CN107880164B - 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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CN107880164B
CN107880164B CN201610872790.1A CN201610872790A CN107880164B CN 107880164 B CN107880164 B CN 107880164B CN 201610872790 A CN201610872790 A CN 201610872790A CN 107880164 B CN107880164 B CN 107880164B
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catalyst component
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CN107880164A (en
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王世波
周俊领
宋阳
张磊
吕新平
黄廷杰
周歆
张长礼
邢宝泉
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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
    • 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
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a catalyst component for olefin polymerization, a preparation method thereof, a catalyst containing the catalyst component and application of the catalyst. The catalyst component 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 organosilicon compound, and at least one additive; wherein the additive is a polyethylene oxide block polyisobutylene polymer. The catalyst provided by the invention not only has high catalytic activity, good hydrogen regulation sensitivity of the catalyst and high bulk density of the obtained polymer, but also has good particle shape 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
Since the successful development of efficient polyolefin catalysts in the 70's of the 20 th century, the world's polyolefin industry has changed dramatically. 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 still occupy an important position in the field of polyolefin catalysts due to 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, numerous invention patents are directed to the use of organometallic magnesium compounds, chlorinating agents and transition metal titanium compounds, among other chemical starting materials, with which a number of different types of catalysts have been prepared, which are disclosed in chinese patents CN1158136, CN1299375, CN1795213 and in US patents US3787384, US4148754, US4173547, US4301029, US4508843, US4921920 and US 5124296. In this type of Mg-Ti catalyst, there is a fatal disadvantage in that it is difficult to control the forming step, and thus, the morphology of the prepared catalyst particles. A recent development has been to improve the particle morphology of the resulting catalyst by adding emulsifier-like substances to a dispersion of the catalyst precursor comprising a magnesium/titanium compound to form an emulsion and then reacting to precipitate the catalyst particles, such as perfluoropolyethers as used in EP0258089A to Montedison and perfluorooctanes as used in CN 1537118A. However, these methods have complicated forming steps and are difficult to control, the morphology of the catalyst particles obtained is also difficult to control, and the materials used are expensive and difficult to obtain.
Despite the considerable research efforts in the field of ziegler-natta catalysts, there is still a need for new or improved processes for the preparation of higher performance ziegler-natta catalysts. Therefore, there is a problem that research and development of a catalyst having a simple preparation method, a good particle morphology, a high catalytic activity and a high hydrogen response is urgently needed.
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 present inventors have conducted extensive and intensive experimental studies in the technical fields of olefin polymerization catalyst components and preparation and application thereof, and have found that when an additive, namely, a polyethylene oxide block polyisobutylene polymer, is used in the preparation of a catalyst component for olefin polymerization, not only are the particles of the corresponding catalyst component more uniform, but also the particle size and morphology of an olefin polymerization product can be better controlled, and the corresponding catalyst has high catalytic activity and hydrogen regulation sensitivity, and the bulk density of a polymer resin is high.
To this end, the present invention provides, in a first aspect, 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 organosilicon compound and at least one additive;
wherein the additive is a polyethylene oxide block polyisobutylene 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 di-n-butylmagnesium, diisobutylgagnesium, dioctylmagnesium, butylmagnesium, 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; m-4 or m-0 is preferred because tetravalent titanium compounds are generally liquid at ordinary temperature and have good compatibility with some solvents. Preferably the titanium-containing compound comprisesOne or more of titanium tetrachloride, tetraethyl titanate, and tetrabutyl titanate; more preferably, the titanium-containing compound is 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 organosilicon compound is of the general formula (IV) SiR4 eCl4-eThe compound of the formula (IV) wherein R is4Is straight-chain or branched C2-C20E is more than or equal to 0 and less than 4. Preferably, the chlorine-containing organosilicon compound comprises one or more of trichlorophenylsilane, trichloromethylsilane, trichloroethylsilane, trichlorooctylsilane, trichloromethoxysilane, trichloroethoxysilane, trichlorobutoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane and silicon tetrachloride; more preferably, the chlorine-containing organosilicon compound comprises one or more of trichloromethylsilane, trichloroethylsilane, trichloromethoxysilane, trichloroethoxysilane and silicon tetrachloride.
According to the invention, the additive polyethylene oxide block polyisobutylene (POE-b-PIB) type polymer comprises diblock and triblock and derivatives thereof; preferably, the block type of the polyethylene oxide block polyisobutylene-based polymer is optionally in linear, branched, or star form. The branched forms include comb and dendritic forms. The content of polyisobutylene in the polyethylene oxide block polyisobutylene polymer is 10wt% -95wt%, preferably 20 wt% -90 wt%, and more preferably 48 wt% -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 a chlorine-containing organic silicon 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.
