CN114478857B - Olefin polymerization catalyst carrier and preparation method thereof - Google Patents

Olefin polymerization catalyst carrier and preparation method thereof Download PDF

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Publication number
CN114478857B
CN114478857B CN202011157579.4A CN202011157579A CN114478857B CN 114478857 B CN114478857 B CN 114478857B CN 202011157579 A CN202011157579 A CN 202011157579A CN 114478857 B CN114478857 B CN 114478857B
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magnesium
straight
hydrogen
compound
general formula
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CN114478857A (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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Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to TW110139712A priority patent/TWI810689B/en
Priority to PCT/CN2021/126397 priority patent/WO2022089423A1/en
Priority to US18/250,551 priority patent/US20230416424A1/en
Priority to EP21885150.9A priority patent/EP4234590A4/en
Priority to KR1020237017908A priority patent/KR20230097111A/en
Priority to JP2023525540A priority patent/JP2023546624A/en
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    • 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
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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 as shown in the general formula (I), R 1 Is C 1 ～C 12 Straight or branched alkyl of (a); r is R 2 And R is 3 Identical or different, being hydrogen or C 1 ～C 5 Wherein hydrogen on the alkyl group is optionally substituted with a halogen atom; x and Y are selected from halogen; m is 0.1-1.9; n is 0.1 to 1.9; m+n=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 represented by general formula (II). The carrier prepared by the invention has better particle morphology, and the catalyst prepared by the carrier has better hydrogen regulation sensitivity when being used for olefin polymerization, especially propylene polymerization or copolymerization.

Description

Olefin polymerization catalyst carrier and preparation method thereof
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 titanium halides on active anhydrous magnesium chloride. One method for preparing active magnesium chloride is to use anhydrous alpha-MgCl 2 React with alcohol to form adduct, and then the solid component of the olefin polymerization catalyst is prepared by using the adduct as a carrier to load titanium halide. The magnesium chloride alkoxide 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 process for preparing a solid component of a Z-N catalyst by reacting a soluble magnesium dialkyl with a transition metal halide in the presence of a transition metal alkoxide and precipitating the solid component with a liquid hydrocarbon. Wherein the alkoxy in the dialkoxy magnesium is linear alkoxy containing 6-12 carbon atoms or 5-to-5Branched alkoxy groups of 12 carbon atoms so as to be able to form a solution of magnesium alkoxide in liquid hydrocarbon, however such magnesium alkoxides are difficult to obtain. CN1177868C discloses a process for the preparation of a catalyst precursor for olefin polymerization, which precursor is prepared by reacting magnesium alkoxide with titanium alkoxide in the presence of a cleaving agent to form a solid complex. Wherein 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 magnesium dialkoxide with a titanium halide compound or a silane halide compound and an internal electron donor in the presence of an organic solvent. Wherein the dialkoxy magnesium has the general formula of Mg (OR) 2 Wherein R is C1-C6 alkyl and is prepared by reacting magnesium metal with alcohol. CN101190953a discloses a process for preparing a solid component of an olefin polymerization catalyst, which comprises reacting a magnesium-containing complex of the general formula ClMg (OR). N (ROH) with an electron donor compound and titanium tetrahalide, respectively, in the presence of an inert hydrocarbon. The magnesium-containing complex is prepared by reacting metal magnesium powder with alcohol, wherein R in the general formula is selected from C1-C5 alkyl, and n is 0.1-1.0.
The alkoxy magnesium compound is mostly prepared by adopting magnesium powder or alkyl magnesium as raw materials, and compared with magnesium chloride, the alkoxy magnesium compound has high raw material price and complex preparation process.
