CN114478857A - Olefin polymerization catalyst carrier and preparation method thereof - Google Patents
Olefin polymerization catalyst carrier and preparation method thereof Download PDFInfo
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- CN114478857A CN114478857A CN202011157579.4A CN202011157579A CN114478857A CN 114478857 A CN114478857 A CN 114478857A CN 202011157579 A CN202011157579 A CN 202011157579A CN 114478857 A CN114478857 A CN 114478857A
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Abstract
The invention discloses an olefin polymerization catalyst carrier and a preparation method thereof. The olefin polymerization catalyst carrier has a composition of a magnesium compound and a copper compound, R, as shown in the general formula (I)1Is C1～C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1～C5The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be optionally substituted with a halogen atom; x and Y are selected from halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n is 2; a is more than or equal to 0<2，0<b≤2，a+b＝2；0<q<0.1；0≤z<0.1; LB is a compound of the general formula (II). The carrier prepared by the invention has better particle shape, and the carrierThe catalyst prepared by the catalyst has better hydrogen regulation sensitivity when being used for olefin polymerization, particularly propylene polymerization or copolymerization.
Description
Technical Field
The present invention relates to an olefin polymerization catalyst support having a composition of a magnesium-containing compound containing a small amount of a Lewis base and a copper-containing compound, and a process for producing the same. The invention also relates to the application of the olefin polymerization catalyst carrier.
Technical Field
Catalysts for the polymerization of olefins are mostly prepared by supporting a titanium halide on active anhydrous magnesium chloride. Among them, one method for preparing active magnesium chloride is to use anhydrous alpha-MgCl2Reacting with alcohol to form an adduct, and then using the adduct as a carrier to support 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.
The activated magnesium chloride carrier can be prepared by taking alkoxy magnesium as a raw material. CN1016422B discloses a method for preparing a solid component of a Z-N catalyst, which is carried out in the presence of a transition metal alkoxideThe soluble magnesium dialkyl is reacted with a transition metal halide and the solid component is precipitated with a liquid hydrocarbon. The alkoxy group in the dialkoxy magnesium used is a linear alkoxy group having 6 to 12 carbon atoms or a branched alkoxy group having 5 to 12 carbon atoms so as to form a magnesium alkoxide solution soluble in liquid hydrocarbon, but such alkoxy magnesium is difficult to obtain. CN1177868C discloses a method for preparing a precursor of an olefin polymerization catalyst, which is prepared by reacting magnesium alkoxide with titanium alkoxide in the presence of a blocking agent to form a solid complex. Wherein the magnesium alkoxide is diethoxymagnesium and the titanium alkoxide is tetraethoxytitanium. CN101056894A discloses a catalyst for propylene polymerization, which is prepared by reacting dialkoxy magnesium with titanium halide compound or silane halide compound and internal electron donor in the presence of organic solvent. Wherein the dialkoxymagnesium has the formula Mg (OR)2Wherein R is C1-C6 alkyl and is prepared by the reaction of magnesium metal and alcohol. CN101190953A discloses a preparation method of a solid component of an olefin polymerization catalyst, which comprises the step of reacting a magnesium-containing complex with a general formula of ClMg (OR) n (ROH) with an electron donor compound and titanium tetrahalide respectively in the presence of inert hydrocarbon to prepare the catalyst. The magnesium-containing complex is prepared by reacting metal magnesium powder with alcohol, wherein R in the general formula is selected from alkyl of C1-C5, and n is 0.1-1.0.
The alkoxy magnesium compound is mostly prepared by taking magnesium powder or alkyl magnesium as a raw material, and compared with magnesium chloride, the alkoxy magnesium compound has high raw material price and complex preparation process.
In order to further simplify the preparation process of the carrier and improve the polymerization performance of the catalyst, researchers develop a new process for preparing the spherical magnesium compound carrier by a reaction precipitation method. 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. On the basis, the patents CN111072804A, CN111072811A, CN107915792A, CN107915793A, CN107915795A, CN109400763A, CN109400778A and CN111072803A successively disclose that metal halides such as zinc halide, chromium halide, manganese halide, iron halide and alkali metal halide are added in the preparation process of the carrier to improve the particle morphology and the polymerization performance of the carrier, but the addition of the metal halide has no obvious influence on the particle size of the carrier.
Disclosure of Invention
It is a first object of the present invention to provide a catalyst support for olefin polymerization comprising a composition of a magnesium-containing compound and a copper-containing compound containing a small amount of a Lewis base. The catalyst carrier has simple preparation process and low energy consumption in the preparation process. The catalyst prepared by the carrier shows higher polymerization activity and stereospecificity when used for olefin polymerization, particularly propylene polymerization or copolymerization.
