloride is preferred. SaidMgX2The compounds may be used alone or in admixture thereof.
According to some preferred embodiments of the present invention, a trace amount of water in each of the raw materials added in the step (a) may participate in the reaction for forming a solution.
According to some preferred embodiments of the present invention, the specific compound of the epoxy compound in the step (b) is ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, butylene bromide oxide, or the like.
According to some preferred embodiments of the present invention, the reaction temperature in step (b) is 30 to 160 ℃, preferably 40 to 120 ℃. Wherein the amount of the ethylene oxide compound added is 1 to 10 moles, preferably 2 to 6 moles, per mole of magnesium.
In order to obtain particles with better particle morphology, it is preferred to add at least one polymeric dispersion stabilizer with a molecular weight of more than 1000, preferably more than 3000, during the preparation of the solution in step (a). Specifically, one or a mixture of polyacrylate, styrene-maleic anhydride copolymer, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkyl phenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, polymer of oxyalkyl acrylate copolymer modified polyethyleneimine, 1-dodeca-4-vinylpyridine bromide, polyvinyl benzyl trimethylamine salt, polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, polyethylene glycol, polyoxyethylene condensed alkyl phenyl ether and polyalkylmethacrylate can be selected. Polyvinylpyrrolidone and polyethylene are preferred.
According to some preferred embodiments of the present invention, the polymeric dispersion stabilizer is used in an amount of the magnesium compound and R1The total amount of OH compounds used is 0.1 to 10% by weight, preferably 0.2 to 5% by weight.
According to the present invention, there is further included the step of (c) recovering the resulting solid component particles. The solid recovery in step (c) means that solid particles are obtained by using solid-liquid separation techniques known in the art, such as filtration, decantation, centrifugation, and the like, and the obtained spherical carrier particles are washed by an inert hydrocarbon solvent and dried. Wherein the inert hydrocarbon solvent is preferably straight chain or branched chain liquid alkane and arene with carbon chain length more than 4 carbons; the method specifically comprises the following steps: hexane, heptane, octane, decane, toluene, and the like.
In a preferred embodiment, the method of preparing the solid component comprises:
(1) in a closed container, magnesium halide MgX is added in the presence of at least one high molecular dispersion stabilizer2Organic alcohol R1Reacting a mixture of OH and a compound of formula (II) at 30-160 deg.C (preferably 40-120 deg.C) for 0.1-5 hours (preferably 0.5-2 hours) to form a solution;
(2) reacting the solution with an alkylene oxide compound represented by the formula (III) at 30-160 ℃ (preferably 40-120 ℃) for 0.1-5 hours (preferably 0.2-1 hour), and precipitating solid particles;
(3) and recovering the solid particles by a solid-liquid separation technology to obtain the spherical carrier.
Another preferred embodiment is that in step (1) above, MY is added in addition to the compounds already presentaThe remaining steps are unchanged.
In a more preferred embodiment, the method for preparing the spherical carrier comprises:
(1) heating a mixture of magnesium halide, organic alcohol, the compound of formula (II) and at least one polymeric dispersion stabilizer to 30-160 ℃, preferably 40-120 ℃, under stirring in a closed vessel for 0.1-5 hours, preferably 0.5-2 hours to form a mixture solution, wherein the organic alcohol is used in an amount of 3-30 moles, preferably 4-25 moles per mole of magnesium; the amount of the compound represented by the general formula (II) is 0.01 to 0.5 mol, preferably 0.02 to 0.3 mol. The amount of the polymeric dispersion stabilizer is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total amount of the magnesium halide and the organic alcohol. If the structure MY is added in this stepaThe metal halide of (1), the metal halide is added in an amount of 0.01 to 0.1 mol, preferably 0.01 to 0.05 mol, per mol of magnesium.
(2) Adding the alkylene oxide compound shown in the formula (III) into the mixture solution under stirring, and reacting at 30-160 ℃ (preferably 40-120 ℃) for 0.1-5 hours, preferably 0.2-1 hour to form solid particles, wherein the amount of the alkylene oxide compound is 1-10 moles, preferably 2-6 moles per mole of magnesium;
(3) and recovering the solid particles by a solid-liquid separation technology to obtain the spherical carrier.