In order to further simplify the carrier preparation process and improve the polymerization performance of the catalyst, researchers develop a new process for preparing the spherical magnesium compound carrier by utilizing a reaction precipitation method. Patent CN200910235565 discloses a compound useful as a carrier for olefin polymerization catalysts and a process for its preparation by heating a magnesium halide, an alcohol compound and an inert dispersion medium to form a magnesium halide alkoxide solution, and then reacting the solution with an oxirane compound to form a spherical carrier. The patent CN2013104913936 can obtain solid particles with good particle morphology and narrow particle size distribution under the condition of no need of adding inert dispersion medium by adding the macromolecular dispersion stabilizer in the preparation process of the carrier, thereby improving the yield of a single kettle and reducing the recovery cost of the solvent. Based on this, patent CN111072804A, CN111072811A, CN107915792A, CN107915793A, CN107915795A, CN109400763A, CN109400778A, CN111072803a successively discloses that zinc halide, chromium halide, manganese halide, iron halide, alkali metal halide and other metal halides are added during the preparation of the above-mentioned carrier to improve the particle morphology and polymerization properties of the carrier, but no significant influence of the addition of the metal halide on the particle size of the carrier was found.
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 containing a small amount of a lewis base and a copper-containing compound. 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, especially propylene polymerization or copolymerization.
The second object of the present invention is to provide a process for preparing an olefin polymerization catalyst support.
It is a third object of the present invention to provide an olefin polymerization catalyst carrier prepared by the above-mentioned 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 a process for the polymerization of olefins.
The invention provides an olefin polymerization catalyst carrier which comprises the following components shown in a general formula (I):
R 1 is C 1 ～C 12 Straight or branched alkyl of (a); r is R 2 And R is 3 Identical or different, being hydrogen or C 1 ～C 5 Wherein hydrogen on the alkyl group is optionally substituted with a halogen atom; x and Y are selected from halogen; m is 0.1-1.9; n is 0.1 to 1.9; m+n=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 shown as a general formula (II),
in the general formula (II), R 5 And R is 7 Identical or different, being hydrogen or C 1 ～C 8 A linear or branched alkyl group wherein the hydrogen on the alkyl group may be substituted with a hydroxyl group; r is R 6 Is C 1 ～C 8 Straight or branched alkylene groups.
According to the invention, the general formula (I) isCuYa(OR 4 ) b And LB formed compositions.
According to some embodiments of the invention, in formula (I), R 1 Is C 1 ～C 8 Straight or branched alkyl groups of (a). According to some embodiments, R 1 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 embodiments of the invention, in formula (I), R 2 And R is 3 Each independently is hydrogen, C 1 -C 3 Straight-chain or branched alkyl or halogen substituted C 1 -C 3 Straight or branched alkyl groups of (a). According to some embodiments, R 2 And R is 3 Each independently is methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl.
According to some embodiments of the invention, in formula (II), R 5 And R is 7 Is hydrogen or C 1 ～C 5 Straight-chain or branched alkyl, R 6 Is C 1 ～C 5 Straight or branched alkylene groups. In some embodiments, R 5 And R is 7 Hydrogen, methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, etc. In some embodiments, R 6 Is methylene, ethylene, propylene, etc.
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 10-100 microns, preferably 30-70 microns, and a particle size distribution of less than 1.2, preferably 0.7-0.9.
The invention also provides a preparation method of the olefin polymerization catalyst carrier, which comprises the following steps:
(a) Will have the general formula MgX 2 Magnesium halide, metal halide with structural formula of CuYc and metal halide with general formula of R 1 The alcohol compound shown in OH reacts with the compound shown in the general formula (II) to form a solution,
wherein R is 1 Is C 1 ～C 12 Straight-chain or branched alkyl, R 5 And R is 7 Identical or different, being hydrogen or C 1 ～C 8 A linear or branched alkyl group wherein the hydrogen on the alkyl group may be substituted with a hydroxyl group; r is R 6 Is C 1 ～C 8 Is a straight or branched alkylene group, X 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 invention, the epoxy compound is represented by general formula (III),
wherein R is 2 And R is 3 Identical or different, being hydrogen or C 1 ～C 5 Straight chain or of (2)Branched alkyl groups wherein the hydrogen on the alkyl group may be optionally substituted with halogen.