The second object of the present invention is to provide a method for preparing a carrier for an olefin polymerization catalyst.
The third object of the present invention is to provide an olefin polymerization catalyst support 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 an olefin polymerization catalyst carrier, which comprises the following components shown in a general formula (I):
R1is C1～C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1～C5Linear or branched alkyl ofWherein hydrogen on the alkyl group is optionally substituted with a halogen atom; x and Y are selected from halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n is 2; a is more than or equal to 0<2，0<b≤2，a+b＝2；0<q<0.1；0≤z<0.1；
LB is a compound of the general formula (II),
in the general formula (II), R5And R7Same or different, is hydrogen or C1～C8The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be substituted with a hydroxyl group; r is6Is C1～C8Linear or branched alkylene groups of (a).
According to the invention, the general formula (I) represents
CuYa(OR4)bAnd LB-forming compositions.
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, in formula (I), 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 independently being methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl.
According to some embodiments of the invention, in formula (II), R5And R7Is hydrogen or C1～C5Linear or branched alkyl of R6Is C1～C5Linear or branched alkylene groups of (a). In some embodiments, R5And R7Hydrogen or methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, etc. In some embodiments, R6Methylene, ethylene, propylene, and the like.
According to some embodiments of the invention, the compound of formula (II) is selected from one or more of ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, N-diethylethanolamine, and N-methyldiethanolamine.
In the context of the present application, the halogen is selected from chlorine, bromine and iodine, preferably chlorine.
According to some embodiments of the invention, the spherical support 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 also provides a preparation method of the olefin polymerization catalyst carrier, which comprises the following steps:
(a) the general formula is MgX2Magnesium halide, metal halide with the structural formula of CuYc and the general formula of R1Reacting an alcohol compound represented by OH with a compound represented by the general formula (II) to form a solution,
wherein R is1Is C1～C12Linear or branched alkyl of R5And R7Same or different, is hydrogen or C1～C8The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be substituted with a hydroxyl group; r6Is C1～C8X and Y are halogen, c ═ 1 or 2;
(b) reacting the solution of (a) with an epoxy compound to form spherical solid particles.
According to some preferred embodiments of the present invention, the epoxy compound is represented by the general formula (III),
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 for example: 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 embodiments of the invention, in formula (II), R5And R7Is hydrogen or C1～C5Linear or branched alkyl of R6Is C1～C5Linear or branched alkylene groups of (a). In some embodiments, R5And R7Hydrogen or methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, etc. In some embodiments, R6Methylene, ethylene, propylene, and the like.
According to some embodiments of the invention, the compound of formula (II) is selected from one or more of ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, N-diethylethanolamine, and N-methyldiethanolamine.
According to some preferred 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). Preferably, R2And R3Each independently of the other being methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromineAnd (4) ethyl.
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: 200-1: 10, preferably 1: 200-1: 20. 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, the metal halide of formula CuYc is added in an amount of 0.001 to 0.1 mole, preferably 0.003 to 0.08, per mole of magnesium.
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. The amount of inert dispersion medium added and 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 for formula (I), specific compounds are as follows: magnesium dichloride, magnesium dibromide and magnesium diiodide, wherein magnesium dichloride is preferred. The MgX2The compounds may be used alone or in admixture thereof.
According to some preferred embodiments of the present invention, said CuYc in said step (a) is cuprous halide, most preferably cuprous chloride. The CuYc compounds can be used alone or in combination.
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 epoxy compound is added in an amount of 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, the preparation method further comprises a step (c) of recovering the obtained solid 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 for preparing the olefin polymerization catalyst support 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 metal halide having the structure CuYc 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.
In a more preferred embodiment, the method for preparing the olefin polymerization catalyst support comprises:
(1) heating a mixture of magnesium halide, organic alcohol, metal halide with a structure of CuYc, compound with a general formula (II) and at least one high molecular dispersion stabilizer to 30-160 ℃, preferably 40-120 ℃ in a closed container under stirring to react 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) to be added is 0.005 to 0.1 mol, preferably 0.005 to 0.05 mol. A metal halide having the structure CuYc, which is added in an amount of 0.01 to 0.1 mol, preferably 0.01 to 0.05 mol, per mol of magnesium. 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.
(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 linear or linear liquid alkane or aromatic hydrocarbon having a carbon chain length of more than 4 carbons, and specifically, for example, hexane, heptane, octane, decane, toluene, and the like.
The invention also provides a carrier prepared by the preparation method. According to an embodiment of the invention, the support 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 also provides a catalyst component for olefin polymerization, which contains a reaction product of the olefin polymerization catalyst carrier and/or the olefin polymerization catalyst carrier prepared by the preparation method, a titanium compound and an internal electron donor compound.
