CN116023549A - Prepolymerized catalyst, preparation method and application thereof - Google Patents

Prepolymerized catalyst, preparation method and application thereof Download PDF

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CN116023549A
CN116023549A CN202111258056.3A CN202111258056A CN116023549A CN 116023549 A CN116023549 A CN 116023549A CN 202111258056 A CN202111258056 A CN 202111258056A CN 116023549 A CN116023549 A CN 116023549A
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catalyst
phthalate
compound
preparation
mixture
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周奇龙
张锐
宋维玮
徐秀东
李凤奎
尹珊珊
郎旭东
于金华
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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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    • 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
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    • 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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Abstract

The invention discloses a prepolymerized catalyst and a preparation method and application thereof. The preparation method of the prepolymerized catalyst comprises the following steps: screening the carrier for preparing the catalyst, carrying out contact reaction on the carrier subjected to screening treatment and a titanium compound and an electron donor compound in the presence of an inert diluent, filtering, washing the obtained solid by adopting low-boiling alkane B to obtain a first mixture, and mixing the first mixture with white oil C to obtain a second mixture; removing the low-boiling alkane B in the second mixture in vacuum to obtain a slurry catalyst of the solid catalyst component A in the white oil C; the slurry catalyst is mixed with a hydrocarbon compound D, an alkylaluminum compound E, and optionally a silane compound F, and prepolymerized with an olefin monomer G. The prepolymerized catalyst of the invention can be directly used for olefin polymerization, and has good activity, orientation capability and hydrogen regulation sensitivity. The polymer obtained had very little fines and lumps.

Description

Prepolymerized catalyst, preparation method and application thereof
Technical Field
The present invention relates to a prepolymerized catalyst and a process for preparing the same, a catalyst system comprising the same, and a process for polymerizing olefins.
Background
Ziegler-Natta catalysts are widely used in the preparation of polyolefins. The Ziegler-Natta catalyst for industrial use mainly consists of 3 parts: (1) a Ziegler-Natta procatalyst; (2) an alkyl aluminum compound as a cocatalyst; (3) an external electron donor. In the industrial application process, the Ziegler-Natta main catalyst can directly enter the reactor or can enter the reactor after being prepolymerized. The magnification of the prepolymerization is generally 1 to 300 times.
In propylene polymerization industrial devices such as Hypol and horizons, the catalyst prepolymerization steps are as follows: (1) Adding hexane, alkyl aluminum and silane (optional) into a reactor; (2) adding a Ziegler-Natta procatalyst in dry powder form; (3) propylene is gradually introduced to carry out prepolymerization. The prepolymerized catalyst enters a reactor for propylene polymerization. This method has the following disadvantages: (1) The Ziegler-Natta procatalyst in dry powder form is difficult to leave residues or adhere by entering the reactor through a pipeline or short circuit and is extremely prone to corrosion. Embroidery residues generated by corrosion can enter the prepolymerization reactor along with dry powder, so that a filter screen, a pipeline and even a catalyst nozzle are blocked, and the device is stopped when serious. (2) The addition of the dry powder Ziegler-Natta procatalyst must be hoisted and the operational risks are great. (3) The stirring and rubbing process of the dry powder Ziegler-Natta procatalyst during drying, sieving increases the amount of fines in the catalyst which, after polymerization, form fines in the polymer powder. (4) The packaging barrel of the dry powder catalyst is not easy to recycle, thereby increasing the generation of dangerous waste and being unfavorable for green production.
During polyolefin production using Ziegler-Natta catalysts, the powder particles of the polymer replicate the particle morphology of the catalyst. Meanwhile, the amount of fine powder in the polymer is a very important control index. The fine powder can gradually gather along with the gas entering into the pipeline, the heat exchanger and other parts, even further react and plasticize, and caking, blocking and the like are generated, so that the long-period stable operation of the device is affected. Agglomerates produced during the catalyst preparation run the risk of forming local hot spots during the polymerization reaction, which in turn causes fluctuations in the reactor temperature.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel prepolymerized catalyst, and a preparation method and application thereof. The prepolymerized catalyst of the invention can be directly used for olefin polymerization, and has good activity, orientation capability and hydrogen regulation sensitivity. At the same time, little fines and lumps of polymer are obtained.
The first aspect of the present invention provides a method for preparing a prepolymerized catalyst, comprising:
step 1, screening a carrier for preparing a catalyst to obtain a screened carrier;
step 2, using a carrier subjected to screening treatment, carrying out contact reaction with a titanium compound and an electron donor compound in the presence of an inert diluent, filtering, washing the obtained solid by adopting low-boiling alkane B to obtain a first mixture of a solid catalyst component A dispersed in the alkane B, and mixing the first mixture with white oil C to obtain a second mixture;
Step 3, removing low-boiling alkane B in the second mixture in vacuum to obtain a slurry catalyst of the solid catalyst component A in the white oil C;
step 4, mixing the slurry catalyst with a hydrocarbon compound D, an aluminum alkyl compound E and an optional silane compound F, and carrying out a prepolymerization reaction with an olefin monomer G.
According to some embodiments of the preparation process of the present invention, the hydrocarbon compound D may be an alkane or a mixture of alkanes having a boiling point below 100 ℃, preferably at least one selected from pentane, isopentane, hexane, cyclohexane and heptane, more preferably at least one selected from pentane, isopentane and hexane.
According to some embodiments of the preparation method of the present invention, the alkylaluminum compound E as a cocatalyst may be various alkylaluminum compounds commonly used in the field of olefin polymerization, which can be used as cocatalysts of Ziegler-Natta catalysts. In a preferred case, the aluminum alkyl compound may be a compound represented by the formula (I),
AlR' n' X' 3-n' (I)
wherein R' is one of the following: hydrogen, C 1 -C 20 Alkyl or C of (2) 6 -C 20 Aryl of (a); x 'is halogen, and n' is an integer of 1-3.
The alkyl aluminum compound is preferably at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride. More preferably triethylaluminum and/or triisobutylaluminum.
According to some embodiments of the preparation method of the present invention, the alkyl aluminum compound may be used in an amount conventional in the art. Typically, the molar ratio of the aluminum alkyl compound to titanium in the solid catalyst component, calculated as aluminum, is from 0.05 to 50:1; preferably 1-20:1; more preferably 1-10:1.
According to some embodiments of the catalyst system of the present invention, a silane compound may be selectively added as an external electron donor, the kind and content of which are not particularly limited. Preferably, the molar ratio of the alkyl aluminum compound to the external electron donor compound, calculated as aluminum, is from 0.1 to 500:1, preferably from 1 to 100:1, more preferably from 2 to 20:1.
According to some embodiments of the preparation process of the present invention, the prepolymerization temperature is from 5 to 80 ℃, preferably from 10 to 60 ℃, more preferably from 15 to 35 ℃.
According to some embodiments of the preparation process of the present invention, the prepolymerization pressure is from 0 to 3.5MPa, preferably from 0.01 to 1.0MPa, more preferably from 0.02 to 0.6MPa.
And (3) the prepolymerization multiplying power of the catalyst, filtering the obtained prepolymerized catalyst, washing with hexane, and drying to obtain the solid prepolymerized catalyst. And dissolving a certain amount of solid prepolymerization catalyst in ethanol, separating out a polymer, and calculating the weight ratio of the polymer to the catalyst to obtain the prepolymerization multiplying power.