In the above preferred embodiment, the process of recovering the solid particles can be performed according to the conventional solid-liquid separation technique in the art, for example, filtration, decantation, centrifugation, etc. can be used. Furthermore, the step (3) may further comprise washing and drying the resulting spherical support particles with an inert hydrocarbon solvent. The inert hydrocarbon solvent is preferably a straight-chain or straight-chain liquid alkane or aromatic hydrocarbon having a carbon chain length of more than 4 carbons, and specifically, for example, hexane, heptane, octane, decane, toluene, or the like can be mentioned.
The invention also provides the solid component prepared by the preparation method. According to an embodiment of the invention, the solid component is spherical, has a mean particle diameter of 10 to 100 microns, preferably 30 to 70 microns, and a particle size distribution of less than 1.2, preferably 0.7 to 0.9.
The invention also provides a catalyst component for olefin polymerization, which contains a reaction product of the solid component and/or the solid component prepared by the preparation method, a titanium compound and an internal electron donor compound. The catalyst component can be synthesized by known synthesis method, such as described in Chinese patent CN1091748, by directly reacting spherical magnesium-containing composition particles with titanium halide; or as described in Chinese patent CN201310469927, a spherical magnesium-containing composition is firstly mixed with a magnesium-containing material with a structural formula of Ti (OR)4The alkoxy titanium compound is reacted to obtain an intermediate product, and then the intermediate product is reacted with titanium halide to prepare the catalyst. In the preparation of the catalyst, some internal electron donor compounds known in the industry may be optionally added according to the actual application.
The invention also provides a catalyst system for olefin polymerization, which comprises the catalyst component, an alkyl aluminum compound and an optional external electron donor compound.
The invention also provides an olefin polymerization process comprising contacting one or more olefins with the catalyst system under olefin polymerization conditions. In an embodiment of the invention, the olefin has the general formula CH2Wherein R is hydrogen or C1-C7An alkyl group. Preferably, the olefin is selected from one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
The invention has some or all of the following advantages: (1) the solid component of the composition of the present invention has improved particle morphology, reducing particle blocking; (2) the catalyst prepared by taking the solid component as the carrier has higher stereospecificity when being used for olefin polymerization, particularly propylene polymerization or copolymerization; (3) the catalyst prepared by using the solid component as the carrier has higher strength and less breakage.
Drawings
FIG. 1 is an optical microscope photograph showing the morphology of solid component particles prepared in example 1.
FIG. 2 is an optical microscope photograph showing the morphology of the solid component particles prepared in example 4.
FIG. 3 is an optical microscope photograph showing the morphology of the solid component particles prepared in example 10.
Fig. 4 is an optical microscope photograph of the morphology of the solid component prepared in comparative example 1.
FIG. 5 is an optical micrograph of the morphology of solid catalyst component particles prepared in example 1.
Fig. 6 is an optical microscope photograph of the morphology of the catalyst component prepared in comparative example 1.
Detailed Description
The following examples further illustrate the invention and are not intended to limit the scope of the invention.
The test method comprises the following steps:
1. polymer melt index: measured according to ASTM D1238-99.
2. Polymer isotactic index: the determination is carried out by adopting a heptane extraction method (boiling extraction for 6 hours by heptane), namely, a 2g dried polymer sample is taken and placed in an extractor to be extracted for 6 hours by boiling heptane, then, the residue is dried to constant weight, and the ratio of the weight (g) of the obtained polymer to 2 is the isotactic index.
3. Testing the particle size distribution: the average particle diameter and particle size distribution of the carrier (i.e., solid component) particles were measured using a Masters Sizer 2000 particle Sizer (manufactured by Malvern Instruments Ltd.). Wherein the particle size distribution value SPAN ═ D90-D10)/D50.
4. The apparent morphology of the catalyst support for olefin polymerization was observed by means of an optical microscope of Eclipse E200, commercially available from Nikon.
