CN107880162B - Catalyst component for olefin polymerization and preparation and application thereof - Google Patents

Catalyst component for olefin polymerization and preparation and application thereof Download PDF

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CN107880162B
CN107880162B CN201610872772.3A CN201610872772A CN107880162B CN 107880162 B CN107880162 B CN 107880162B CN 201610872772 A CN201610872772 A CN 201610872772A CN 107880162 B CN107880162 B CN 107880162B
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compound
catalyst component
catalyst
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CN107880162A (en
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王世波
周俊领
黄廷杰
刘东兵
张磊
吕新平
周歆
张长礼
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • C08F110/02—Ethene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/651—Pretreating with non-metals or metal-free compounds
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6546—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof organo-magnesium compounds

Abstract

The present invention relates to a catalyst component for the polymerization of olefins, which is the reaction product comprising at least one organomagnesium compound, at least one titanium-containing compound, at least one hydroxyl-containing compound, at least one chlorine-containing organophosphorus compound and at least one additive; wherein the additive is a polystyrene block polyethylene oxide polymer. The catalyst component provided by the invention has high catalytic activity, good hydrogen regulation sensitivity of the catalyst and high bulk density of the obtained polymer, and the corresponding catalyst also has good particle morphology and distribution, thereby being more beneficial to the use of the catalyst on polymerization process devices such as gas phase, slurry and the like.

Description

Catalyst component for olefin polymerization and preparation and application thereof
Technical Field
The invention belongs to the technical field of catalyst components and preparation thereof, and particularly relates to a catalyst component for olefin polymerization and preparation and application thereof.
Background
In recent 20 years, with the development of olefin polymerization processes, catalysts compatible with the polymerization processes have been advanced greatly, and high-efficiency catalysts have still occupied an important position in the field of polyolefin catalysts by virtue of their excellent polymerization performance and mature application technology. Through research and research for many years, the preparation method of the Mg-Ti series high-efficiency catalyst is developed to a chemical reaction method from a co-grinding method and a suspension impregnation method. In chemical reaction processes, many of the prior art processes involve the use of organometallic magnesium compounds, chlorinating agents, and transition metal titanium compounds, among other chemical starting materials, from which a variety of different types of catalysts have been prepared.
In this type of Mg-Ti catalysts, there is a fatal disadvantage in that it is difficult to control the forming step and thus to control the morphology of the catalyst particles produced, and recent development has been made in that the particle morphology of the resulting catalyst can be improved by adding a certain emulsifier-like substance to a dispersion system containing a magnesium/titanium compound as a catalyst precursor to form an emulsion and then precipitating the catalyst particles by reaction, but these methods are complicated in forming step and difficult to control, the particle morphology of the resulting catalyst is also difficult to control, and the substances used are expensive and difficult to obtain.
Despite the considerable research work that has been done in the area of ziegler-natta catalysts, there is still a need for new or improved processes for the preparation of ZN catalysts with higher performance requirements.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst component for olefin polymerization, and its preparation and application, aiming at the defects of the prior art. The inventor of the invention carries out extensive and intensive experimental research in the technical field of olefin polymerization catalyst components and preparation and application thereof and finds that the catalyst synthesis method is simple and easy by selecting a proper modification additive, and catalyst particles with better shapes, such as spheres and narrow particle size distribution, can be obtained and have higher catalytic activity and hydrogen regulation sensitivity.
To this end, the present invention provides, in a first aspect, a catalyst component for olefin polymerization which is a reaction product comprising at least one organomagnesium compound, at least one titanium-containing compound, at least one hydroxyl-containing compound, at least one chlorine-containing organophosphorus compound, and at least one additive;
wherein the chlorine-containing organophosphorus compound is represented by a general formula (IV) OpPR4 qCl3-qThe compound of the formula (IV) wherein R is4Is C2-C200. ltoreq. q < 3, p. gtoreq 0 or 1;
the additive is a polystyrene block polyethylene oxide polymer.
According to the invention, the organomagnesium compound is MgR of the general formula (I)1 nCl2-nThe compound shown in the general formula (I), R1Is a saturated or unsaturated, linear or branched C2-C20C of a hydrocarbon group or a cyclic chain3-C20N is more than 0 and less than or equal to 2. Preferably, the organomagnesium compound includes one or more of dibutylmagnesium, diisobutylgagnesium, dioctylmagnesium, butyloctylmagnesium, ethylmagnesium chloride, and butylmagnesium chloride.