According to some preferred embodiments of the invention, R 1 Is C 1 ～C 8 Straight or branched alkyl groups of (a). According to some embodiments, R 1 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 invention, R in step (a) 1 The OH compound may be an 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 may be used alone or in combination.
According to some embodiments of the invention, in formula (II), R 5 And R is 7 Is hydrogen or C 1 ～C 5 Straight-chain or branched alkyl, R 6 Is C 1 ～C 5 Straight or branched alkylene groups. In some embodiments, R 5 And R is 7 Hydrogen, methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, etc. In some embodiments, R 6 Is methylene, ethylene, propylene, etc.
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, R 2 And R is 3 Each independently is hydrogen, C 1 -C 3 Straight-chain or branched alkyl or halogen substituted C 1 -C 3 Straight or branched alkyl groups of (a). Preferably, R 2 And R is 3 Each independently is methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl.
According to some preferred embodiments of the present invention, the preparation of the solution in step (a) is carried out at a temperature of 30-160 ℃, preferably 40-120 ℃. According to the inventionIn embodiments, R 1 The 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 molar ratio of the compound represented by the general formula (II) to the magnesium halide added is 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 vessel. According to some preferred embodiments of the invention, the step (a) is performed during the preparation of the solution, without any sequence of addition.
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 mole, per mole of magnesium.
According to some preferred embodiments of the invention, the 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 of liquid aliphatic, aromatic, cycloaliphatic hydrocarbon, silicone oil or a mixture thereof. The amount of inert dispersion medium added and R 1 The ratio (volume ratio) of the addition amount of OH is 0-5: 1, preferably 0 to 2:1.
according to some preferred embodiments of the invention, the MgX described in step (a) 2 X is as defined in formula (I), and specific compounds are as follows: magnesium dichloride, magnesium dibromide, magnesium diiodide, with magnesium dichloride being preferred. The MgX is 2 The compounds may be used singly or in combination.
According to some preferred embodiments of the invention, cuYc in step (a) is a cuprous halide, most preferably cuprous chloride. The CuYc compounds may be used alone or in combination.
According to some preferred embodiments of the invention, a small amount of water in each of the raw materials added in step (a) may participate in the solution forming reaction.
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, butylene oxide, propylene oxide or butylene oxide, etc.
According to some preferred embodiments of the invention, the reaction temperature in step (b) is 30-160 ℃, preferably 40-120 ℃. 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 a better 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 alkyl phenol polyoxyethylene ether phosphate, polyoxyethylene imine modified by oxyalkyl acrylate copolymer, polymer of 1-dodecyl-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 polymethyl methacrylate can be selected. Polyvinylpyrrolidone and polyethylene are preferable.
According to some preferred embodiments of the present invention, the polymer dispersion stabilizer is used in an amount of magnesium compound and R 1 The total amount of OH compounds used is from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight.
According to the invention, the preparation process further comprises a step (c) of recovering the solid particles obtained. The solid recovery in the step (c) means that solid particles are obtained by using solid-liquid separation techniques well known in the art, such as filtration, decantation, centrifugal separation, etc., and the obtained spherical carrier particles are also washed with an inert hydrocarbon solvent and dried. Wherein the inert hydrocarbon solvent is preferably linear or branched liquid alkane and arene with carbon chain length of more than 4 carbons; the method specifically comprises the following steps: hexane, heptane, octane, decane, toluene, and the like.
In a preferred embodiment, the process for preparing an olefin polymerization catalyst support comprises:
(1) In a closed container, in the presence of at least one polymer dispersion stabilizer, the magnesium halide MgX 2 Organic alcohol R 1 OH and junctionThe mixture of metal halides constituting CuYc is reacted at 30-160 c (preferably 40-120 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 above formula (III) at 30-160 ℃ (preferably 40-120 ℃) for 0.1-5 hours (preferably 0.2-1 hour) to precipitate solid particles;
(3) And recovering the solid particles through a solid-liquid separation technology to obtain the spherical carrier.