5. Content of metal elements in the carrier: inductively coupled plasma mass spectrometer measurements.
6. Catalyst activity is the weight of polymer obtained/weight of catalyst used.
A. Preparation of spherical support
Example 1
In a 1.0L reaction vessel, 1.6g of polyvinylpyrrolidone (PVP, molecular weight 58000), 2.8mol of ethanol, 0.2mol of magnesium chloride, and 0.015mol of formamide were sequentially added, and the temperature was raised to 70 ℃ with stirring (450 rpm). After reacting for 1 hour at constant temperature, adding 0.6mol of epichlorohydrin, maintaining the temperature for reacting for 0.5 hour, filtering out liquid, washing the solid with hexane for 5 times, and drying in vacuum to obtain solid component particles. The composition of the solid component particles was characterized by nuclear magnetic resonance, elemental analysis and gas chromatography as follows:
Figure BDA0002742976230000081
the particle size distribution of the solid component particles D50 ═ 63.5 μm and Span ═ 0.67, and the particle morphology is shown in fig. 1.
Example 2
The preparation method differs from example 1 only in 0.03mol of formamide and 80 ℃ of reaction temperature. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the composition of the solid component particles was as follows:
Figure BDA0002742976230000082
the particle size distribution of the solid component particles D50 ═ 45.2 μm and Span ═ 0.65.
Example 3
The preparation process differs from example 1 only in 0.005mol of formamide. The composition of the solid component particles was characterized by nuclear magnetic resonance, elemental analysis and gas chromatography as follows:
Figure BDA0002742976230000083
the carrier particle size distribution D50 ═ 78.5 μm and Span ═ 0.67.
Example 4
The preparation method differs from example 1 only in that 2mmol of ferrous chloride is additionally added. The bulk composition of the solid component particles was the same as in example 1 and contained 0.046% Fe (by weight) as characterized by nmr, elemental analysis and gas chromatography.
The particle size distribution of the solid component particles D50 ═ 61.4 μm and Span ═ 0.69, and the particle morphology is shown in fig. 2.
Example 5
The preparation process differs from example 4 only in that 9mmol of ferrous chloride are added. The bulk composition of the solid component particles was the same as in example 1 and contained 0.59% Fe (by weight) as characterized by nmr, elemental analysis and gas chromatography.
The particle size distribution of the solid component particles D50 ═ 47.1 μm, Span ═ 0.76.
Example 6
The preparation method differs from example 1 only in that 5mmol of additional cuprous chloride is added. The bulk composition of the solid component particles was the same as in example 1 and contained 0.038% Cu (by weight) as characterized by nmr, elemental analysis and gas chromatography.
The particle size distribution of the solid component particles D50 ═ 53.1 μm and Span ═ 0.68.
Example 7
The preparation process differed from example 1 only in that 0.015mol of formamide was replaced by 0.02mol of N, N-dimethylacetamide. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the bulk composition of the solid component particles was as follows:
Figure BDA0002742976230000091
the particle size distribution of the solid component particles D50 ═ 65.1 μm and Span ═ 0.65.
Example 8
The preparation process differed from example 1 only in that 0.015mol of formamide was replaced by 0.02mol of N-methylacetamide. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the bulk composition of the solid component particles was as follows:
Figure BDA0002742976230000092
the particle size distribution of the solid component particles D50 ═ 57.8 μm and Span ═ 0.67.
Example 9
The preparation process differs from example 1 only in that the amount of formamide added is changed to 0.04mol and the reaction temperature is 60 ℃. The composition of the solid component particles was characterized by nuclear magnetic resonance, elemental analysis and gas chromatography as follows:
Figure BDA0002742976230000093
the particle size distribution of the solid component particles D50 ═ 43.6 μm and Span ═ 0.66.
Example 10
The preparation process differed from example 1 only in that 0.015mol of formamide was replaced by 0.01mol of carbamide. The composition of the solid component particles was characterized by nuclear magnetic resonance, elemental analysis and gas chromatography as follows:
Figure BDA0002742976230000101
the particle size distribution D50 of the solid component particles was 65.3 μm and Span was 0.65, and the particle morphology of the solid component particles is shown in fig. 3.