According to the invention, the titanium-containing compound is of the general formula (II) Ti (OR)2)mCl4-mA compound represented by the general formula (II) wherein R2Is a saturated or unsaturated, linear or branched C2-C20C of a hydrocarbon group or a cyclic chain3-C20M is more than or equal to 0 and less than or equal to 4; since the tetravalent titanium compound is generally in a liquid state at ordinary temperature and also has good compatibility with some solvents. Preferably, the titanium-containing compound comprises one or more of titanium tetrachloride, tetraethyl titanate, and tetrabutyl titanate, more preferably titanium tetrachloride.
According to the invention, the hydroxyl-containing compound is HOR of the general formula (III)3A compound represented by the general formula (III) wherein R3Is a saturated or unsaturated, linear or branched C2-C20C of a hydrocarbon group or a cyclic chain3-C20A hydrocarbon group of (1). Preferably, the hydroxyl-containing compound comprises aliphatic alcohol and/or aromatic alcohol; more preferably, the hydroxyl group-containing compound includes one or more of n-butanol, n-hexanol, isooctanol, benzyl alcohol, and phenethyl alcohol.
According to the invention, the chlorine-containing organophosphorus compound comprises at least one of phosphorus methyl dichloride, ethyl phosphorus dichloride, butyl phosphorus dichloride, methoxy phosphorus dichloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, methyl dichlorophosphate, ethyl dichlorophosphate and butyl dichlorophosphate, and preferably at least one of phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride.
According to the invention, the additive polystyrene block polyethylene oxide (PS-b-POE) based polymer comprises di-and tri-blocks and derivatives thereof; preferably the block type of the polystyrene block polyethylene oxide polymer is optionally in linear, branched or star form. The polystyrene content in the polystyrene block polyethylene oxide polymer is 5 wt% to 95 wt%, preferably 10 wt% to 90 wt%.
In a second aspect, the present invention provides a process for preparing a catalyst component according to the first aspect of the present invention, which comprises:
a, reacting an organic magnesium compound with a hydroxyl-containing compound to obtain a transparent solution;
step B, dispersing the additive in the step C4-C20Alkane or C6-C20Forming a solution in the aromatic hydrocarbon solvent, and reacting the solution with the transparent solution obtained in the step A to obtain a mixed solution;
and step C, sequentially adding chlorine-containing organic phosphorus compounds and titanium-containing compounds into the mixed solution obtained in the step B to obtain a catalyst component suspension, and recovering solid particles in the catalyst component suspension to obtain the catalyst component.
According to the method of the present invention, the titanium-containing compound is 0.01 to 10 moles, the hydroxyl-containing compound is 0.1 to 20 moles, the chlorine-containing organophosphorus compound is 0.1 to 50 moles, and the concentration of the additive in the reaction system is 0.001 to 100g/L per mole of the organomagnesium compound. Preferably, the titanium-containing compound is 0.05 to 5 moles, the hydroxyl-containing compound is 0.2 to 10 moles, the chlorine-containing organophosphorus compound is 0.5 to 20 moles, and the concentration of the additive in the reaction system is 0.01 to 50 g/L.
According to the process of the invention, it is generally advantageous to choose the reaction temperature of the organomagnesium compound and the hydroxyl group-containing compound in step A to be carried out at a relatively high temperature, preferably below the boiling temperature of the reactants, which is generally not higher than 90 ℃ and generally not higher than 70 ℃. The reaction time depends on the nature of the reactants and the operating conditions, and the time required is generally from 5 minutes to 2 hours, preferably from 10 minutes to 1 hour. After the reaction of the organomagnesium compound and the hydroxyl group-containing compound, the resulting solution can be used in admixture with an inert diluent, which is generally selected from inert solvents of aliphatic or aromatic hydrocarbons, such as isobutane, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, and mixtures thereof, with hexane, heptane, or toluene generally being suitable inert solvents.