In a more preferred embodiment, the process for preparing an olefin polymerization catalyst support comprises:
(1) Heating a mixture of magnesium halide, an organic alcohol, a metal halide of the structure CuYc, a compound of the general formula (ii) and at least one polymeric dispersion stabilizer to 30-160 ℃, preferably 40-120 ℃, in a closed vessel under stirring, for 0.1-5 hours, preferably 0.5-2 hours, to form a mixture solution, wherein the amount of the organic alcohol is 3-30 moles, preferably 4-25 moles, per mole of magnesium; the compound represented by the general formula (II) is added in an amount of 0.005 to 0.1 mol, preferably 0.005 to 0.05 mol. The metal halide of the structure CuYc is added in an amount of 0.01 to 0.1 mole, preferably 0.01 to 0.05 mole, per mole of magnesium. The polymer dispersion stabilizer is used in an amount of 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 an alkylene oxide compound represented by the above formula (III) to the above 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 through a solid-liquid separation technology to obtain the spherical carrier.
In the above preferred embodiments, the process of recovering the solid particles may be performed according to conventional solid-liquid separation techniques in the art, for example, filtration, decantation, centrifugal separation, and the like. Furthermore, step (3) may further comprise washing and drying the obtained spherical support particles with an inert hydrocarbon solvent. The inert hydrocarbon solvent is preferably a linear or linear liquid alkane having a carbon chain length of more than 4 carbons, aromatic hydrocarbon, and specifically, for example, hexane, heptane, octane, decane, toluene, etc.
The invention also provides a carrier prepared by the preparation method. According to an embodiment of the invention, the support is spherical and has an average particle diameter of 10-100 microns, preferably 30-70 microns, and a particle size distribution of less than 1.2, preferably 0.7-0.9.
The invention also provides a catalyst component for olefin polymerization, which contains the reaction product of the olefin polymerization catalyst carrier prepared by the olefin polymerization catalyst carrier and/or the preparation method, a titanium compound and an internal electron donor compound.
The synthesis of the catalyst component may be carried out by known synthesis methods, such as described in chinese patent CN1091748, by reacting spherical particles of the magnesium-containing composition directly with titanium halide; OR the spherical magnesium-containing composition is firstly combined with a magnesium-containing compound with a structural formula of Ti (OR) as described in Chinese patent CN201310469927 4 The alkoxy titanium compound of (2) is reacted to obtain an intermediate product, and then the intermediate product is reacted with titanium halide to prepare the titanium-halide. In the above catalyst preparation process, some internal electron donor compounds known in the industry can be optionally added according to the actual application requirements.
The invention also provides a catalyst system for olefin polymerization comprising the catalyst component, an alkyl aluminum compound and optionally an external electron donor compound.
The invention also provides a process for the polymerization of olefins comprising contacting one or more olefins with the catalyst system under olefin polymerization conditions. In an embodiment of the invention, the olefins have the general formula CH 2 =chr, wherein R is hydrogen or C 1 -C 7 An alkyl group. Preferably, the olefin is selected from one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
The support provided by the present invention has some or all of the following advantages over the magnesium compounds prepared in the prior art: (1) The carrier composed of the invention has improved particle morphology, and particle adhesion is reduced; (2) The particle size of the carrier can be adjusted by adjusting the addition amount of the metal halide CuY with reducibility under the condition of not adjusting the stirring rotation speed, and particularly, the carrier with small particle size can be obtained under the condition of not changing the stirring rotation speed by compounding with the compound with the general formula (II), so that the equipment cost is reduced and the preparation stability of the carrier is improved; (3) When the carrier with smaller particle size is obtained by increasing the stirring rotation speed, the particle morphology of the carrier can be improved, and the particle size distribution can be reduced; (4) The catalyst prepared by the carrier has higher hydrogen regulation sensitivity when being used for olefin polymerization, especially propylene polymerization or copolymerization.