According to some embodiments of the preparation method of the present invention, the silane compound F may be various external electron donor compounds commonly used in the field of olefin polymerization, which can be used as cocatalysts of ziegler-natta catalysts. Preferably, the silane compound F may be an organosilicon compound represented by the formula (II),
R1” m” R2” n” Si(OR3”)4 -m”-n” (II)
in the formula (II), R1 'and R2' may be the same or different and are each independently halogen, hydrogen atom, C 1 -C 20 Alkyl, C of (2) 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 Is one of the haloalkyl groups; r3' is C 1 -C 20 Alkyl, C of (2) 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 Is one of the haloalkyl groups; m 'and n' are integers from 0 to 3, respectively, and m '+n'.<4. Specific examples of the silane compound F include trimethylmethoxysilane and trimethylethoxysilane Phenylsilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyldimethoxysilane, t-butylisobutyldimethoxysilane, t-butylbutyldimethoxysilane, t-butyl (sec-butyl) dimethoxysilane, t-butylpentyldimethoxysilane, t-butylnonyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane tert-butyloctyldimethoxy silane, tert-butyldecyldimethoxy silane, methyl tert-butyldimethoxy silane, cyclohexylmethyldimethoxy silane, cyclohexylethyldimethoxy silane, cyclohexylpropyldimethoxy silane, cyclohexylisobutyldimethoxy silane, dicyclohexyldimethoxy silane, cyclohexyltert-butyldimethoxy silane, cyclopentylmethyldimethoxy silane, cyclopentylethyl dimethoxy silane, cyclopentylpropyl dimethoxy silane, cyclopentyltert-butyldimethoxy silane, dicyclopentyldimethoxy silane, cyclopentylcyclohexyldimethoxy silane, bis (2-methylcyclopentyl) dimethoxy silane, diphenyldimethoxy silane, diphenyldiethoxy silane, phenyltriethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, ethyltrimethoxy silane, ethyl triethoxysilane, propyl trimethoxysilane, isopropyl trimethoxysilane, butyl triethoxysilane, isobutyl trimethoxysilane, t-butyl trimethoxysilane, sec-butyl trimethoxysilane, amyl trimethoxysilane, isopentyl trimethoxysilane, cyclopentyl trimethoxysilane, cyclohexyl trimethoxysilane, diphenyl dimethoxy silane, diphenyl diethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, n-propyl trimethoxy silane, vinyl trimethoxy silane, tetramethoxy silane At least one of silane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxy silane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxy silane, and (1, 1-trifluoro-2-propyl) -methyldimethoxy silane. More preferably, the external electron donor compound may be at least one of dicyclopentyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl tert-butyl dimethoxy silane, and tetramethoxy silane.
According to some embodiments of the preparation process of the present invention, the molar ratio of the alkylaluminum compound to the silane compound, calculated as aluminum, is 0.1-500:1, preferably 1-100:1, more preferably 1-20:1.
According to some embodiments of the process of the invention, the olefinic monomers G are at least one of the monomers represented by the general formula CH 2 Olefins expressed by =chr, wherein R is hydrogen or C 1 -C 6 Is a hydrocarbon group. Specific examples include, but are not limited to: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the alpha-olefin CH 2 =chr is one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene. More preferably, the olefin monomer G is one or more of propylene and ethylene.
According to some embodiments of the preparation process of the present invention, the weight ratio of olefin monomer to solid catalyst component a is from 0.5 to 1000:1, preferably from 1 to 100:1, more preferably from 1 to 10:1.
According to some embodiments of the preparation process of the present invention, the conditions under which the mixture of solid catalyst component a dispersed in alkane B is mixed with white oil C include: the temperature is 20-40 ℃ and the time is 5-60 minutes.
According to some embodiments of the preparation process of the present invention, the temperature of the prepolymerization is from 5 to 80 ℃, preferably from 10 to 60 ℃, more preferably from 15 to 35 ℃.
According to some embodiments of the preparation process of the present invention, the pressure (gauge pressure) of the prepolymerization is 0-3.5MPa, preferably 0.01-1.0MPa, more preferably 0.02-0.6MPa.
According to some embodiments of the preparation process according to the invention, the preparation of the catalyst support refers to a magnesium-containing precursor that can be finally reacted to an active magnesium chloride support for the preparation of Ziegler-Natta polyolefin catalysts. The particle size and morphology of the magnesium-containing precursor (carrier) are determined, and the particle size and morphology of the catalyst are basically replicated to those of the carrier. Such supports include, but are not limited to, the magnesium alkoxide support prepared in CN102453150B, the magnesium chloride alkoxide support prepared in CN 1289542C. The support is a magnesium-containing support for the preparation of Ziegler-Natta polyolefin catalysts, preferably the support is one or more of a spheroidal magnesium alkoxide support and a spheroidal magnesium chloride alkoxide support.
The solid catalyst components prepared by the solution precipitation method known in the art are not suitable for the preparation method of the prepolymerized catalyst according to the present invention. Specifically, as described in CN85100997a, magnesium chloride is dissolved in a solvent, and then active magnesium chloride particles are precipitated under certain conditions, and then the preparation method of the solid catalyst component loaded with titanium and ester is performed. Since the precipitated active magnesium chloride particles (as a carrier) cannot be subjected to screening separation to remove part of irregular or agglomerated reject particles, the solid catalyst component prepared based on the method cannot be used for preparing the prepolymerized catalyst according to the invention.
According to some embodiments of the preparation method of the present invention, the carrier may need to be sieved before use. If not sized, the large particles or agglomerates of the support may enter the catalyst preparation process, resulting in a large particle size or agglomerated catalyst. The catalyst preparation method of the invention does not have the separation and screening processes of the catalyst dry powder. The large particle size or agglomeration catalyst can form hot spots in the polymerization reactor, thereby creating unstable reactor temperature and risk of polymer agglomeration, which in turn can affect plant operation. Thus, the sieving of the carrier is one of the keys to ensure a successful implementation of the method. Preferably, the sieving treatment gives the support an average particle size of not more than 100. Mu.m, preferably from 10 to 80. Mu.m. Preferably, sieving is performed using, for example, but not limited to, 80-250 mesh screens.
According to some embodiments of the preparation method of the present invention, step 2 does not undergo a drying treatment during the process of obtaining the solid catalyst component a. Namely, the carrier subjected to screening treatment is used for carrying out contact reaction with the titanium compound and the electron body compound in the presence of an inert diluent, and the drying treatment is not carried out in the filtering process.
In the present invention, the solid catalyst component a can be carried out by a method for producing an olefin catalyst component which is conventional in the art. The solid catalyst component of the present invention can be prepared, for example, by the following method.
In the first method, an alkoxy magnesium or an alkoxy magnesium halide is suspended in an inert diluent to form a suspension, and the suspension is mixed and contacted with the titanium compound and the internal electron donor to obtain a solid dispersion system, which is commonly called a mother solution. Filtering mother liquor, and suspending the obtained solid matters in a solution containing titanium tetrachloride for contact treatment, which is commonly called titanium treatment; and then filtering and washing to obtain the solid catalyst component.
Specific examples of the above-mentioned alkoxymagnesium in the first process include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropylmagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, dihexyloxymagnesium, di (2-ethyl) hexyloxymagnesium and the like or a mixture thereof, and preferably diethoxymagnesium or a mixture of diethoxymagnesium and other alkoxymagnesium. The preparation of the magnesium alkoxide compound may be carried out by methods known in the art, such as disclosed in patent CN101906017a by reacting magnesium metal with a fatty alcohol in the presence of a small amount of iodine.
Specific examples of the alkoxymagnesium halide in the first method include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, and the like, and ethoxymagnesium chloride is preferable. The alkoxy magnesium halide compound can be prepared by methods well known in the art, such as mixing the grignard reagent butyl magnesium chloride with tetraethoxytitanium and tetraethoxysilicon to prepare magnesium ethoxychloride.
The inert diluent used in the formation of the mother liquor in process one may be at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
The amount of each component used for forming the mother liquor in the first method is 0.5 to 100 moles, preferably 1 to 50 moles, of the titanium compound per mole of magnesium; the inert diluent is used in an amount of usually 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the internal electron donor compound is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.
The contacting temperature of the components in the formation of the mother liquor in process one is typically from-40 to 200 ℃, preferably from-20 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.
During the titanium treatment process described in method one, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene may be optionally added to the titanium tetrachloride-containing solution used.
In the titanium treatment process in the first method, the amount of each component in the titanium tetrachloride-containing solution used is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0 to 100 mol, preferably 0 to 50 mol.
The number of titanium treatments in the first process is 0 to 10, preferably 1 to 5.
The electron donor compound described above may optionally be added during the titanium treatment in process one, wherein the internal electron donor is used in an amount of usually 0.005 to 10 moles, preferably 0.01 to 1 mole.
The titanium treatment temperature in process one is typically from 0 to 200 ℃, preferably from 30 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 6 hours.
In the second method, an alcohol compound of magnesium dihalide is suspended in an inert diluent to form a suspension, and the suspension is mixed and contacted with the titanium compound and the internal electron donor to obtain a solid dispersion system, which is hereinafter referred to as a mother liquid. Filtering the mother liquor, and suspending the obtained solid matters in a solution containing titanium tetrachloride for contact treatment, which is hereinafter generally referred to as titanium treatment; and then filtering and washing to obtain the solid catalyst component.
The magnesium dihalide alkoxide in process two may be prepared by the following process: mixing an alcohol (such as methanol, ethanol, propanol or isopropanol) with magnesium halide in the presence of an inert solvent (such as hexane, heptane, octane, decane, benzene, toluene, xylene, etc.) which is not miscible with the adduct to form an emulsion, and rapidly quenching and dispersing the emulsion to obtain spherical particles which are the alcohol compound of the magnesium dihalide.