According to the process of the invention, in step B, the additive is dispersed in C4-C20Preferably, the solvent (A) is dispersed in hexane, heptane or toluene or a mixture thereof to form a solution, and the solution is then thoroughly mixed with the transparent solution obtained in step A to obtain a mixed solution. Depending on the nature and nature of the additive, C4-C20The prepared concentration of the alkane or aromatic hydrocarbon solution is controlled to be 0.1 to 100g/l, preferably 1 to 50g/l, and the amount is added so that the concentration of the additive in the reaction system is 0.001 to 100g/l, preferably 0.01 to 50 g/l. The mixing temperature is generally below the boiling point of the system and is generally chosen, for convenience, between 0 and 90 c, preferably between 10 and 50 c. The mixing time of the two is generally selected from 0.5 minutes to 5 hours, preferably from 10 minutes to 1 hour.
According to the process of the present invention, in step C, the homogeneous mixing of all the substances is rapidly completed at a temperature, the solution system obtained in the first two steps is first lowered to a temperature at which the solution remains clear and transparent without turbidity or precipitation, the temperature may be controlled between-90 and 30 ℃, preferably between-70 and 0 ℃, and then the chlorine-containing organophosphorus compound and the titanium-containing compound are gradually and gradually added in sequence, and during the addition, sufficient stirring is usually carried out to facilitate the sufficient mixing of the various substances, and the addition rate is usually selected so as not to cause significant reaction or to significantly raise the temperature of the system. After thorough mixing, the temperature can be raised by any known suitable method, such as slow, gradual, rapid or programmed temperature raising, and different temperature raising methods can be used to obtain catalysts with different performance characteristics. During the temperature rise, the system changes from clear to turbid and precipitates, and in the precipitation reaction step, the reaction time of the precipitation step should be long enough to obtain complete precipitation, and the reaction time can last from 1 minute to 10 hours, preferably from 3 minutes to 5 hours.
It has been found that the aging treatment after the precipitation step at a certain temperature for a certain period of time is advantageous for the particle shape of the catalyst, and it can improve the strength of the catalyst particles, thereby reducing the particle breakage of the catalyst during the polymerization. The temperature of the aging treatment is generally equal to or higher than the final temperature of the precipitation reaction, and the time of the aging reaction may be controlled to 0.5 to 10 hours, preferably 1 to 5 hours.
After the maturation, washing is generally carried out to remove excess reactants and by-products formed during the preparation, any inert solvent can be used for this washing step, for example isobutane, pentane, hexane, heptane, cyclohexane, toluene or various aromatic hydrocarbons and mixtures thereof can be chosen, and in the experiments it was generally chosen to wash twice with toluene and then thoroughly with hexane. After washing, the catalyst suspension was dried under nitrogen to obtain a catalyst powder.
In a third aspect, the present invention provides a catalyst for the homopolymerization or copolymerization of olefins, comprising a catalyst component according to the first aspect of the present invention or a catalyst component prepared by the process according to the second aspect of the present invention, and at least one AlR of formula (V)5 hX3-hAn organoaluminum compound represented by the general formula (V) wherein R5Are identical or different C1-C8X is halogen, and h is more than or equal to 1 and less than or equal to 3. Preferably the organoaluminium compound comprises triethylaluminium (AlEt)3) Triisobutylaluminum (Al (iso-Bu)3) Tri-n-hexylaluminum (Al (n-C)6H13)3) Tri-n-octylaluminum (Al (n-C)8H17)3) And diethylaluminum chloride (AlEt)2Cl).
The catalysts of the present invention may be used in a manner well known in the art for olefin polymerization Ziegler-Natta catalysts, such as with another cocatalyst or electron donor, and the catalysts of the present invention may also be used in combination with one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalysts.
In a fourth aspect, the present invention provides a catalyst component according to the first aspect of the present invention, a catalyst component prepared according to the method of the second aspect of the present invention or a catalyst according to the third aspect of the present invention for use in the homopolymerization or copolymerization of olefins.
The catalyst components and catalysts of the present invention are suitable for use in any olefin that can undergo coordination polymerization, including homopolymerization of one olefin or copolymerization of multiple olefins, preferably the olefin comprises α -olefin such as ethylene, propylene, butylene, or a mixture of ethylene, propylene, butylene and one or more α -olefin(s)4-C10Olefins such as 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methyl-1-pentene, dienes such as butadiene, 1, 4-hexadiene and 1, 7-octadiene, cycloalkenes such as norbornene, and any mixtures thereof.