Drawings
Fig. 1 is an optical photomicrograph of the morphology of the support particles prepared in example 1.
Fig. 2 is an optical photomicrograph of the morphology of the support particles prepared in example 3.
Fig. 3 is an optical photomicrograph of the morphology of the support particles prepared in example 7.
Fig. 4 is an optical photomicrograph of the morphology of the carrier particles prepared in example 9.
Fig. 5 is an optical micrograph of the morphology of the carrier particles prepared in comparative example 1.
FIG. 6 is an optical micrograph of the morphology of the support particles prepared in comparative example 2.
Fig. 7 is an optical micrograph 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 thereof.
The testing method comprises the following steps:
1. polymer melt index: measured according to ASTM D1238-99.
2. Polymer isotactic index: the measurement was carried out by heptane extraction (boiling extraction with heptane for 6 hours), i.e. 2g of a dried polymer sample was taken, placed in an extractor and extracted with boiling heptane for 6 hours, after which the residue was dried to constant weight, and the ratio of the weight (g) of the obtained polymer to 2 was the isotactic index.
3. Particle size distribution testing: the average particle diameter and particle size distribution of the carrier particles were measured by a Master Sizer 2000 particle size machine (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 commercially available from Nikon under the model Eclipse E200.
5. Content of metal element in carrier: and (5) measuring by an inductively coupled plasma mass spectrometer.
6. Catalyst activity = weight of polymer obtained/weight of catalyst used.
A. Preparation of olefin polymerization catalyst supports
Example 1
Into 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 successively added, and the temperature was raised to 70℃under stirring (stirring rotation speed 450 rpm). After reacting at constant temperature for 1 hour, adding epichlorohydrin 0.6mol, maintaining the temperature for 0.5 hour, filtering out liquid, washing solid with hexane for 5 times, and drying in vacuum to obtain solid component particles. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
the carrier particle size distribution d50=68.2 μm, span=0.64, and the particle morphology is shown in fig. 1.
Example 2
The preparation process differs from example 1 only in that the addition of cuprous chloride is 6mmol. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
carrier particle size distribution d50=54.8 μm, span=0.64.
Example 3
The preparation process differs from example 1 only in that the addition of cuprous chloride is 0.01mol. Carrier particle size distribution d50=45.4 μm, span=0.64. The morphology of the particles is shown in figure 2.
Example 4
The preparation process differs from example 3 only in that the reaction temperature is 60 ℃. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
carrier particle size distribution d50=31 μm, span=0.64.
Example 5
The preparation method was different from example 3 only in that the ethanol addition amount was 2.4mol and the cuprous chloride addition amount was 0.01mol. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
carrier particle size distribution d50=36.2 μm, span=0.64.
Example 6
The preparation process differs from example 2 only in that the amount of triethanolamine added is 0.01mol. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
carrier particle size distribution d50=57.8 μm, span=0.7.
Example 7
The preparation differs from example 1 only in that triethanolamine 2mmol is replaced by N, N dimethylethanolamine 4mmol. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
the carrier particle size distribution d50=52.8 μm, span=0.64, and the particle morphology is shown in fig. 3.
Example 8
The preparation process differs from example 4 only in that the stirring speed is 1200rpm.
Carrier particle size distribution d50=24.5 μm, span=0.64.
Example 9
The preparation process differs from example 1 only in that no triethanolamine is added. By nuclear magnetic resonance, elemental analysis and gas chromatography, the carrier composition was as follows:
the carrier particle size distribution d50=60.4 μm, span=0.63, and the particle morphology is shown in fig. 4.
Example 10
The preparation differs from example 9 only in that 6mmol of cuprous chloride is present and no triethanolamine is added.
Carrier particle size distribution d50=57.2 μm, span=0.64.
Example 11
The preparation process differs from example 10 only in that 12mmol of cuprous chloride are present and no triethanolamine is added.