The inert diluent used in the formation of the mother liquor in process two may be at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
The amount of each component used for forming the mother liquor in the second method is 0.5 to 100 moles, preferably 1 to 50 moles, of the titanium compound per mole of magnesium; the inert diluent is used in an amount of usually 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the electron donor compound is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.
The contacting temperature of the components in the formation of the mother liquor in process two is typically from-40 to 200 ℃, preferably from-20 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.
In the titanium treatment process described in method II, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene may be optionally added to the titanium tetrachloride-containing solution used.
In the titanium treatment process in the second method, the amount of each component in the titanium tetrachloride-containing solution used is 0.5 to 100 moles, preferably 1 to 50 moles, of the titanium compound per mole of magnesium; the inert diluent is used in an amount of usually 0 to 100 mol, preferably 0 to 50 mol.
The number of titanium treatments in the second method is 0 to 10, preferably 1 to 5.
The electron donor compound described above may be optionally added during the titanium treatment in the second method, wherein the internal electron donor is used in an amount of usually 0.005 to 10 moles, preferably 0.01 to 1 mole.
The titanium treatment temperature in the second process is generally 0-200 ℃, preferably 30-150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 6 hours.
In the above-mentioned method one and method two, the internal electron donor compound may be at least one selected from the group consisting of phthalate compounds, glycol ester compounds, cyano succinate compounds, diether compounds and succinate compounds; preferably at least one selected from the group consisting of glycol ester compounds, cyano succinic acid ester compounds, diether compounds and succinic acid ester compounds.
Examples of the phthalate compound include, but are not limited to, phthalate compounds selected from those represented by formula (III),
Figure BDA0003324733810000081
in the formula (III), R 15 And R is 16 Identical or different, each independently selected from C 1 -C 20 Straight-chain alkane, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Alkylaryl or C of (C) 7 -C 20 The hydrogen atom on the carbon in the alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl group may be optionally substituted with a heteroatom, alkyl or alkoxy group and the carbon atom on the alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl backbone may be optionally substituted with a heteroatom. Preferably, R 15 And R is 16 Each independently selected from C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl or C of (C) 6 -C 10 Aryl of (a); more preferably, R 15 And R is 16 Each independently selected from C 1 -C 6 Straight-chain alkyl or C 1 -C 6 Branched alkyl of (a); further preferably, R 15 And R is 16 Each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or phenyl.
According to some embodiments of the preparation method of the present invention, examples of the phthalate compound represented by formula (III) include, but are not limited to: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di (1-methyl) propyl phthalate, di-t-butyl phthalate, di-n-pentyl phthalate, di (1-methyl) butyl phthalate, di (2-methyl) butyl phthalate, diisopentyl phthalate, di (1, 1' -dimethyl) propyl phthalate, dipentyl phthalate, di (1, 2-dimethyl) propyl phthalate, n-hexyl phthalate, di (1-methyl) pentyl phthalate, di (2-methyl) pentyl phthalate, di (3-methyl) pentyl phthalate, diisohexyl phthalate, di (1, 1' -dimethyl) butyl phthalate, di (2, 2' -dimethyl) butyl phthalate, di (1, 2-dimethyl) butyl phthalate, di (2, 3-dimethyl) butyl phthalate, di (1, 1' -dimethyl) butyl phthalate; 2-trimethyl) propyl phthalate, di (1, 2' -trimethyl) propyl phthalate, n-heptyl phthalate, di (1-methyl) hexyl phthalate, di (2-methyl) hexyl phthalate, di (3-methyl) hexyl phthalate, di (4-methyl) hexyl phthalate, diisoheptyl phthalate, di (1, 1' -dimethyl) pentyl phthalate, di (2, 2' -dimethyl) pentyl phthalate, di (3, 3' -dimethyl) pentyl phthalate, dithienyl phthalate, di (1, 2-dimethyl) pentyl phthalate, di (1, 3-dimethyl) pentyl phthalate, di (1, 4-dimethyl) pentyl phthalate, di (2, 3-dimethyl) pentyl phthalate, di (2, 4-dimethyl) pentyl phthalate, di (3, 4-dimethyl) pentyl phthalate, di (1, 1', 2-trimethyl) butyl phthalate, di (1, 1', 3-trimethyl) butyl phthalate, di (1, 2' -trimethyl) butyl phthalate, di (2, 2', 3-trimethyl) butyl phthalate, di (1, 3' -trimethyl) butyl phthalate, di (2, 3' -trimethyl) butyl phthalate, di (1, 1', 2' -tetramethyl) propyl phthalate, n-octyl phthalate, di (1-methyl) heptyl phthalate, di (2-methyl) heptyl phthalate, di (3-methyl) heptyl phthalate, di (4-methyl) heptyl phthalate, and, di (5-methyl) heptyl phthalate, diisooctyl phthalate, di (1, 1' -dimethyl) hexyl phthalate, di (2, 2' -dimethyl) hexyl phthalate, di (3, 3' -dimethyl) hexyl phthalate, di (4, 4' -dimethyl) hexyl phthalate, di (5, 5' -dimethyl) hexyl phthalate, di (1, 2-dimethyl) hexyl phthalate, di (1, 3-dimethyl) hexyl phthalate, di (1, 4-dimethyl) hexyl phthalate, di (1, 5-dimethyl) hexyl phthalate, di (2, 3-dimethyl) hexyl phthalate, di (2, 4-dimethyl) hexyl phthalate, di (2, 5-dimethyl) hexyl phthalate, di (3, 4-dimethyl) hexyl phthalate, di (3, 5-dimethyl) hexyl phthalate, di (4, 5-dimethyl) hexyl phthalate, di (1, 1 '; 2-trimethyl) pentyl ester, di (1, 1', 3-trimethyl) pentyl phthalate, di (1, 1', 4-trimethyl) pentyl phthalate, di (1, 2' -trimethyl) pentyl phthalate, di (2, 2', 3-trimethyl) pentyl phthalate, di (2, 2', 4-trimethyl) pentyl phthalate, bis (1, 3 '-trimethyl) pentyl phthalate, bis (2, 3' -trimethyl) pentyl phthalate, bis (3, 3', 4-trimethyl) pentyl ester, di (1, 4' -trimethyl) pentyl ester of phthalic acid, di (2, 4 '-trimethyl) pentyl ester of phthalic acid, di (3, 4' -trimethyl) pentyl ester of phthalic acid, di (1, 1', 2' -tetramethyl) butyl ester of phthalic acid, di (1, 1',3,3' -tetramethyl) butyl phthalate, di (2, 2', 3' -tetramethyl) butyl phthalate, diphenyl phthalate, di (o-methyl) phenyl phthalate, di (p-methyl) phenyl phthalate, di (m-methyl) phenyl phthalate, di (o-methoxy) phenyl phthalate, di (p-methoxy) phenyl phthalate, di (m-methoxy) phenyl phthalate; preferably selected from the group consisting of dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, n-hexyl phthalate, diisohexyl phthalate, n-heptyl phthalate, isoheptyl phthalate, n-octyl phthalate, isooctyl phthalate, diphenyl phthalate, di (methyl) phenyl phthalate, di (p-methyl) phenyl phthalate, di (m-methyl) phenyl phthalate, di (o-methoxy) phenyl phthalate, di (p-methoxy) phenyl phthalate; more preferably selected from the group consisting of dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, n-hexyl phthalate, isohexyl phthalate, diphenyl phthalate, di (methyl) phenyl phthalate, di (p-methyl) phenyl phthalate, di (methoxy) phenyl phthalate, di (p-methoxy) phenyl phthalate.
Examples of the glycol ester compound include, but are not limited to, a glycol ester compound selected from the group consisting of those represented by formula (IV),
Figure BDA0003324733810000101
in the formula (IV), R 17 And R is 18 Identical or different, each independently of the other is a substituted or unsubstituted C 1 -C 20 Straight-chain alkane, substituted or unsubstituted C 3 -C 20 Branched alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 6 -C 20 Aryl, substituted or unsubstituted C 7 -C 20 Alkylaryl, substituted or unsubstituted C 7 -C 20 Aralkyl, substituted or unsubstituted C 2 To C 10 Or substituted or unsubstituted C 10 -C 20 Condensed ring aryl of (a); r is R 19 -R 24 The same or differentEach independently hydrogen, halogen, substituted or unsubstituted straight chain C 1 -C 20 Straight-chain alkyl, substituted or unsubstituted C 3 -C 20 Branched alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 6 -C 20 Aryl, substituted or unsubstituted C 7 -C 20 Alkylaryl, substituted or unsubstituted C 7 -C 20 Aralkyl, substituted or unsubstituted C 2 -C 10 Or substituted or unsubstituted C 10 -C 20 Condensed ring aryl of (a); or R is 19 -R 22 At least one of which is together with R 23 -R 24 Is formed into a ring.