The catalyst of the present invention may be polymerized in one or more polymerization reactors by conventional polymerization techniques, either gas phase, slurry or bulk polymerization, which may be a batch or continuous polymerization process.
For slurry or bulk reactors, the reaction temperature is generally in the range of 40 to 130 ℃, preferably 60 to 110 ℃; the reactor pressure is generally between 0.2 and 8MPa, preferably between 1 and 6 MPa; the residence time is generally from 0.2 to 6 hours, preferably from 0.5 to 3 hours. Aliphatic hydrocarbons having a boiling point in the range from-70 to 100 ℃ are generally selected for use as diluents; if desired, the polymerization can be carried out under supercritical conditions.
For gas phase reactors, the reaction temperature is generally between 60 and 130 ℃ and preferably between 70 and 110 ℃; the reactor pressure is generally between 0.5 and 4MPa, preferably between 1 and 3 MPa; the residence time is generally from 0.5 to 10 hours, preferably from 1 to 8 hours. If desired, the polymerization can be carried out under condensed conditions by using an appropriate aliphatic hydrocarbon as a diluent.
The amount of catalyst generally depends on the nature of the catalyst, the type of reactor and the operating conditions and the requirements placed on the properties of the polymerization product, and conventional amounts of catalyst may be used.
In the preparation process of the catalyst component for olefin polymerization, the additive polystyrene block polyethylene oxide polymer is used, so that the catalyst component which has good particle morphology, is approximately spherical, has narrow particle size distribution, and has high catalytic activity and hydrogen regulation sensitivity can be obtained, and the morphology of the polymerization product can better replicate the particle morphology of the catalyst, namely the replication effect, so that the control of the particle size and the morphology of the olefin polymerization product can be better realized, so that the catalyst has excellent comprehensive performance.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method used in the present invention is as follows:
(1) the particle size distribution of the carrier and the catalyst adopts a MASTERSIZE particle size distribution instrument, n-hexane is used as a dispersing agent, and the measuring range is 0.02-2000 mu m.
(2) The relative weight percentages of metals (mainly titanium, magnesium) in the catalyst system were measured using plasma emission spectroscopy (ICP).
(3) Melt Index (MI)2.16) Measured using ASTM-D1238.
(4) Bulk Density (BD) was determined using DIN-53194.
Examples
Example 1
Preparation of catalyst component: taking 30mL of toluene, 3.15mL of hexane solution (1M) of dibutyl magnesium and 1.0mL of isooctanol in sequence, heating to 50 ℃, maintaining stirring and reacting for half an hour to obtain a transparent solution, then adding 2mL of toluene solution (10g/L) of polystyrene diblock polyethylene oxide copolymer A (polystyrene content is 42 wt%), cooling to-50 ℃, adding 0.6mL of toluene solution (1M) of phosphorus trichloride and 0.35mL of titanium tetrachloride in sequence, maintaining low temperature for half an hour, quickly heating to 50 ℃ within 10 minutes, and reacting for 2 hours at the temperature. Cooling the catalyst suspension to room temperature, standing, settling, washing with toluene for three times, wherein the amount of toluene used in each time is 50mL, drying after washing to obtain brown solid fluidity powder, namely the catalyst component, and measuring the average particle size of the catalyst component to be 22.2 mu m. Elemental analysis (ICP): 10.49 wt% of Ti and 18.15 wt% of Mg.
Evaluation of ethylene polymerization: 1L of hexane, 1mmol of triethylaluminum and a certain amount of catalyst components are added into a 2L stainless steel stirring kettle, then the temperature is increased to 85 ℃, 0.18MPa of hydrogen is added at a time, then the total pressure of the system is maintained at 1.03MPa by using ethylene for polymerization reaction, after 2 hours of reaction, the addition of ethylene is stopped, the temperature is reduced, the pressure is released, polyethylene powder is weighed, the activity of the catalyst is calculated, and the bulk density and the melt index under the load of 2.16Kg of the polyethylene powder are tested, and the results are shown in Table 1.
Example 2
The catalyst component was prepared in the same manner as in example 1 except that 2mL of the toluene solution (10g/L) of the polystyrene diblock polyethylene oxide copolymer A (polystyrene content: 42% by weight) was changed to 10mL of the toluene solution (10g/L) of the polystyrene diblock polyethylene oxide copolymer A (polystyrene content: 42% by weight). The average particle diameter was found to be 11.3. mu.m. Elemental analysis (ICP): 8.21 wt% of Ti and 17.03 wt% of Mg.