Carrier particle size distribution d50=35.3 μm, span=0.67.
Example 12
The preparation process differs from example 1 only in that the cuprous chloride is replaced by cupric chloride.
Carrier particle size distribution d50=62.5 μm, span=0.69.
Example 13
The preparation process differs from example 12 only in that the copper chloride addition is 6mmol.
Carrier particle size distribution d50=60.2 μm, span=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 atmosphere, cooled to-10℃for 0.5hr, tetraethyl titanate (TET) 2.5mL (molar ratio TET/Mg=0.2) was added, and the temperature was slowly raised to 60℃for 0.5hr. 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 of titanium tetrachloride was added under an inert atmosphere, cooled to-20℃and 8g of the intermediate product prepared in the above (1) was added, and the temperature was raised to 110 ℃. During the heating process, 1.5ml of diisobutyl phthalate is added, liquid is filtered, the mixture is washed twice with titanium tetrachloride and three times with hexane, and the spherical catalyst component is obtained after vacuum drying.
C. Propylene polymerization
The propylene liquid phase bulk polymerization was carried out in a 5L stainless steel autoclave. To the reaction vessel under nitrogen, 5ml of a hexane solution of triethylaluminum (concentration: 0.5 mmol/ml), 1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1 mmol/ml) and 9mg of the above spherical catalyst component were successively added. 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, reducing the temperature, releasing the 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 atmosphere, cooled to-10℃for 0.5hr, tetraethyl titanate (TET) 2.5mL (molar ratio TET/Mg=0.2) was added, and the temperature was slowly raised to 60℃for 0.5hr. 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 of titanium tetrachloride was added under an inert atmosphere, cooled to-20℃and 8g of the intermediate product prepared in the above (1) was added, and the temperature was raised to 110 ℃. During the heating process, 1.5ml of diisobutyl phthalate is added, liquid is filtered, the mixture is washed twice with titanium tetrachloride and three times with hexane, and the spherical catalyst component is obtained after vacuum drying.
C. Propylene polymerization
The propylene liquid phase bulk polymerization was carried out in a 5L stainless steel autoclave. To the reaction vessel under nitrogen, 5ml of a hexane solution of triethylaluminum (concentration: 0.5 mmol/ml), 1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1 mmol/ml) and 9mg of the above spherical catalyst component were successively added. 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, reducing the temperature, releasing the 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 atmosphere, cooled to-10℃for 0.5hr, tetraethyl titanate (TET) 2.5mL (TET/Mg molar ratio=0.2) was added, and the temperature was slowly raised to 60℃for 0.5hr. 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 of titanium tetrachloride was added under an inert atmosphere, cooled to-20℃and 8g of the intermediate product prepared in the above (1) was added, and the temperature was raised to 110 ℃. During the heating process, 1.5ml of diisobutyl phthalate is added, liquid is filtered, the mixture is washed twice with titanium tetrachloride and three times with hexane, and the spherical catalyst component is obtained after vacuum drying.
C. Propylene polymerization
The propylene liquid phase bulk polymerization was carried out in a 5L stainless steel autoclave. To the reaction vessel under nitrogen, 5ml of a hexane solution of triethylaluminum (concentration: 0.5 mmol/ml), 1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1 mmol/ml) and 9mg of the above spherical catalyst component were successively added. 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, reducing the temperature, releasing the pressure, discharging, drying the obtained propylene homopolymer, and weighing. The results are shown in Table 1.
Comparative example 1
The same procedure as in example 1 was followed except that cuprous chloride and triethanolamine were not added.
Catalyst preparation and propylene polymerization contract example 14, carrier particle morphology is shown in FIG. 5, and polymerization results are shown in Table 1. It can be seen from the figure that there are parts of the carrier particles that adhere to form shaped particles.
Comparative example 2
The same procedure as in example 4 is followed, except that cuprous chloride and the compound of formula (II) are not added. Carrier particle size distribution d50=56.8 μm, span=0.65. The morphology of the carrier particles is shown in FIG. 6. It can be seen from the figure that the carrier carries a lot of fine slag and that caking occurs.