Examples of the glycol ester compound represented by the formula (IV) include, but are not limited to: at least one of 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 1, 3-butanediol dimethylbenzoate, 2-methyl-1, 3-butanediol diisochlorobenzoate, 2, 3-dimethyl-1, 3-butanediol dibenzoate, 1, 3-pentanediol pivalate, 2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol benzoic acid cinnamate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and 2-methyl-3, 5-heptanediol dibenzoate; preferably at least one of 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate and 2, 4-pentanediol dibenzoate; more preferably 3, 5-heptanediol dibenzoate.
Examples of the cyano succinic acid ester compounds include, but are not limited to, those selected from the group consisting of cyano succinic acid ester compounds represented by formula (V),
Figure BDA0003324733810000111
in the formula (V), R 25 And R is 26 Identical or different, each independently selected from hydrogen, C 1 -C 14 Straight chain alkyl, C 3 -C 14 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C of (2) 7 -C 10 Alkylaryl or C of (C) 7 -C 10 Aralkyl of (a); r is R 27 And R is 28 Identical or different, each independently selected from C 1 -C 10 Straight chain alkyl, C 1 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C of (2) 7 -C 20 Alkylaryl or C of (C) 7 -C 20 An aralkyl group of (a).
Examples of the cyano succinic acid ester compounds represented by the formula (V) include, but are not limited to: 2, 3-Diisopropyl-2-cyanosuccinic acid dimethyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid diethyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid di-n-propyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid diisopropyl ester, 2, 3-Din-butyl-2, 3-Diisopropyl-2-cyanosuccinic acid diisobutyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid-1-methyl-4-ethyl ester (R) 25 Methyl, R 26 =ethyl), 2, 3-diisopropyl-2-cyano-butanedioic acid-1-ethyl-4-methyl ester (R 25 =ethyl, R 26 =methyl), 2, 3-diisopropyl-2-cyano-butanedioic acid-1-n-butyl-4-ethyl ester (R 25 N-butyl, R 26 =ethyl), 2, 3-diisopropyl-2-cyano-butanedioic acid 1-ethyl-4-n-butyl ester (R 25 =ethyl, R 26 =n-butyl), 2, 3-diisobutyl-2-cyanobuty-anedioic acid dimethyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid diethyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid di-n-propyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid di-n-butyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid diisobutyl ester, 2, 3-diisobutyl-2-cyanobuty-1-methyl-4-ethyl ester (R) 25 Methyl, R 26 =ethyl), 2, 3-diisobutyl-2-cyano-succinic acid-1-ethyl-4-methyl ester (R 25 =ethyl, R 26 =methyl), 2, 3-diisobutyl-2-cyanobutanedioic acid-1-n-butyl-4-ethyl ester (R 25 N-butyl, R 26 =ethyl), 2, 3-diisobutyl-2-cyano-butanedioic acid-1-ethyl-4-n-butyl ester(R 25 =ethyl, R 26 2, 3-di-sec-butyl-2-cyanobutyanedioic acid diethyl ester, 2, 3-di-sec-butyl-2-cyanobutyanedioic acid diisopropyl ester, 2, 3-di-sec-butyl-2-cyanobutyanedioic acid di-n-butyl ester, 2, 3-di-sec-butyl-2-cyanobutyronic acid diisobutyl ester, 2, 3-di-sec-butyl-2-cyanobutyronic acid-1-methyl-4-ethyl ester (R) 25 Methyl, R 26 =ethyl), 2, 3-di-sec-butyl-2-cyano succinic acid-1-ethyl-4-methyl ester (R 25 =ethyl, R 26 Methyl), 2, 3-di-sec-butyl-2-cyano-butanedioic acid-1-n-butyl-4-ethyl ester (R 25 N-butyl, R 26 =ethyl), 2, 3-di-sec-butyl-2-cyano succinic acid-1-ethyl-4-n-butyl ester (R 25 =ethyl, R 26 =n-butyl), dimethyl 2, 3-dicyclopentyl-2-cyanobutyrate, diethyl 2, 3-dicyclopentyl-2-cyanobutyrate, di-n-propyl 2, 3-dicyclopentyl-2-cyanobutyrate, diisopropyl 2, 3-dicyclopentyl-2-cyanobutyrate, di-n-butyl 2, 3-dicyclopentyl-2-cyanobutyrate, diisobutyl 2, 3-dicyclopentyl-2-cyanobutyrate, 1-methyl 2-cyanobutyrate-4-ethyl ester (R) 25 Methyl, R 26 =ethyl), 2, 3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl-4-methyl ester (R 25 =ethyl, R 26 =methyl), 2, 3-dicyclopentyl-2-cyanobuccinic acid-1-n-butyl-4-ethyl ester (R 25 N-butyl, R 26 =ethyl), 2, 3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl-4-n-butyl ester (R 25 =ethyl, R 26 =n-butyl), dimethyl 2, 3-dicyclohexyl-2-cyanobutyrate, diethyl 2, 3-dicyclohexyl-2-cyanobutyrate, di-n-propyl 2, 3-dicyclohexyl-2-cyanobutyrate, di-isopropyl 2, 3-dicyclohexyl-2-cyanobutyrate, di-n-butyl 2, 3-dicyclohexyl-2-cyanobutyrate, di-isobutyl 2, 3-dicyclohexyl-2-cyanobutyrate, 1-methyl-4-ethyl 2, 3-dicyclohexyl-2-cyanobutyrate (R) 25 Methyl, R 26 =ethyl), 2, 3-dicyclohexyl-2-cyanobuccinic acid-1-ethyl-4-methyl ester (R 25 =ethyl, R 26 =methyl), 2, 3-dicyclohexyl-2-cyanobuccinic acid-1-n-butylEster-4-ethyl ester (R) 25 N-butyl, R 26 =ethyl), 2, 3-dicyclohexyl-2-cyanobuccinic acid-1-ethyl-4-n-butyl ester (R 25 =ethyl, R 26 N-butyl); preferably diethyl 2, 3-diisopropyl-2-cyanobuccinate, di-n-propyl 2, 3-diisopropyl-2-cyanobuccinate, di-isopropyl 2, 3-diisopropyl-2-cyanobuccinate, di-n-butyl 2, 3-diisopropyl-2-cyanobuccinate, diisobutyl 2, 3-diisopropyl-2-cyanobuccinate; more preferably diethyl 2, 3-diisopropyl-2-cyano succinate.
Examples of the diether compound include, but are not limited to, diether compounds selected from those represented by formula (VI),
Figure BDA0003324733810000121
in the formula (VI), R 29 And R is 30 Identical or different, each independently selected from C 1 -C 10 Straight chain or C of (2) 3 -C 10 Branched alkyl of (a); r is R 32 And R is 33 Identical or different, each independently selected from C 1 -C 20 Straight chain of C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Substituted or unsubstituted aryl or C 7 -C 20 Alkylaryl groups of (a); r is R 31 And R is 34 The same or different are each independently selected from hydrogen, C 1 -C 10 Straight-chain alkyl or C 3 -C 10 Branched alkyl groups of (a).
Examples of the diether compounds represented by the formula (VI) include, but are not limited to: 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 9-bis (methoxymethyl) fluorene, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2-dicyclopentyl dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 9-bis (methoxymethyl) fluorene are preferred.
Examples of the succinate compound include, but are not limited to, a succinate compound selected from the group consisting of those represented by formula (VII),
Figure BDA0003324733810000131
in the formula (VII), R 35 And R is 36 Identical or different, each independently selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 2 -C 20 Alkenyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7-20 Aralkyl or C of (C) 7 -C 20 Alkylaryl groups of (a); r is R 37 -R 40 Are identical or different from each other and are each independently selected from hydrogen, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 2 -C 20 Alkenyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl groups of (a); the R is 35 And R is 36 Optionally containing heteroatoms.