According to the process of the present invention, the titanium-containing compound is in the range of 0.01 to 10 moles, the hydroxyl-containing compound is in the range of 0.1 to 20 moles, the chlorine-containing organosilicon compound is in the range of 0.05 to 50 moles, and the concentration of the additive in the reaction system is in the range of 0.001 to 100 g/L, preferably the titanium-containing compound is in the range of 0.05 to 5 moles, the hydroxyl-containing compound is in the range of 0.2 to 10 moles, the chlorine-containing organosilicon compound is in the range of 0.1 to 20 moles, and the concentration of the additive in the reaction system is in the range of 0.01 to 50 g/L, per mole of the organomagnesium compound.
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 aliphatic hydrocarbons, such as isobutane, pentane, hexane, heptane or cyclohexane and mixtures thereof, hexane or heptane being generally suitable inert solvents.
According to the process of the invention, in step B, the additive is dispersed in C4-C20Alkane or C6-C20Preferably, the aromatic hydrocarbon solvent of (a) is dispersed in hexane, heptane or toluene or a mixture solvent thereof to form a solution, and then sufficiently mixed with the transparent solution obtained in step (a) to obtain a mixed solution. According to the kind of additiveClass and nature of which are different, C4-C20Alkane or C6-C20The prepared concentration of the aromatic hydrocarbon solution of (a) is controlled to be 0.1 to 100 g/l, preferably 1 to 50 g/l, and the amount is added so that the concentration of the additive in the reaction system is 0.001 to 100 g/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 method of the invention, in step C, the uniform mixing of all the substances is rapidly completed at a temperature, the solution system obtained in the first two steps is firstly reduced to a temperature at which the solution remains clear and transparent without turbidity or precipitation, the temperature can be controlled between-90 ℃ and 30 ℃, preferably between-70 ℃ and 0 ℃, then the chlorine-containing organosilicon compound and the titanium-containing compound are gradually and gradually added, the stirring is usually carried out fully during the addition process to facilitate the full mixing of the various substances, and the adding speed is usually selected based on no obvious reaction or obvious temperature rise 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 homo-or co-polymerisation of olefins comprising a catalyst component according to the first aspect of the present invention or prepared by a 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 which 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 -olefinsThe comonomer is C2-C12Olefins, preferably C4-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.
The catalyst of the invention has higher catalytic activity and better hydrogen regulation sensitivity, the morphology of a polymerization product can better replicate the particle morphology of the catalyst, namely the so-called replication effect, and the bulk density of the polymerization resin is high, 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) The morphology of the catalyst as well as the polymer was measured using a Scanning Electron Microscope (SEM).
(4) Melt Index (MI)2.16) Measured using ASTM-D1238.
(5) Bulk Density (BD) was determined using DIN-53194.
Examples
Example 1
The preparation of the catalyst component comprises the steps of taking 30M L hexane, 3.15M L hexane solution (1M) of di-n-butyl magnesium and 1.0M L isooctanol in sequence, heating to 50 ℃, maintaining stirring and reacting for half an hour to obtain a transparent solution, then adding hexane solution (10 g/L) 2M L of polyethylene oxide polyisobutylene diblock copolymer (with the polyisobutylene content of 48 wt%), cooling to-10 ℃, adding 0.36M L silicon tetrachloride and 0.35M L titanium tetrachloride in sequence, after the materials are added, rapidly heating to 50 ℃ within 10min, maintaining the reaction for 2 hours, cooling the temperature of the catalyst suspension to room temperature, standing, settling, washing for three times with hexane, wherein the hexane dosage is 50M L each time, drying to obtain brown solid fluidity powder, namely the catalyst component, and measuring the average particle size of the catalyst component to be 28.5 mu M.
Evaluation of ethylene polymerization 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyst components were added to a 2L stainless steel stirred tank, then the temperature was raised to 85 ℃, 0.18MPa hydrogen was added at a time, then the total pressure of the system was maintained at 1.03MPa with ethylene to carry out polymerization, after 2 hours of reaction, the addition of ethylene was stopped, the temperature was lowered, the pressure was released, the polyethylene powder was weighed, the activity of the catalyst was calculated, and the bulk density and melt index under a load of 2.16Kg of the polyethylene powder were 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 "a hexane solution (10 g/L) 2m L" of a polyoxyethylene polyisobutylene diblock copolymer (having a polyisobutylene content of 48 wt%) added during the preparation of the catalyst component was changed to "a hexane solution (10 g/L) 4m L" of a polyoxyethylene polyisobutylene diblock copolymer (having a polyisobutylene content of 48 wt%), and the average particle diameter thereof was found to be 22.9 μm.