Comparative example 3
In the same manner as in example 4, cuCl and the compound represented by the formula (II) were not added, and the stirring speed was increased to 1600rpm. Carrier particle size distribution d50=35.4 μm, span=0.9. The morphology of the carrier particles is shown in FIG. 7. From the figure, it can be seen that the carrier particle size distribution is significantly broadened.
As can be seen from the particle size distribution of the carrier and the results of the drawings, the cuprous chloride is added in the preparation process of the carrier, so that 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); in particular, when the compound is used in combination with an amine compound shown in the general formula (II), 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 low-speed stirring (see example 4). When the stirring rotation speed is increased, the particle diameter of the carrier can be further reduced to 25 μm and has a narrow particle diameter distribution (see example 8). When cuprous chloride was not added, the particle size of the carrier was 35 μm even if the stirring speed was increased to 1600rpm, and the particle size distribution was remarkably widened (see comparative example 3 and fig. 7). Examples 12 and 13 show that the addition of copper chloride does not significantly regulate the particle size of the support particles.
Table 1 example carrier preparation catalyst performance
As can be seen from the results in Table 1, the addition of the alcohol amine compound during the preparation of the carrier can improve the hydrogen regulation sensitivity of the catalyst, and has no influence on the polymerization activity of the catalyst.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (17)

1. An olefin polymerization catalyst support having a composition represented by the general formula (I):
R 1 is C 1 ～C 12 Straight or branched alkyl of (a); r is R 2 And R is 3 Identical or different, being hydrogen or C 1 ～C 5 Wherein hydrogen on the alkyl group is optionally substituted with a halogen atom; r is R 4 1, 3-dichloro-2-propyl; x and Y are selected from halogen; m is 0.1-1.9; n is 0.1 to 1.9; m+n=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 shown as a general formula (II),
in the general formula (II), R 5 And R is 7 Identical or different, being hydrogen or C 1 ～C 8 A linear or branched alkyl group wherein the hydrogen on the alkyl group may be substituted with a hydroxyl group; r is R 6 Is C 1 ～C 8 Straight or branched alkylene groups.
2. The olefin polymerization catalyst support according to claim 1, wherein in the general formula (I), R 1 Is C 1 ～C 8 Straight or branched alkyl of (a); r is R 2 And R is 3 Each independently is hydrogen, C 1 -C 3 Straight-chain or branched alkyl or halogen substituted C 1 -C 3 Straight or branched alkyl of (a);
in the general formula (II), R 5 And R is 7 Is hydrogen or C 1 ～C 5 Straight-chain or branched alkyl, R 6 Is C 1 ～C 5 Straight or branched alkylene of (a);
the halogen is selected from chlorine, bromine and iodine.
3. The olefin polymerization catalyst support according to claim 2, wherein R 1 Selected from ethyl, n-propyl, isopropyl,N-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl and 2-ethylhexyl; and/or R 2 And R is 3 Each independently methyl, ethyl, chloromethyl, chloroethyl, bromomethyl and bromoethyl;
and/or, the halogen is chlorine;
and/or the compound shown in the general formula (II) is selected from one or more of ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, N-diethylethanolamine and N-methyldiethanolamine.
4. The olefin polymerization catalyst support according to any one of claims 1 to 3, wherein the average particle diameter is 10 to 100 μm and the particle size distribution is less than 1.2.
5. The olefin polymerization catalyst support according to claim 4, wherein the average particle diameter is 30 to 70 μm and/or the particle size distribution is 0.7 to 0.9.