Examples of the succinic acid ester compounds represented by the formula (VII) include, but are not limited to: diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropyl succinate, diethyl 2, 3-diisopropyl succinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2,3- (bistrimethylsilyl) succinate, diethyl 2- (, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisopentylsuccinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropyl succinate diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2, 3-methylsuccinate diethyl 2, 3-tetraethyl succinate, diethyl 2, 3-tetrapropyl succinate, diethyl 2, 3-diethyl-2, 3-diisopropyldisuccinate diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-di-tert-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2,3- (bistrimethylsilyl) succinate, diisobutyl 2- (, 3-trifluoropropyl) -3-methylsuccinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisoamyl succinate, diisobutyl 2,3- (1-trifluoromethyl-ethyl) succinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl 2-tert-butyl-3-isopropylsuccinate diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2, 3-methylsuccinate diisobutyl 2, 3-tetraethyl succinate, diisobutyl 2, 3-tetrapropyl succinate, diisobutyl 2, 3-diethyl-2, 3-diisopropyldisuccinate; preferably diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-diisopropylsuccinate; 2, 3-diisopropylsuccinate.
According to some embodiments of the preparation method of the present invention, the internal electron donor may be used alone or in combination of two or more internal electron donor compounds.
According to some embodiments of the preparation process of the present invention, the solid catalyst component a obtained by washing is not subjected to drying and corresponding sieving treatments, so as to reduce the damage to the morphology of the catalyst particles by the drying process and corresponding sieving process.
According to some embodiments of the preparation process of the present invention, the low boiling alkane B is an alkane or a mixture of alkanes having a boiling point below 100 ℃, preferably at least one selected from pentane, isopentane, hexane, cyclohexane and heptane.
According to some embodiments of the preparation method of the present invention, the weight ratio of the solid catalyst component a to the low boiling alkane B may be well stirred in a suspension.
According to some embodiments of the preparation method of the present invention, the white oil C may be selected from various types of white oils or mixtures thereof in industrial white oil or food additive white oil according to the national standard of the people's republic of petrochemical industry, NB/SH/T0006-2017 or the national standard of the people's republic of China, GB 1886.215-2016. Preferably, the white oil C is 68# industrial white oil and/or 100# industrial white oil.
According to some embodiments of the preparation process of the present invention, the ratio of the weight of white oil C added to the weight of solid catalyst component A is from 1 to 10:1, preferably from 4 to 7:1.
According to some embodiments of the preparation method of the present invention, when the white oil C is added, the mixture of the solid catalyst component a and a part of the alkane B is maintained in a state of stirring dispersion so as to prevent catalyst agglomeration. Wherein the weight ratio of A to B is not critical, so as to keep the system well-stirred and dispersed, and the preferred weight ratio of A to B is 1:1-1:10, and more preferred is 1:2-1:4.
According to some embodiments of the preparation process of the present invention, the removal of the low boiling alkane B by vacuum may be carried out at a certain temperature. Increasing the temperature may increase the removal efficiency, but too high a temperature may deteriorate the performance of the solid catalyst component a. Preferably, the conditions for vacuum removal of the low boiling alkane B include: the temperature is 20-100deg.C, preferably 40-80deg.C. The lower vacuum degree is beneficial to the high-efficiency removal of alkane B, and simultaneously, the removal temperature is reduced so as to be beneficial to the performance maintenance of the solid catalyst component A. Thus, the lower the vacuum, the more advantageous is the removal of alkane B.
According to some embodiments of the preparation method of the invention, the materials can be mixed in any form when vacuuming to remove the low boiling alkane B so as to ensure uniformity of alkane B removal, such as rotation, stirring and the like; the stirring is preferably carried out at a low speed with less shearing of the mass to reduce damage to the solid catalyst components, such as ribbon stirring.
According to some embodiments of the preparation method of the present invention, the lower the residue of the final alkane B in the white oil C, the better, but the longer it takes to reach the lower alkane B content, thereby reducing the production efficiency and increasing the production cost. The residual amount of alkane B in white oil C is 0.3-5.0 wt%, more preferably 0.8-3.0 wt%, most preferably 1.0-2.0 wt%.
According to some embodiments of the preparation method of the present invention, it is necessary to filter the slurry catalyst in step 3 while ensuring that the slurry flows smoothly. But due to the presence of white oil, the fluid volume of the particles increases; and, the liquid filtration area on-line is limited. In order to ensure the timeliness of the filtration, the mesh number of the filtration needs to be reduced. However, this reduces the effectiveness of the filtration. For example, the dried powder of the solid catalyst component A having a particle size of 30 to 40 μm may be sieved using a 150 to 200 mesh sieve, while the slurry catalyst obtained from the solid catalyst component A having the same particle size may be filtered using a 40 to 60 mesh sieve. In other words, the slurry filtration effect is lower than the sieving effect of the dried solid catalyst component, which results in more agglomerated catalyst residues. This is also why the preparation of the prepolymerized catalyst according to the invention requires the use of a sieved support. Agglomerated particles are removed during carrier sieving and the risk of subsequent catalyst agglomeration is reduced.
The second aspect of the invention provides a pre-catalyst prepared according to the preparation method described above.
In a third aspect, the present invention provides a catalyst system for the polymerization of olefins comprising:
(1) The prepolymerized catalyst described above; and
(2) An alkylaluminum compound as a cocatalyst;
(3) Optionally an external electron donor.
According to some embodiments of the catalyst system of the present invention, the alkyl aluminum compound may be a compound represented by formula (I),
AlR' n' X' 3-n' (VIII)
wherein R' is one of the following: hydrogen, C 1 -C 20 Alkyl or C of (2) 6 -C 20 Aryl of (a); x 'is halogen, and n' is an integer of 1-3.
The alkyl aluminum compound is preferably at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride. More preferably triethylaluminum and/or triisobutylaluminum.
According to some embodiments of the catalyst system of the present invention, the external electron donor may be an organosilicon compound represented by formula (VIII),
R1” m” R2” n” Si(OR3”)4 -m”-n” (VIIII)，
in formula (VIIII), R1 'and R2' may be the same or different and each is a halogen atom, a hydrogen atom, C 1 -C 20 Alkyl, C of (2) 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 Is one of the haloalkyl groups; r3' is C 1 -C 20 Alkyl, C of (2) 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 Is one of the haloalkyl groups; m 'and n' are integers from 0 to 3, respectively, and m '+n'.<4. Specific examples of the external electron donor include trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutyldimethoxysilane, tert-butyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl (sec-butyl) dimethoxysilane, tert-butylpentylmethoxysilane, tert-butylnonyldimethoxysilane, tert-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butyldecyldimethoxysilane, methyl tert-butyldimethoxysilane, cyclohexylmethylmethyldimethoxysilane A vinyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylt-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentylt-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetraethoxysilane, 2-ethyl-1, 2-1-dimethylpiperidine and 1, 2-dimethylpiperidine (1, 2-1-dimethylpiperidine) 1-2-fluoro-1-propyl-1-2-dimethylpiperidine, the external electron donor compound may be at least one of dicyclopentyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl tert-butyl dimethoxy silane, and tetramethoxy silane.
In a fourth aspect the present invention provides a process for the polymerisation of olefins comprising contacting one or more olefins with a pre-polymerisation catalyst as described above to obtain a polymer.
According to some embodiments of the process for the polymerization of olefins according to the present invention, at least one of the olefin monomers is of the formula CH 2 Olefins expressed by =chr, whereinR is C 1 -C 6 Is a hydrocarbon group. Specific examples include, but are not limited to: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the alpha-olefin CH 2 =chr is one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene. More preferably, said compound represented by the general formula CH 2 The olefins expressed by =chr are one or more of propylene and ethylene.
According to some embodiments of the process for the polymerization of olefins according to the invention, the weight ratio of olefin monomer to solid catalyst component a is from 0.5 to 1000:1, preferably from 1 to 100:1, more preferably from 1 to 10:1.
According to some embodiments of the process for the polymerization of olefins according to the present invention, the polymerization temperature is from 5 to 80 ℃, preferably from 10 to 60 ℃, more preferably from 15 to 35 ℃.
According to some embodiments of the slurry catalyst of the present invention, the polymerization pressure is from 0 to 3.5MPa, preferably from 0.01 to 1.0MPa, more preferably from 0.02 to 0.6MPa.
The invention has the beneficial effects that:
(1) The prepolymerized catalyst prepared by the method can be directly used for olefin polymerization, and has good activity, orientation capability and hydrogen regulation sensitivity. At the same time, little fines and lumps of polymer are obtained. Compared with the prepolymerized catalyst directly prepared by the dry powder catalyst, the prepolymerized catalyst prepared by the direct slurry has less fine powder; the polymer lump prepared by the prepolymerized catalyst prepared by the method is obviously reduced compared with the solid catalyst component prepared by a carrier without sieving; compared with a dry powder catalyst, the production efficiency of the method for preparing the prepolymerized catalyst by using the direct slurry provided by the invention is greatly improved.