The ethylene slurry polymerization evaluation method of the catalyst was the same as in example 1, and the polymerization results are shown in Table 1.
Example 3
The preparation method of the catalyst component was the same as that of example 1 except that 1.0mL of isooctanol was changed to 3.0mL of isooctanol, the temperature was rapidly raised to 50 ℃ within 10 minutes, and the temperature was naturally and slowly raised to room temperature, followed by heating to 50 ℃. The average particle diameter was found to be 25.9. mu.m. Elemental analysis (ICP): 10.22 wt% of Ti and 18.75 wt% of Mg.
The ethylene slurry polymerization evaluation method of the catalyst was the same as in example 1, and the polymerization results are shown in Table 1.
Comparative example 1
The catalyst component was prepared in the same manner as in example 1, except that "a toluene solution of a polystyrene diblock polyethylene oxide copolymer A (polystyrene content: 42% by weight)" was not added during the preparation of the catalyst component. The average particle size was found to be 64.76 μm with a broad particle size distribution. Elemental analysis (ICP): 10.07 wt% of Ti and 13.16 wt% of Mg.
The ethylene slurry polymerization evaluation method of the catalyst was the same as in example 1, and the polymerization results are shown in Table 1.
Comparative example 2
Preparation of catalyst component: 30mL of hexane, 3.15mL of dibutyl magnesium hexane solution (1M) and 1.0mL of isooctanol are taken in sequence, the temperature is raised to 50 ℃ and the stirring reaction is maintained for half an hour to obtain a transparent solution, then 3mL of FG1901 hexane solution (10g/L) of Kraton is added, the temperature is lowered to-50 ℃, 3.15mL of phosphorus trichloride hexane solution (1M) and 0.35mL of titanium tetrachloride are added in sequence, the reaction is maintained at low temperature for half an hour, then the temperature is rapidly raised to 50 ℃ within 10 minutes, and the reaction is maintained at 50 ℃ for 2 hours. The catalyst suspension was cooled to room temperature, allowed to stand, settled, washed three times with 50ml of hexane each time, and after washing, dried to give a brown solid flowable powder having an average particle size of 17.6 μm. Elemental analysis (ICP): 9.86 wt% of Ti and 12.69 wt% of Mg.
The ethylene slurry polymerization evaluation method of the catalyst was the same as in example 1, and the polymerization results are shown in Table 1.
TABLE 1
Figure BDA0001124632700000071
It can be seen from the experimental data of the examples and comparative examples in table 1 that the polystyrene block polyethylene oxide polymer additive is used in the preparation process of the catalyst component, the obtained catalyst and polymer have good particle morphology, high ethylene polymerization activity, high bulk density of the polymer resin and excellent comprehensive performance 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 (15)

1. A catalyst component for the polymerization of olefins which is the reaction product comprising at least one organomagnesium compound, at least one titanium-containing compound, at least one hydroxyl-containing compound, at least one chlorine-containing phosphorus compound, and at least one additive; wherein the additive is a polystyrene block polyethylene oxide polymer, and the polystyrene content in the polystyrene block polyethylene oxide polymer is 5-95 wt%;
the organic magnesium compound is MgR with a general formula (I)1 nCl2-nThe compound shown in the general formula (I), R1Is a saturated or unsaturated, linear or branched C2-C20C of a hydrocarbon group or a saturated or unsaturated cyclic chain3-C20N is more than 0 and less than or equal to 2;
the titanium-containing compound is Ti (OR) with a general formula (II)2)mCl4-mA compound represented by the general formula (II) wherein R2Is a saturated or unsaturated, linear or branched C2-C20C of a hydrocarbon group or a saturated or unsaturated cyclic chain3-C20M is more than or equal to 0 and less than or equal to 4;
the hydroxyl-containing compound is HOR with a general formula (III)3A compound represented by the general formula (III) wherein R3Is a saturated or unsaturated, linear or branched C2-C20C of a hydrocarbon group or a saturated or unsaturated cyclic chain3-C20A hydrocarbon group of (a);
the chlorine-containing phosphorus compound is dichloromethylphosphorus, dichloromethoxyphosphorus, methyl dichlorophosphate, phosphorus pentachloride or general formula (IV) OpPR4 qCl3-qThe compound of the formula (IV) wherein R is4Is C2-C20Alkyl or C2-C20Q is 0. ltoreq. q < 3, and p is 0 or 1.