6. A process for preparing an olefin polymerization catalyst support comprising the steps of:
(a) Will have the general formula MgX 2 Magnesium halide, metal halide with structural formula of CuYc and metal halide with general formula of R 1 The alcohol compound shown in OH reacts with the compound shown in the general formula (II) to form a solution,
wherein R is 1 Is C 1 ～C 12 Straight-chain or branched alkyl, R 5 And R is 7 Identical or different, being hydrogen or C 1 ～C 8 A linear or branched alkyl group wherein the hydrogen on the alkyl group may be substituted with a hydroxyl group; r is R 6 Is C 1 ～C 8 Straight-chain or branched alkylene of (a), X and Y are halogen, c=1;
(b) Reacting the solution of (a) with an epoxy compound to produce spherical solid particles.
7. The process for producing an olefin polymerization catalyst carrier according to claim 6, wherein the epoxy compound is represented by the general formula (III),
wherein R is 2 And R is 3 Identical or different, being hydrogen or C 1 ～C 5 Wherein hydrogen on the alkyl group may be optionally substituted with halogen.
8. The process of claim 7, wherein R 1 Is C 1 ～C 6 Straight or branched alkyl of (a); in the general formula (II), R 5 And R is 7 Is hydrogen or C 1 ～C 5 Straight-chain or branched alkyl, R 6 Is C 1 ～C 5 Straight or branched alkylene of (a); r is R 2 And R is 3 Each independently is hydrogen, C 1 -C 3 Straight-chain or branched alkyl or halogen substituted C 1 -C 3 Straight or branched alkyl groups of (a).
9. The method according to claim 6, wherein in the step (a), a polymer dispersion stabilizer having a molecular weight of more than 1000 is added during the preparation of the solution, and the magnesium halide is one or more selected from the group consisting of magnesium dichloride, magnesium dibromide and magnesium diiodide.
10. The method of claim 9, wherein in step (a), a polymeric dispersion stabilizer having a molecular weight of greater than 3000 is added during the preparation of the solution.
11. The process according to any one of claims 6 to 10, wherein the preparation of the solution in step (a) is carried out at a temperature of 30 to 160 ℃; wherein R is 1 Of OH compoundsThe addition amount is 3-30 mol per mol of magnesium; the molar ratio of the compound of formula (II) to the magnesium halide added was 1: 100-1: 5, a step of; the metal halide is added in an amount of 0.001 to 0.1 mole per mole of magnesium; the reaction temperature in the step (b) is 30-160 ℃, wherein the addition amount of the epoxy compound is 1-10 moles per mole of magnesium.
12. The method of claim 11, wherein the preparation of the solution in step (a) is performed at a temperature of 40-120 ℃; and/or R 1 The addition amount of the OH compound is 4-25 mol per mol of magnesium; and/or the molar ratio of the compound represented by the general formula (II) to the magnesium halide added is 1: 50-1: 5, a step of; and/or, the metal halide is added in an amount of 0.003 to 0.08 per mole of magnesium; and/or the reaction temperature in step (b) is 40-120 ℃, and/or the epoxy compound is added in an amount of 2-6 moles per mole of magnesium.
13. A catalyst support prepared by the preparation method of any one of claims 6 to 12, the support having an average particle diameter of 10 to 100 microns and a particle size distribution of less than 1.2.
14. The catalyst support according to claim 13, characterized in that the average particle diameter of the support is 30-70 microns and/or the particle size distribution is 0.7-0.9.
15. A catalyst component for the polymerization of olefins comprising the reaction product of the support according to any of claims 1 to 5 and/or of the support according to claims 13 to 14 with a titanium compound and an internal electron donor compound.
16. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 15, an alkyl aluminum compound, and optionally an external electron donor compound.
17. An olefin polymerization process comprising contacting one or more olefins under olefin polymerization conditions with the catalyst system of claim 16.
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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
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
EP21885150.9A EP4234590A4 (en) 2020-10-26 2021-10-26 Solid component for preparing olefin polymerization catalyst, and preparation method therefor 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
KR1020237017908A KR20230097111A (en) 2020-10-26 2021-10-26 Solid component for preparing olefin polymerization catalyst, method for preparing the same and application thereof
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