(2) The prepolymerized catalyst of the invention can be directly injected into an industrial device such as a Hypol device or a Horiozone for polymerization.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method and the equipment used in the test are as follows:
1. hexane content in white oil was determined using Agilent 7890 gas chromatography.
2. Polymer fines analysis: and screening the polymer powder obtained by polymerizing the catalyst by adopting a 150-mesh screen, wherein the weight ratio of the powder smaller than 150 meshes is characterized as the content of fine powder.
3. Polymer block analysis: and screening the polymer powder obtained by polymerizing the catalyst by using a 5-mesh screen, wherein the weight ratio of the powder with the size larger than 5 meshes is characterized as the lump material content.
4. Determination of the Melt Index (MI) of the Polymer: measured according to GB/T3682-2000.
5. Polymer isotacticity (II) was determined using heptane extraction: after 2g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, the residue was dried to constant weight and the ratio of the weight (g) of the polymer to 2 (g) was isotacticity.
6. Titanium content in the catalyst: according to 721 spectrophotometer testing.
7. And (3) the prepolymerization multiplying power of the catalyst, filtering the obtained prepolymerized catalyst, washing with hexane, and drying to obtain the solid prepolymerized catalyst. And dissolving a certain amount of solid prepolymerization catalyst in ethanol, separating out a polymer, and calculating the weight ratio of the polymer to the catalyst to obtain the prepolymerization multiplying power.
8. Polymerization activity = polymer weight (kg)/solid catalyst component weight (g Cat).
[ example 1 ]
1. Preparation of slurry catalyst A1:
(1) Preparation of dialkoxy magnesium carrier:
after a 16L pressure-resistant reactor equipped with a stirrer was sufficiently replaced with nitrogen, 10000mL of ethanol, 300mL of 2-ethylhexanol and 200mL of isopropanol were added to the reactor, and 12g of iodine and 8g of magnesium chloride were added to dissolve the materials. After stirring, heating up until the reflux temperature of the reaction system is reached. Then 640g of magnesium powder was added successively. The reaction is carried out until completion, i.e. no more hydrogen is discharged. Then washing, separating and drying. The obtained dialkoxy magnesium carrier is screened by a 150-mesh screen to remove blocks, and the screened dialkoxy magnesium carrier is obtained.
(2) Preparation of the catalyst component:
taking 650g of dialkoxy magnesium carrier and 3250mL of toluene and 65mL of di-n-butyl phthalate (DNBP) to prepare a suspension; adding 2600mL of toluene and 3900mL of titanium tetrachloride into a 16L pressure-resistant reaction kettle repeatedly replaced by high-purity nitrogen, cooling to-5 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, slowly heating to 110 ℃, adding 65mL of DNBP when the temperature is raised to 80 ℃, keeping the temperature for 2 hours, and then press-filtering the liquid clean. Then, 5070mL of toluene and 3380mL of titanium tetrachloride were added, and the mixture was stirred at 110℃for 1 hour, thereby treating 3 times, filtering off the liquid, washing the obtained solid with hexane 4 times each time of 6000mL, and filtering off the liquid to obtain a solid catalyst component product. The above solid catalyst component was not dried, and 2000mL of hexane was again added to obtain a mixture in which the solid catalyst component was dispersed in hexane.
(3) Preparing a slurry catalyst:
the mixture obtained in the step (2) was stirred (the titanium content of the solid catalyst component after separation was 2.55%) while 1668 g of dehydrated oxygen-treated 68# technical white oil was directly added, and the mixture was stirred while drying at 60℃under vacuum for 12 hours to remove the residual hexane, to obtain a slurry catalyst A1 of the catalyst in white oil. The catalyst concentration was 30.2 wt% and the hexane content in the white oil was 0.3 wt%.
2. Preparation of prepolymerized catalyst B1:
50 g of slurry catalyst A1 which is uniformly stirred is added with 360 ml of hexane for dispersion, 30ml of 0.5mol/L triethylaluminum hexane solution and 25ml of 0.1mol/L methylcyclohexyl dimethoxy silane are added, and after stirring and reacting for 10 minutes at 20 ℃, 30 g of propylene is introduced at a constant speed within 8 hours for polymerization, and a prepolymerization catalyst is obtained. The reactor pressure was controlled at 0.02MPa and the temperature 25 ℃. The concentration of the prepolymerized catalyst B1 was 12.5% by weight. The prepolymerization multiplying power is 1.95.
3. Evaluation of the prepolymerization agent B1:
after the gas phase propylene was sufficiently replaced in a 5 liter autoclave, 5mL of a hexane solution of triethylaluminum (triethylaluminum concentration: 0.5 mmol/mL), L mL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (CHMMS concentration: 0.1 mmol/mL), 1L of liquid propylene, 4.5NL of hydrogen were added at room temperature, and the temperature was raised to 60℃to add 1L of propylene and 0.3mL of the prepolymerized catalyst B1. The autoclave was closed and the temperature was raised to 70 ℃ with stirring. Polymerization was carried out at 70℃for 1 hour, stirring was stopped after the completion of the reaction, unpolymerized propylene monomer was removed, and the polymer was collected, dried in vacuo and weighed. Catalyst activity= (polymer mass x prepolymerization ratio)/(prepolymerization catalyst mass x prepolymerization catalyst concentration). The results are shown in Table 1.
[ example 2 ]
1. Preparation of prepolymerized catalyst B2: slurry catalyst A1 was prepared as in example 1. 50 g of slurry catalyst A1 which is uniformly stirred is added into 400 ml of hexane for dispersion, 15ml of 0.5mol/L triethylaluminum hexane solution is added, and after stirring reaction is carried out for 10 minutes at 25 ℃, 30 g of propylene is introduced into the mixture at a uniform speed within 8 hours for polymerization, thus obtaining the prepolymerized catalyst. The reactor pressure was controlled at 0.02MPa and the temperature 25 ℃. The concentration of the prepolymerized catalyst B1 was 12.6% by weight. The prepolymerization multiplying power is 1.97.
2. Evaluation of the prepolymerization agent B2: polymerization evaluation of the prepolymerized catalyst B2 was carried out as in example 1. The results are shown in Table 1.
[ example 3 ]
1. Preparation of prepolymerized catalyst B3: slurry catalyst A1 was prepared as in example 1. 50 g of slurry catalyst A1 which is uniformly stirred is added with 412 ml of hexane for dispersion, 3ml of 0.5mol/L triisobutyl aluminum hexane solution is added, and after stirring reaction is carried out for 10 minutes at 25 ℃, 15 g of ethylene is uniformly introduced in 4 hours for polymerization, thus obtaining the prepolymerized catalyst. The reactor pressure was controlled at 0.02MPa and the temperature 25 ℃. The concentration of the prepolymerized catalyst B3 was 8.8% by weight. The prepolymerization multiplying power is 0.98.
2. Evaluation of the prepolymerization agent B3: polymerization evaluation of the prepolymerized catalyst B3 was carried out as in example 1. The results are shown in Table 1.
[ example 4 ]
1. Preparation of slurry catalyst A4:
(1) Preparation of an alkoxy magnesium carrier:
after a 16L pressure-resistant reactor equipped with a stirrer was sufficiently replaced with nitrogen, 10L of ethanol, 300mL of 2-ethylhexanol, 11.2g of iodine, 8g of magnesium chloride and 640g of magnesium powder were added to the reactor. Stirring while heating the system to 75 ℃ for reflux reaction until no more hydrogen is discharged. Stopping the reaction, washing with 3L ethanol, filtering and drying. Obtaining the alkoxy magnesium carrier. The obtained alkoxyl magnesium carrier d50=30.2 μm, span value 0.81 and m value 0.015, to obtain an alkoxyl magnesium carrier, and the alkoxyl magnesium carrier was sieved with a 150 mesh sieve to remove the block, to obtain a sieved alkoxyl magnesium carrier.