The catalyst component can be synthesized by a known synthesis method, such as that described in Chinese patent CN1091748, spherical magnesium-containing composition particles are directly reacted 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 the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexeneOne or more of them.
Compared with the magnesium compound prepared by the prior art, the carrier provided by the invention has the following partial or whole advantages: (1) the carrier formed by the invention has improved particle morphology, and reduces particle adhesion; (2) under the condition of not adjusting the stirring speed, the particle size of the carrier can be adjusted by adjusting the addition of the metal halide CuY with reducibility, and particularly, the carrier with small particle size can be obtained by compounding the metal halide CuY with the compound with the general formula (II) without changing the stirring speed, so that the equipment cost is reduced and the stability of the preparation of the carrier is improved; (3) when the stirring speed is increased to obtain the carrier with smaller particle size, the particle shape of the carrier can be improved, and the particle size distribution is reduced; (4) the catalyst prepared by the carrier has higher hydrogen regulation sensitivity when being used for olefin polymerization, particularly propylene polymerization or copolymerization.
Drawings
Fig. 1 is an optical microscope photograph of the morphology of the carrier particles prepared in example 1.
Fig. 2 is an optical microscope photograph of the morphology of the carrier particles prepared in example 3.
Fig. 3 is an optical microscope photograph of the morphology of the carrier particles prepared in example 7.
Fig. 4 is an optical microscope photograph of the morphology of the carrier particles prepared in example 9.
Fig. 5 is an optical microscope photograph of the morphology of the carrier particles prepared in comparative example 1.
Fig. 6 is an optical microscope photograph of the morphology of the carrier particles prepared in comparative example 2.
Fig. 7 is an optical microscope photograph of the morphology of the carrier particles prepared in comparative example 3.
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 the particle size distribution of the carrier particles were measured with 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 olefin polymerization catalyst 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, 3mmol of cuprous chloride, and 2mmol of triethanolamine were sequentially added, and the temperature was raised to 70 ℃ with stirring (stirring speed 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. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the carrier particle size distribution D50 is 68.2 μm, Span is 0.64, and the particle morphology is shown in fig. 1.
Example 2
The preparation process differed from example 1 only in that the amount of cuprous chloride added was 6 mmol. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the carrier particle size distribution D50 was 54.8 μm, and Span was 0.64.
Example 3
The preparation method is different from that of example 1 only in that 0.01mol of cuprous chloride is added. The carrier particle size distribution D50 was 45.4 μm, and Span was 0.64. The particle morphology is shown in FIG. 2.
Example 4
The preparation method differs from example 3 only in that the reaction temperature is 60 ℃. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the carrier particle size distribution D50 was 31 μm, Span was 0.64.
Example 5
The preparation method is different from that of example 3 only in that the addition amount of ethanol is 2.4mol, and the addition amount of cuprous chloride is 0.01 mol. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the carrier particle size distribution D50 was 36.2 μm and Span was 0.64.
Example 6
The preparation method is different from that of example 2 only in that the amount of triethanolamine added is 0.01 mol. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the carrier particle size distribution D50 ═ 57.8 μm, Span ═ 0.7.
Example 7
The preparation process differs from example 1 only in that 2mmol of triethanolamine is replaced by 4mmol of N, N-dimethylethanolamine. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the particle size distribution D50 is 52.8 μm, Span is 0.64, and the particle morphology is shown in fig. 3.
Example 8
The preparation process differed from example 4 only in that the stirring speed was 1200 rpm.
The carrier particle size distribution D50 is 24.5 μm and Span is 0.64.
Example 9
The preparation process differed from example 1 only in that no triethanolamine was added. By nuclear magnetic resonance, elemental analysis and gas chromatography characterization, the carrier composition was as follows:
the particle size distribution D50 is 60.4 μm, Span is 0.63, and the particle morphology is shown in FIG. 4.
Example 10
The preparation method is different from that of example 9 only in that 6mmol of cuprous chloride is added and triethanolamine is not added.
The carrier particle size distribution D50 was 57.2 μm, and Span was 0.64.
Example 11
The preparation method is different from that of example 10 only in that cuprous chloride is 12mmol, and triethanolamine is not added.
The carrier particle size distribution D50 was 35.3 μm, and Span was 0.67.
Example 12
The preparation method differs from example 1 only in that cuprous chloride is replaced by cupric chloride.
The particle size distribution D50 of the support was 62.5. mu.m, and Span was 0.69.