B. Preparation of spherical catalyst component
Example 11
(1) Preparation of intermediate reaction products
In a 300mL glass reaction flask with mechanical stirring, 10g of the solid component particles prepared in example 1 were dispersed in 100mL of hexane under a nitrogen atmosphere, cooled to-10 ℃ for 0.5hr, added with 2.5mL of tetraethyl titanate (TET) (TET/Mg molar ratio 0.2), slowly heated to 60 ℃ for 0.5 hr. The liquid was filtered off, washed three times with hexane and dried in vacuo to give the intermediate product.
(2) Preparation of the catalyst component
In a 300mL glass reaction flask, 100mL titanium tetrachloride was added, cooled to-20 deg.C, 8g of the intermediate product prepared above was added, and the temperature was raised to 110 deg.C under an inert atmosphere. Adding 1.5ml of diisobutyl phthalate in the temperature rising process, filtering out liquid, washing twice with titanium tetrachloride and three times with hexane, and drying in vacuum to obtain the spherical catalyst component.
C. Polymerization of propylene
The liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. 5ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1mmol/ml) and 9mg of the above spherical catalyst component were successively added to the reaction vessel under a nitrogen blanket. The autoclave was closed and a quantity of hydrogen (standard volume) and 2.3L of liquid propylene were added. Heating to 70 ℃, reacting for 1 hour, cooling, releasing pressure, discharging, drying the obtained propylene homopolymer and weighing. The results are shown in Table 1.
Example 12
Substantially the same as in example 11 except that the solid component particles used were prepared for example 6.
Example 13
Essentially the same as example 10, except that the solid component particles used were prepared for example 7.
Comparative example 1
Preparation of spherical support
The same procedure as in example 1 was followed, except that the amide-based compound of the formula (II) was not added. The morphology of the solid component particles is shown in FIG. 4, from which it can be seen that some of the solid component particles are adhered to form irregular particles.
Catalyst preparation and propylene polymerization example 11, polymerization results are shown in table 1.
As can be seen from the particle size distribution of the solid components and the results of the attached drawings, the amide compound shown in the general formula (II) is added in the preparation process of the carrier, so that the particle morphology of the carrier is improved, and the particle adhesion is further reduced.
TABLE 1 examples Properties of Supported catalysts
Figure BDA0002742976230000111
As can be seen from the results in Table 1, the addition of the amide-based compound during the preparation of the support improves the stereospecificity of the catalyst and has substantially no effect on the polymerization activity of the catalyst.
The picture of the catalyst component of example 1 above is shown in fig. 5, and the picture of the catalyst component of comparative example 1 is shown in fig. 6. As can be seen from the figure, the catalyst prepared by adding the solid component particles of the compound represented by the general formula (II) as a carrier was less broken.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (12)

1. A solid component for the preparation of an olefin polymerization catalyst comprising a composition represented by the general formula (I):
Figure FDA0002742976220000011
in the general formula (I), R1Is C1～C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1～C5Linear or branched alkyl of (a), wherein hydrogen on the alkyl is optionally substituted with halogen; x is halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n is 2; 0<z<0.5; LB is an amide compound shown as a general formula (II),
Figure FDA0002742976220000012
in the general formula (II), R10Is hydrogen, amino or C1～C8Linear or branched alkyl of R11And R12Same or different, is hydrogen or C1～C8Linear or branched alkyl groups of (1).
2. The solid component according to claim 1, wherein in the general formula (I), R1Is C1～C8Preferably, R is a linear or branched alkyl group1Selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl; r2And R3Each independently of the other is hydrogen, C1-C3Linear or branched alkyl or halogen substituted C1-C3Linear or branched alkyl of (2), preferablyEarth, R2And R3Each independently is methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl;
in the general formula (II), R10Is hydrogen, amino or C1～C5Linear or branched alkyl of R11And R12Is hydrogen or C1～C5Linear or branched alkyl of (a);
the halogen is selected from chlorine, bromine and iodine, preferably chlorine;
preferably, the amide compound is selected from one or more of formamide, acetamide, propionamide, N-methylacetamide, N-dimethylacetamide and carbamide.
3. The solid component according to claim 1 or 2, further comprising a further metal component other than magnesium, preferably the further metal component is selected from one or both of the elements iron and copper; preferably, the other metal component accounts for 0-1% of the solid component by weight.