(2) Preparation of the catalyst component:
650g of the sieved magnesium alkoxide support and 3250mL of toluene and 65mL of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were taken and prepared as a suspension. Adding 2600mL of toluene and 3900mL of titanium tetrachloride into a 16L pressure-resistant reaction kettle repeatedly replaced by high-purity nitrogen, heating to 80 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, adding 65mL of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (1 # ether), slowly heating to 110 ℃, keeping the temperature for 2 hours, and performing filter pressing to obtain a solid. The resulting solid was stirred at 110℃for 1 hour with a mixture of 5070mL of toluene and 3380mL of titanium tetrachloride added thereto, and the mixture was treated 3 times. The resulting solid was washed 4 times with 6000mL of hexane, and the liquid was filtered off to obtain a solid catalyst component product. The above solid catalyst component was not dried, and 2000mL of hexane was again added to obtain a mixture in which the solid catalyst component was dispersed in hexane.
(3) Preparing a slurry catalyst:
stirring the mixture obtained in the step (2) (the titanium content of the solid catalyst after separation is 4.1%) and directly adding 1668 g of dehydrated oxygen-treated 68# industrial white oil, stirring and drying at 60 ℃ for 8 hours under vacuum to remove residual hexane to obtain a slurry catalyst A4 of the catalyst in the white oil. The catalyst concentration was 30.5 wt% and the hexane content in the white oil was 1.0 wt%.
2. Preparation of the prepolymerized catalyst:
50 g of slurry catalyst A4 which is uniformly stirred is added into 412 ml of hexane for dispersion, 3ml of 0.5mol/L triisobutyl aluminum hexane solution is added, and after stirring reaction is carried out for 10 minutes at 25 ℃, 15 g of ethylene is uniformly introduced into the mixture for polymerization within 4 hours, thus obtaining the prepolymerized catalyst. The reactor pressure was controlled at 0.02MPa and the temperature 25 ℃. The concentration of the prepolymerized catalyst B4 was 8.7%. The prepolymerization multiplying power is 0.98.
3. Evaluation of the prepolymerization agent B4: polymerization evaluation of the prepolymerized catalyst B4 was carried out as in example 1. The results are shown in Table 1.
[ example 5 ]
1. Slurry catalyst A5 was prepared in the same manner as in A1 of example 1 except that the evacuation time was changed from 12 hours to 4 hours. The hexane content therein was tested to be 1.5% by weight.
2. The preparation method of the prepolymerized catalyst B5 was the same as that of B1 in example 1, except that the slurry catalyst A1 was replaced with the slurry catalyst A5. The concentration of prepolymerized catalyst B5 was 12.3% by weight. The prepolymerization multiplying power is 1.95.
3. Evaluation of the prepolymerization agent B5: polymerization evaluation of the prepolymerized catalyst B5 was carried out as in example 1. The results are shown in Table 1.
[ example 6 ]
1. Preparation of slurry catalyst A6:
the preparation of slurry catalyst A6 was the same as the preparation of steps (1) and (2) of slurry catalyst A1 of example 1, except that it was correspondingly scaled up. Wherein slurry catalyst A1 was enlarged 169-fold. After the obtained solid was washed with hexane 4 times, part of the liquid was filtered off to obtain a mixture in which the solid catalyst component was dispersed in hexane. (3) And (3) directly adding 280kg of dehydrated oxygen treated 68# industrial white oil into the mixture obtained in the step (2) while stirring, and removing residual hexane by drying at 60 ℃ for 12 hours while stirring to obtain slurry of the catalyst in the white oil. The catalyst concentration was 30.5 wt% and the hexane content in the white oil was 0.5 wt%.
2. Preparation of prepolymerized catalyst B6: same as B1
3. Evaluation of the prepolymerization agent B6: polymerization evaluation of the prepolymerized catalyst B6 was carried out as in example 1. The results are shown in Table 1.
[ example 7 ]
1. The slurry catalyst A7 was prepared in the same manner as in A1 of example 1 except that the obtained dialkoxy magnesium carrier was subjected to screening to remove the lump by using a 150 mesh screen in the step (1), and the obtained dialkoxy magnesium carrier was subjected to screening to remove the lump by using an 80 mesh screen instead of the step (1) to obtain a screened alkoxy magnesium carrier. And finally slurry catalyst A7 was obtained.
2. The preparation method of the prepolymerized catalyst B7 was the same as that of B1 in example 1, except that the slurry catalyst A1 was replaced with the slurry catalyst A7.
3. Evaluation of the prepolymerization agent B7: polymerization evaluation of the prepolymerized catalyst B7 was carried out as in example 1. The results are shown in Table 1.
[ example 8 ]
1. The slurry catalyst A8 was prepared in the same manner as in A1 of example 1 except that the obtained dialkoxy magnesium carrier was subjected to screening to remove the lump by using a 150 mesh screen in the step (1), and the obtained dialkoxy magnesium carrier was subjected to screening to remove the lump by using a 200 mesh screen instead of the sieving to obtain a sieved alkoxy magnesium carrier. And finally slurry catalyst A8 was obtained.
2. The preparation method of the prepolymerized catalyst B8 was the same as that of B1 in example 1, except that the slurry catalyst A1 was replaced with the slurry catalyst A8.
3. Evaluation of the prepolymerization agent B8: polymerization evaluation of the prepolymerized catalyst B8 was carried out as in example 1. The results are shown in Table 1.
Comparative example 1
1. Preparation of dry powder catalyst D1:
the support and catalyst components were prepared as in example 1 except that the solid catalyst component after washing with hexane 4 times was dried to give dry powder catalyst D1, which was specifically as follows:
(1) Preparation of dialkoxy magnesium carrier:
after a 16L pressure-resistant reactor equipped with a stirrer was sufficiently replaced with nitrogen, 10000mL of ethanol, 300mL of 2-ethylhexanol and 200mL of isopropanol were added to the reactor, and 12g of iodine and 8g of magnesium chloride were added to dissolve the materials. After stirring, heating up until the reflux temperature of the reaction system is reached. Then 640g of magnesium powder was added successively. The reaction is carried out until completion, i.e. no more hydrogen is discharged. Then washing, separating and drying. The obtained dialkoxy magnesium carrier is screened by a 150-mesh screen to remove blocks, and the screened dialkoxy magnesium carrier is obtained.
(2) Preparation of the catalyst component:
taking 650g of dialkoxy magnesium carrier and 3250mL of toluene and 65mL of di-n-butyl phthalate (DNBP) to prepare a suspension; adding 2600mL of toluene and 3900mL of titanium tetrachloride into a 16L pressure-resistant reaction kettle repeatedly replaced by high-purity nitrogen, cooling to-5 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, slowly heating to 110 ℃, adding 65mL of DNBP when the temperature is raised to 80 ℃, keeping the temperature for 2 hours, and then press-filtering the liquid clean. Then, 5070mL of toluene and 3380mL of titanium tetrachloride were added, and the mixture was stirred at 110℃for 1 hour, thus treated 3 times, and the liquid was filtered off to obtain a solid catalyst component product, which was dried under vacuum at 60℃for 20 hours, and then sieved through a 200-mesh sieve, to obtain a powdery solid catalyst component D1.
2. Preparation of the prepolymerized catalyst D1:
15 g of dry powder catalyst D1 is taken, 412 ml of hexane is added for dispersion, 3ml of hexane solution of 0.5mol/L triisobutylaluminum is added, and after stirring reaction is carried out for 10 minutes at 20 ℃, 15 g of ethylene is introduced at a constant speed within 4 hours for polymerization, thus obtaining the prepolymerized catalyst D1. The reactor pressure was controlled at 0.02MPa and the temperature 25 ℃. The concentration of the prepolymerized catalyst was 8.9% by weight. The prepolymerization multiplying power is 0.99.
3. Evaluation of the prepolymerization agent D1: polymerization evaluation of the prepolymerized catalyst D1 was carried out as in example 1. The results are shown in Table 1.
Comparative example 2
1. The preparation method of the prepolymerized catalyst D2 was the same as in example 1, except that the catalyst carrier was prepared without sieving to remove the lump (i.e., the dialkoxy magnesium carrier obtained in step (1) was not sieved to remove the lump), to obtain the prepolymerized catalyst D2.
2. Evaluation of the prepolymerization agent D2: polymerization evaluation of the prepolymerized catalyst D2 was carried out as in example 1. The results are shown in Table 1.