Example 13
The preparation process differed from example 12 only in that copper chloride was added in an amount of 6 mmol.
The carrier particle size distribution D50 was 60.2 μm, and Span was 0.68.
B. Preparation of spherical catalyst component
Example 14
(1) Preparation of intermediate reaction products
In a 300mL glass reaction flask with mechanical stirring, 10g of the support prepared in example 1 above was dispersed in 100mL of hexane under nitrogen, cooled to-10 ℃ for 0.5hr, 2.5mL of tetraethyl titanate (TET) (TET/Mg molar ratio 0.2) was added, and the temperature was slowly raised 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 under an inert atmosphere, cooled to-20 deg.C, and 8g of the intermediate product prepared in (1) above was added and the temperature was raised to 110 deg.C. 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. To the reaction vessel were added, under a nitrogen blanket, 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 in this order. 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 15
(1) Preparation of intermediate reaction products
In a 300mL glass reaction flask with mechanical stirring, 10g of the support prepared in example 7 above was dispersed in 100mL of hexane under nitrogen, cooled to-10 ℃ for 0.5hr, 2.5mL of tetraethyl titanate (TET) (TET/Mg molar ratio 0.2) was added, and the temperature was slowly raised 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 under an inert atmosphere, cooled to-20 deg.C, and 8g of the intermediate product prepared in (1) above was added and the temperature was raised to 110 deg.C. 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 16
(1) Preparation of intermediate reaction products
In a 300mL glass reaction flask with mechanical stirring, 10g of the support prepared in example 9 above was dispersed in 100mL of hexane under nitrogen, cooled to-10 ℃ for 0.5hr, 2.5mL of tetraethyl titanate (TET) (TET/Mg molar ratio 0.2) was added, and the temperature was slowly raised 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 under an inert atmosphere, cooled to-20 ℃, added with 8g of the intermediate product prepared in (1) above, and warmed to 110 ℃. 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. Propylene polymerization
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.
Comparative example 1
The same procedure was followed as in example 1 except that cuprous chloride and triethanolamine were not added.
Catalyst preparation and propylene polymerization example 14, the support particle morphology is shown in FIG. 5, and the polymerization results are shown in Table 1. It can be seen from the figure that some of the carrier particles were adhered to form irregular particles.
Comparative example 2
The same procedure was followed as in example 4 except that cuprous chloride and the compound represented by the formula (II) were not added. The carrier particle size distribution D50 is 56.8 μm, Span is 0.65. The carrier particle morphology is shown in FIG. 6. It can be seen from the figure that the carrier carries a large amount of fine slag and that caking occurs.
Comparative example 3
In the same manner as in the preparation of example 4, CuCl and the compound represented by the general formula (II) were not added, and the stirring speed was increased to 1600 rpm. The carrier particle size distribution D50 was 35.4 μm, Span was 0.9. The carrier particle morphology is shown in FIG. 7. It can be seen from the figure that the particle size distribution of the carrier is remarkably broadened.
As can be seen from the particle size distribution of the carrier and the results of the attached figures, cuprous chloride is added in the preparation process of the carrier, the particle morphology of the carrier can be obviously improved, the particle adhesion is reduced, and the particle size of the carrier is obviously reduced along with the increase of the addition amount of the cuprous chloride (examples 1-3 and 9-11); particularly, the carrier is compounded with the amine compound shown in the general formula (II) for use, the surface of the carrier is smoother, the sphericity is better, the particle size adjusting effect is more obvious, and the carrier with small particle size can be obtained under the condition of low-speed stirring (see example 4). When the stirring rotation speed was increased, the particle size of the carrier could be further reduced to 25 μm and had a narrow particle size distribution (see example 8). When cuprous chloride was not added, the particle size of the carrier was 35 μm and the particle size distribution was remarkably broadened even if the stirring speed was increased to 1600rpm (see comparative example 3 and fig. 7). Examples 12 and 13 show that the particle size of the carrier particles is not significantly adjusted by the addition of copper chloride.
TABLE 1 examples Properties of Supported catalysts
As can be seen from the results in Table 1, the addition of the alkanolamine during the preparation of the carrier improves the hydrogen response of the catalyst and has no substantial effect on the polymerization activity of the catalyst.
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. The invention can be modified, as prescribed, within the scope of the claims and 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 (11)
1. An olefin polymerization catalyst support having a composition represented by the general formula (I):
R1is C1～C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1～C5The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be optionally substituted with a halogen atom; x and Y are selected from halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n is 2; a is more than or equal to 0<2，0<b≤2，a+b＝2；0<q<0.1；0≤z<0.1；
LB is a compound of the general formula (II),
in the general formula (II), R5And R7Same or different, is hydrogen or C1～C8The linear or branched alkyl group of (1), wherein a hydrogen on the alkyl group may be substituted with a hydroxyl group; r6Is C1～C8Linear or branched alkylene groups of (a).