4. The solid component according to any one of claims 1 to 3, characterized in that it is spherical, has a mean particle diameter of 10 to 100 microns, preferably 30 to 70 microns, and a particle size distribution of less than 1.2, preferably 0.7 to 0.9.
5. A method for preparing a solid component for use in the preparation of an olefin polymerization catalyst, comprising the steps of:
(a) the general formula is MgX2Magnesium halide and a compound of formula R1Reacting an alcohol compound shown by OH with an amide compound shown by a general formula (II) to form a solution,
Figure FDA0002742976220000021
wherein R is1Is C1～C12Linear or branched alkyl of R10Is hydrogen, amino or C1～C8Linear or branched alkyl of R11And R12Same or different, is hydrogen or C1～C8X is halogen;
(b) reacting the solution formed in step (a) with an epoxy compound, preferably of formula (III),
Figure FDA0002742976220000022
wherein R is2And R3Identical or different and is hydrogen or C1～C5Wherein hydrogen on the alkyl group is optionally substituted with halogen.
6. The method of claim 5, wherein R is1Is C1～C8Linear or branched alkyl of (a); in the general formula (II), R10Is hydrogen, amino or C1～C5Linear or branched alkyl of R11And R12Is hydrogen or C1～C5Linear or branched alkyl of (a); r2And R3Each independently is hydrogen, C1-C3Linear or branched alkyl or halogen substituted C1-C3Linear or branched alkyl groups of (1).
7. The method according to claim 5 or 6, wherein a reducing metal halide is added during the preparation of the solution in step (a), preferably the metal halide has the formula MYaWherein Y is halogen, M is selected from one or more of copper and iron, a is 1 or 2; more preferably, the metal halide is selected from cuprous chloride and ferrous chloride;
in step (a), a polymeric dispersion stabilizer having a molecular weight greater than 1000, preferably greater than 3000, is added during the preparation of the solution.
8. The method of any one of claims 5 to 7, wherein the preparation of the solution in step (a) is carried out at a temperature of 30-160 ℃, preferably 40-120 ℃; wherein R is1The amount of the OH compound added is 3 to 30 moles, preferably 4 to 25 moles, per mole of magnesium; the molar ratio of the amount of the compound represented by the general formula (II) added to the magnesium halide added is 1: 100-1: 5, preferably 1: 50-1: 5; structural formula is MYaThe metal halide of (b) is added in an amount of 0.001 to 0.1 mole, preferably 0.003 to 0.08 mole, per mole of magnesium; the reaction temperature in the step (b) is 30-160 ℃, preferably 40-120 ℃, wherein the addition amount of the ethylene oxide compound is 1-10 mol, preferably 2-6 mol, per mol of magnesium.
9. A solid component prepared by the preparation method of any one of claims 5 to 8, which is spherical, has an average particle diameter of 10 to 100 microns, preferably 30 to 70 microns, and a particle size distribution of less than 1.2, preferably 0.7 to 0.9.
10. A catalyst component for the polymerization of olefins comprising the reaction product of the solid component according to any of claims 1 to 4 and/or the solid component according to claim 9 with a titanium compound and an internal electron donor compound.
11. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 10, an aluminum alkyl compound and optionally an external electron donor compound.
12. A process for the polymerization of olefins comprising contacting one or more olefins with the catalyst system of claim 11 under olefin polymerization conditions.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60219206A (en) * 1984-04-16 1985-11-01 Mitsui Toatsu Chem Inc Novel polymerization of ethylene or alpha-olefin
CN104558283A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Solid composition as well as preparation method and application thereof
CN110498871A (en) * 2019-08-23 2019-11-26 上海化工研究院有限公司 A kind of alkoxyl magnesium carrier granular and its application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60219206A (en) * 1984-04-16 1985-11-01 Mitsui Toatsu Chem Inc Novel polymerization of ethylene or alpha-olefin
CN104558283A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Solid composition as well as preparation method and application thereof
CN110498871A (en) * 2019-08-23 2019-11-26 上海化工研究院有限公司 A kind of alkoxyl magnesium carrier granular and its application

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