[ comparative example 3 ]
1. Preparation of slurry catalyst D3:
the catalyst components were prepared as in CN85100997a example 1, but without drying, and were as follows:
in a reactor fully replaced by high-purity nitrogen, 0.05 mol of anhydrous magnesium chloride, 75 ml of toluene, 0.1 mol of epichlorohydrin and 0.03 mol of tributyl phosphate were added in sequence, the temperature was raised to 50 ℃ with stirring and maintained for 2 hours, the solid was completely dissolved, then 0.008 mol of phthalic anhydride was added and maintained for 1 hour. The melt was cooled to-25 ℃, 55 ml of titanium tetrachloride was added dropwise over 1 hour, the temperature was slowly raised to 80 ℃, and during the temperature rise, solids were gradually precipitated. Diisobutylphthalate 0.0125 mol was added and maintained at 80℃for 1 hour. After filtration, the mixture was washed twice with 100 ml of toluene to obtain a brown yellow solid precipitate. 60ml of toluene and 40 ml of titanium tetrachloride were then added, the mixture was treated at 90℃for 2 hours, and the filtrate was removed and the treatment was repeated once more. After washing once with 100 ml of dichloroethane and four times with 100 ml of hexane, the solid catalyst component was obtained by filtration. The above solid catalyst component was not dried, and 60mL of hexane was added to obtain a mixture in which the solid catalyst component was dispersed in hexane. The mixture was stirred while directly adding 18.5 g of dehydrated oxygen treated 68# technical white oil, and the residual hexane was removed by vacuum drying at 60 ℃ for 12 hours while stirring to obtain catalyst slurry in white oil catalyst D3. The catalyst concentration was 25.8 wt% and the hexane content in the white oil was 0.2 wt%.
2. Preparation of prepolymerized catalyst D3:
20 g of slurry catalyst D4 which is uniformly stirred is added into 144 ml of hexane for dispersion, 12ml of 0.5mol/L triethylaluminum hexane solution and 10ml of 0.1mol/L methylcyclohexyl dimethoxy silane are added, and after stirring and reacting for 10 minutes at 20 ℃, 12 g of propylene is introduced into the mixture at a uniform speed within 8 hours for polymerization, and the prepolymerized catalyst D3 is obtained. The reactor pressure was controlled at 0.02MPa and the temperature 25 ℃. The concentration of the prepolymerized catalyst was 12.5% by weight. The prepolymerization multiplying power is 1.99.
3. Evaluation of the prepolymerization agent D3: polymerization evaluation of the prepolymerized catalyst D3 was carried out as in example 1. The results are shown in Table 1.
[ comparative example 4 ]
1. Preparation of slurry catalyst D4:
the catalyst components were prepared and dried as in CN85100997a example 1, as follows:
in a reactor fully replaced by high-purity nitrogen, 0.05 mol of anhydrous magnesium chloride, 75 ml of toluene, 0.1mol of epichlorohydrin and 0.03 mol of tributyl phosphate were added in sequence, the temperature was raised to 50 ℃ with stirring and maintained for 2 hours, the solid was completely dissolved, then 0.008 mol of phthalic anhydride was added and maintained for 1 hour. The melt was cooled to-25 ℃, 55 ml of titanium tetrachloride was added dropwise over 1 hour, the temperature was slowly raised to 80 ℃, and during the temperature rise, solids were gradually precipitated. Diisobutylphthalate 0.0125 mol was added and maintained at 80℃for 1 hour. After filtration, the mixture was washed twice with 100 ml of toluene to obtain a brown yellow solid precipitate. 60 ml of toluene and 40 ml of titanium tetrachloride were then added, the mixture was treated at 90℃for 2 hours, and the filtrate was removed and the treatment was repeated once more. Adding dichloroethane 100 ml, washing once, washing hexane 100 ml four times, drying at 60 ℃ for 8 hours, sieving through a 200-mesh screen after drying to obtain 6 g of powdery solid catalyst component, adding 14 g of dehydrated-oxygen-treated 68# industrial white oil, stirring, and simultaneously vacuum-drying at 60 ℃ for 12 hours to remove residual hexane to obtain a slurry catalyst D4 of the catalyst in the white oil. The catalyst concentration was 30.1 wt% and the hexane content in the white oil was 0.2 wt%.
2. Preparation of prepolymerized catalyst D4:
as in example 1. The prepolymerized catalyst concentration was 12.6% by weight. The prepolymerization multiplying power is 1.98.
3. Evaluation of the prepolymerization agent D4: polymerization evaluation of the prepolymerized catalyst D4 was carried out as in example 1. The results are shown in Table 1.
Comparative example 5
1. Preparation of slurry catalyst D5:
the preparation of the carrier and the catalyst component was the same as in example 5, and the obtained solid hexane was washed and then filtered, dried at 60℃for 35 hours, and then sieved with a 150-mesh sieve to obtain a solid catalyst powder having good fluidity. 120kg of the solid powder was gradually added to 280kg of 68# technical white oil and stirred for 8 hours to obtain a slurry of the catalyst in the white oil. The catalyst concentration was 30.0 wt%.
2. Preparation of prepolymerized catalyst D5: same as B6.
3. Evaluation of the prepolymerization agent D5: the evaluation method of the prepolymerized catalyst D5 was the same as in example 1. The results are shown in Table 1.
TABLE 1
Figure BDA0003324733810000251
Figure BDA0003324733810000261
From the above example data, it can be seen that the prepolymerized catalyst prepared by the present process can be directly used for olefin polymerization, and has good activity, orientation ability, and hydrogen sensitivity. At the same time, little fines and lumps of polymer are obtained. Compared with the prepolymerized catalyst directly prepared by the dry powder catalyst, the prepolymerized catalyst prepared by the direct slurry has less fine powder; the polymer lump prepared by the prepolymerized catalyst prepared by the method is obviously reduced compared with the solid catalyst component prepared by using a carrier which is not screened; compared with a dry powder catalyst, the production efficiency of the method for preparing the prepolymerized catalyst by using the direct slurry provided by the invention is greatly improved.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.

Claims (10)

1. A method of preparing a prepolymerized catalyst comprising:
step 1, screening a carrier for preparing a catalyst to obtain a screened carrier;
step 2, using a carrier subjected to screening treatment, carrying out contact reaction with a titanium compound and an electron donor compound in the presence of an inert diluent, filtering, washing the obtained solid by adopting low-boiling alkane B to obtain a first mixture of a solid catalyst component A dispersed in the alkane B, and mixing the first mixture with white oil C to obtain a second mixture;
step 3, removing low-boiling alkane B in the second mixture in vacuum to obtain a slurry catalyst of the solid catalyst component A in the white oil C;
step 4, mixing the slurry catalyst with a hydrocarbon compound D, an aluminum alkyl compound E and an optional silane compound F, and carrying out a prepolymerization reaction with an olefin monomer G.
2. The method of claim 1, wherein the molar ratio of the alkyl aluminum compound to titanium in the solid catalyst component, calculated as aluminum, is 0.05-50:1; preferably 1-20:1; more preferably 1-10:1.
3. The preparation method according to claim 1 or 2, characterized in that the molar ratio of alkylaluminum compound to the silane compound, calculated as aluminum, is 0.1-500:1, preferably 1-100:1, more preferably 1-20:1.
4. A process according to any one of claims 1 to 3, wherein the support is a magnesium-containing support for the preparation of Ziegler-Natta polyolefin catalysts, preferably the support is one or more of a spheroidal magnesium alkoxide support and a spheroidal magnesium chloride alkoxide support; and/or the number of the groups of groups,
the average particle diameter of the carrier obtained by the sieving treatment is not more than 100. Mu.m, preferably 10 to 80. Mu.m.
5. The process according to any one of claims 1 to 4, wherein the solid catalyst component A obtained in step 2 is not subjected to drying treatment.
6. The preparation process according to any one of claims 1 to 5, characterized in that the low-boiling alkane B is an alkane or a mixture of alkanes having a boiling point below 100 ℃, preferably at least one selected from pentane, isopentane, hexane, cyclohexane and heptane.
7. The preparation method according to any one of claims 1 to 6, wherein the white oil C is 68# industrial white oil and/or 100# industrial white oil; and/or the weight ratio of the white oil C added to the weight of the solid catalyst component A is 1-10:1, preferably 4-7:1; and/or, the conditions for vacuum removal of the low boiling alkane B include: the temperature is 20-100deg.C, preferably 40-80deg.C.
8. A prepolymerized catalyst prepared by the preparation method according to any one of claims 1 to 7.
9. A catalyst system for olefin polymerization comprising
(1) The prepolymerized catalyst according to claim 8; and
(2) An alkylaluminum compound as a cocatalyst;
(3) Optionally an external electron donor.
10. A process for the polymerization of olefins comprising contacting one or more olefins with the catalyst system of claim 9 to obtain a polymer.
CN202111258056.3A 2021-10-27 2021-10-27 Prepolymerized catalyst, preparation method and application thereof Pending CN116023549A (en)

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