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 catalyst component was prepared in the same manner as in example 1 except that "0.35 m L titanium tetrachloride" added during the preparation of the catalyst component was changed to "0.50 m L titanium tetrachloride". The average particle diameter was measured to be 30.8 μm.
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 hexane solution (10 g/L) of a polyoxyethylene polyisobutylene diblock copolymer (having a polyisobutylene content of 48 wt%) was not added during the preparation of the catalyst component in 2m L" and the average particle diameter was found to be 79.46. mu.m, the particle diameter distribution was a relatively broad multimodal distribution elemental analysis (ICP): Ti:9.73 wt% and Mg:21.06 wt%.
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
The catalyst component was prepared in the same manner as in example 1 except that "a hexane solution (10 g/L) of a polyoxyethylene polyisobutylene diblock copolymer (having a polyisobutylene content of 48 wt%) added during the preparation of the catalyst component" 2m L "was changed to" a hexane solution (10 g/L) of Kraton FG1901 (polystyrene polybutadiene triblock copolymer, having a polybutadiene content of 70 wt%) 1m L ". The average particle diameter was measured to be 56.2 μm.
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 BDA0001124628760000071
As can be seen from the experimental data of the examples and comparative examples in Table 1, the use of the polyethylene oxide block polyisobutylene polymer additive in the preparation of the catalyst component results in a catalyst and polymer having good particle morphology, high ethylene polymerization activity, higher bulk density of the polymer resin, and excellent catalyst integrity.
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 silicon compound, and at least one additive;
wherein the additive is a polyethylene oxide block polyisobutylene polymer, and the content of polyisobutylene in the polyethylene oxide block polyisobutylene polymer is 10wt% -95 wt%;
the organic magnesium compound is MgR with a general formula (I)1 nCl2-nThe compound shown in the general formula (I), R1Is saturated or notSaturated straight or branched C2-C20C of a hydrocarbon group or a saturated or unsaturated cyclic chain3-C20A hydrocarbon group of 0<n≤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 silicon compound is trichlorophenylsilane, trichloromethylsilane, trichloromethoxysilane, dichlorodimethoxysilane or SiR with a general formula (IV)4 eCl4-eThe compound of the formula (IV) wherein R is4Is straight-chain or branched C2-C20Alkyl or straight or branched C2-C20Alkoxy of 0. ltoreq. e<4。
2. The catalyst component according to claim 1 in which the organomagnesium compound is selected from one or more of di-n-butylmagnesium, di-isobutylmagnesium, 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 selected from aliphatic alcohols and/or aromatic alcohols.
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,
the chlorine-containing silicon compound is selected from one or more of trichloroethylsilane, trichlorooctylsilane, trichloroethoxysilane, trichlorobutoxysilane, dichlorodiethoxysilane and silicon tetrachloride.
7. The catalyst component according to any of claims 1 to 6 wherein the polyethylene oxide block polyisobutylene polymer comprises di-blocks and tri-blocks.
8. The catalyst component according to any of claims 1 to 6 wherein the block type of the polyethylene oxide block polyisobutylene 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 polyethylene oxide block polyisobutylene polymer is in star with form.
10. The catalyst component according to any of claims 1 to 6 wherein the polyisobutylene content of the polyethylene oxide block polyisobutylene polymer is 10wt% to 95 wt%.
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-C20Aromatic hydrocarbon solventB, forming a solution, and reacting with the transparent solution obtained in the step A to obtain a mixed solution;
and step C, sequentially adding a chlorine-containing silicon 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 silicon compound is 0.1 to 50 moles, and the concentration of the additive in the reaction system is 0.001 to 100 g/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 silicon compound is 0.5 to 20 moles, and the concentration of the additive in the reaction system is 0.01 to 50 g/L, per mole of the organomagnesium compound.
14. A catalyst for the homopolymerization or copolymerization of olefins comprising the catalyst component according to any one of claims 1 to 10 or prepared by the process according to any one of claims 11 to 13, and at least one AlR of general 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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KR101040388B1 (en) * 2007-01-30 2011-06-09 주식회사 엘지화학 Catalyst system for olefin polymerization comprising trioxasilocane and method for olefin polymerization using the same

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