2. The catalyst component according to claim 1 in which the organomagnesium compound is selected from one or more of dibutylmagnesium, diisobutylgagnesium, dioctylmagnesium, butyloctylmagnesium, ethylmagnesium chloride and butylmagnesium chloride.
3. The catalyst component according to claim 1 wherein the titanium containing compound is selected from one or more of titanium tetrachloride, tetraethyl titanate and tetrabutyl titanate.
4. The catalyst component according to claim 1 in which the hydroxyl group containing compound is an aliphatic alcohol and/or an aromatic alcohol.
5. The catalyst component according to claim 1, wherein the hydroxyl-containing compound is selected from one or more of n-butanol, n-hexanol, isooctanol, benzyl alcohol and phenethyl alcohol.
6. The catalyst component according to claim 1 in which the chlorine-containing phosphorus compound is selected from at least one of phosphorus ethyl dichloride, phosphorus butyl dichloride, phosphorus trichloride, phosphorus oxychloride, ethyl dichlorophosphate and butyl dichlorophosphate.
7. The catalyst component according to any of claims 1 to 6 characterized in that the polystyrene block polyethylene oxide polymer comprises di-blocks and tri-blocks.
8. The catalyst component according to any of claims 1 to 6 characterized in that the block type of the polystyrene block polyethylene oxide polymer is in linear or branched form.
9. The catalyst component according to any of claims 1 to 6 characterized in that the block type of the polystyrene block polyethylene oxide polymer is in star-with-form.
10. The catalyst component according to any of claims 1 to 6 characterized in that the polystyrene content of the polystyrene block polyethylene oxide polymer is from 10% to 90% by weight.
11. A process for the preparation of the catalyst component according to any one of claims 1 to 10, which comprises:
a, reacting an organic magnesium compound with a hydroxyl-containing compound to obtain a transparent solution;
step B, dispersing the additive in the step C4-C20Alkane or C6-C20Forming a solution in the aromatic hydrocarbon solvent, and reacting the solution with the transparent solution obtained in the step A to obtain a mixed solution;
and step C, sequentially adding a chlorine-containing phosphorus compound and a titanium-containing compound into the mixed solution obtained in the step B to obtain a catalyst component suspension, and recovering solid particles in the catalyst component suspension to obtain the catalyst component.
12. The production method according to claim 11, wherein the titanium-containing compound is 0.01 to 10 moles, the hydroxyl group-containing compound is 0.1 to 20 moles, the chlorine-containing phosphorus compound is 0.1 to 50 moles, and the concentration of the additive in the reaction system is 0.001 to 100g/L, per mole of the organomagnesium compound.
13. The production method according to claim 11, wherein the titanium-containing compound is 0.05 to 5 moles, the hydroxyl group-containing compound is 0.2 to 10 moles, the chlorine-containing phosphorus compound is 0.5 to 20 moles, and the concentration of the additive in the reaction system is 0.01 to 50g/L per mole of the organomagnesium compound.
14. A catalyst for the homopolymerization or copolymerization of olefins comprising a catalyst component according to any one of claims 1 to 10 or prepared by a process according to any one of claims 11 to 13, and at least one AlR of formula (V)5 hX3-hAn organoaluminum compound represented by the general formula (V) wherein R5Are identical or different C1-C8X is halogen, and h is more than or equal to 1 and less than or equal to 3.
15. Use of a catalyst component according to any one of claims 1 to 10, a catalyst component prepared according to the process of any one of claims 11 to 13 or a catalyst according to claim 14 for the homopolymerization or copolymerization of olefins.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102453132A (en) * 2010-10-19 2012-05-16 中国石油化工股份有限公司 Catalyst component for olefin polymerization, and preparation method thereof

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US2969346A (en) * 1958-03-31 1961-01-24 Eastman Kodak Co Three-component catalyst for polymerizing olefins containing a mixture of metals and a halogen
KR100424011B1 (en) * 2000-12-18 2004-03-24 삼성아토피나주식회사 A method for producing ethylene homo- and c0-polymer

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Publication number Priority date Publication date Assignee Title
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