2. The olefin polymerization catalyst support according to claim 1, wherein in the general formula (I), R is1Is C1～C8Preferably, R is a linear or branched alkyl group1Selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl; r2And R3Each independently is hydrogen, C1-C3Linear or branched alkyl or halogen substituted C1-C3Preferably, R is a linear or branched alkyl group2And R3Each independently is methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl;
in the general formula (II)，R5And R7Is hydrogen or C1～C5Linear or branched alkyl of R6Is C1～C5Linear or branched alkylene of (a);
the halogen is selected from chlorine, bromine and iodine, preferably chlorine;
preferably, the compound represented by the general formula (II) is selected from one or more of ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, N-diethylethanolamine, and N-methyldiethanolamine.
3. The olefin polymerization catalyst support according to claim 1 or 2, characterized in that the average particle diameter is 10-100 microns, preferably 30-70 microns, and the particle size distribution is less than 1.2, preferably 0.7-0.9.
4. A method for preparing an olefin polymerization catalyst support, comprising the steps of:
(a) the general formula is MgX2Magnesium halide, metal halide with the structural formula of CuYc and the general formula of R1Reacting an alcohol compound represented by OH with a compound represented by the general formula (II) to form a solution,
wherein R is1Is C1～C12Linear or branched alkyl of R5And R7Same or different, is hydrogen or C1～C8The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be substituted with a hydroxyl group; r6Is C1～C8X and Y are halogen, c ═ 1 or 2;
(b) reacting (a) said solution with an epoxy compound, preferably said epoxy compound is of formula (III),
wherein R is2And R3Identical or different and is hydrogen or C1～C5Wherein hydrogen on the alkyl group is optionally substituted with halogen.
5. The method of claim 4, wherein R is1Is C1～C6Linear or branched alkyl of (a); in the general formula (II), R5And R7Is hydrogen or C1～C5Linear or branched alkyl of R6Is C1～C5Linear or branched alkylene of (a); r2And R3Each independently is hydrogen, C1-C3Linear or branched alkyl or halogen substituted C1-C3Linear or branched alkyl groups of (1).
6. The process according to claim 4 or 5, wherein in step (a), a polymeric dispersion stabilizer having a molecular weight of more than 1000, preferably more than 3000, is added during the preparation of the solution, and the magnesium halide is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide.
7. The method of any one of claims 4 to 6, wherein the preparation of the solution in step (a) is carried out at a temperature of 30 to 160 ℃, preferably 40 to 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; the metal halide 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 said step (b) is 30 to 160 ℃, preferably 40 to 120 ℃, wherein the epoxy compound is added in an amount of 1 to 10 moles, preferably 2 to 6 moles, per mole of magnesium.
8. A catalyst support prepared by the preparation process according to any one of claims 4 to 7, preferably having 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.
9. A catalyst component for the polymerization of olefins comprising the reaction product of the support of any of claims 1 to 4 and/or the support of claim 8 with a titanium compound and an internal electron donor compound.
10. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 9, an aluminum alkyl compound and optionally an external electron donor compound.
11. A process for the polymerization of olefins comprising contacting one or more olefins with the catalyst system of claim 10 under olefin polymerization conditions.
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| CN202011157579.4A CN114478857B (en) | 2020-10-26 | 2020-10-26 | Olefin polymerization catalyst carrier and preparation method thereof |
| PCT/CN2021/126397 WO2022089423A1 (en) | 2020-10-26 | 2021-10-26 | Solid component for preparing olefin polymerization catalyst, and preparation method therefor and application thereof |
| EP21885150.9A EP4234590A1 (en) | 2020-10-26 | 2021-10-26 | Solid component for preparing olefin polymerization catalyst, and preparation method therefor and application thereof |
| JP2023525540A JP2023546624A (en) | 2020-10-26 | 2021-10-26 | Solid component for producing olefin polymerization catalyst, its production method and its utilization |
| KR1020237017908A KR20230097111A (en) | 2020-10-26 | 2021-10-26 | Solid component for preparing olefin polymerization catalyst, method for preparing the same and application thereof |
| TW110139712A TWI810689B (en) | 2020-10-26 | 2021-10-26 | Solid component for the preparation of olefin polymerization catalyst and its preparation method and application |
| US18/250,551 US20230416424A1 (en) | 2020-10-26 | 2021-10-26 | Solid component for preparing olefin polymerization catalyst, and preparation method therefor and application thereof |
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