CN113912755A - Catalyst composition for olefin polymerization and application thereof - Google Patents

Catalyst composition for olefin polymerization and application thereof Download PDF

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CN113912755A
CN113912755A CN202111238808.XA CN202111238808A CN113912755A CN 113912755 A CN113912755 A CN 113912755A CN 202111238808 A CN202111238808 A CN 202111238808A CN 113912755 A CN113912755 A CN 113912755A
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electron donor
catalyst composition
olefin polymerization
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张一锴
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    • C—CHEMISTRY; METALLURGY
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
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    • 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 catalyst composition for olefin polymerization and application thereof, wherein the catalyst composition comprises the following components: (1) a solid catalyst component comprising magnesium, titanium, halogen and an electron donor compound containing a lone pair of electron elements such as oxygen, nitrogen, sulfur, phosphorus, etc.; (2) an alkyl aluminum compound; (3) the external electron donor compound comprises a compound A and a compound B. The catalyst composition for olefin polymerization and the application thereof adopt the structure, and the compound containing hydroxyl groups and the organic siloxane compound or the carboxylic ester compound are used as the external electron donor to be matched with the existing solid catalyst, so that the high activity and high directionality of the catalyst system are maintained, the content of powder blocks during gas phase polymerization is reduced, and the running stability of the device is improved.

Description

Catalyst composition for olefin polymerization and application thereof
Technical Field
The invention relates to the technical field of olefin polymerization catalysts, in particular to a catalyst composition for olefin polymerization and application thereof.
Background
Olefin polymerization reaction is generally a solid titanium catalyst using magnesium, titanium, halogen and an electron donor as basic components, wherein an electron donor compound is one of indispensable components in olefin polymerization, particularly propylene or higher olefin polymerization catalyst components, the electron donor is divided into an internal electron donor and an external electron donor, the internal electron donor is an electron donor compound added during preparation of the catalyst solid component, the external electron donor is an electron donor compound added during catalytic polymerization, polyolefin catalysts are continuously updated with the development of the internal electron donor compound, and the external electron donor also needs to be developed in a matching manner with the internal electron donor. At present, a large number of electron donor compounds have been disclosed, such as mono-or polycarboxylic esters of internal electron donors, ketones, mono-or polyethers, amines, and the like, and derivatives thereof, and the commonly used external electron donors are organosiloxane compounds of the general formula rnsi (or) 4-n. The external electron donor is matched with a solid catalyst, is applied to catalyzing propylene polymerization, can have higher activity and orientation capability, but when applied to certain occasions, particularly gas phase polymerization process, because the gas medium is not so uniform in dispersion and the heat transfer effect is not as good as that of a liquid phase medium, local hot spots can occur in the polymerization process, the agglomeration phenomenon of polymer powder is easy to occur, and the normal operation of a reaction device is influenced under the serious condition.
There are also documents disclosing techniques for reducing agglomeration, mainly by reducing the activity of the catalyst at high temperature, using mono-or dicarboxylic esters as external electron donor, but these esters mostly reduce the orientation ability of the catalyst compared to organosiloxane, for example, patent CN101835812A discloses an external electron donor with high temperature self-extinguishing, but its usage is very large, if the ratio of alkyl aluminum to its usage is required to be less than 4, and the orientation ability is not high, and in addition, the activity is greatly reduced compared to the existing alkoxysilane.
Disclosure of Invention
The invention aims to provide a catalyst composition for olefin polymerization, in particular to propylene polymerization and application thereof.
In order to achieve the above object, the present invention provides a catalyst composition for olefin polymerization and its application, comprising the following components:
(1) a solid catalyst component comprising magnesium, titanium, halogen and an electron donor compound containing a lone pair of electron elements such as oxygen, nitrogen, sulfur, phosphorus, etc.;
(2) an alkylaluminum compound having the general formula AlR1 nX3-nN is more than 1 and less than or equal to 3; wherein R is1Is hydrogen or C1～C20X is halogen; preferably, the alkyl aluminum compound is selected from triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, triisobutyl aluminum, diethyl aluminum monohydrogen, diisobutyl aluminum monohydrogen, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride, and preferably one of triethyl aluminum, triisobutyl aluminum and the like;
(3) an external electron donor compound, wherein the external electron donor compound comprises a compound A and a compound B;
the compound A is a compound containing hydroxyl groups, the general formula of the compound A is ROH (I), and R is C1～C60Substituted or unsubstituted hydrocarbyl of (a); the carbon in the hydrocarbon group can be substituted by O, N, P, S atoms, the hydrogen in the hydrocarbon group can be substituted by F, Cl, Br, I and the like; preferably, the compound a may contain a plurality of hydroxyl groups;
the compound B is one of organic siloxane compound, malonate compound or monocarboxylic ester compound, and the like, wherein the general formula of the organic siloxane compound is (R)1)aSi(OR2)4-a(Ⅱ)，0≤a≤ 3，R1Selected from halogen, hydrogen atom, C substituted or not by oxygen, sulfur, nitrogen, or the like1～C10Alkyl radical, C1～C10Alkylene radical, C3～C10Cycloalkyl radical, C6～C10Aryl radical, C7～C10One or more of alkylaryl or arylalkyl, and the like; r2Is selected from C1-C20One or more of alkyl, cycloalkyl, aryl, haloalkyl or amino, etcSeed growing;
preferably, the general formula (ii) is specifically one selected from the group consisting of dibutylmethyldimethoxysilane, tetraethoxysilane, isopropylisobutyldimethoxysilane, isopropylbutyldimethoxysilane, propylisobutyldimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisobutyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, and the like;
the general formula of the malonate type compound is R3R4C(COOR5)(COOR6)(Ⅲ)，R3、R4、R5And R6All are substituted or unsubstituted C1-C20A hydrocarbon group of (a);
the monocarboxylic ester compound has the general formula R7COOR8(Ⅳ)，R7And R8Selected from substituted or unsubstituted C1～C10Straight chain alkyl, C3～C15Branched alkyl radical, C3～C15Cycloalkyl radical, C6～C20Aryl radical, C7～C20Alkylaryl or arylalkyl, and the like.
Preferably, the content of the magnesium in the solid catalyst component is 8 wt% to 24 wt%, and the content of the titanium is 0.5 wt% to 8 wt%; more preferably, the content of magnesium is 15 wt% -20 wt%, and the content of titanium is 1.0 wt% -4.5 wt%;
the molar ratio of the solid catalyst component to the aluminum alkyl compound is as follows: the aluminum is 1 (5-1000), preferably 1 (20-250), the molar ratio of the solid catalyst component to the external electron donor compound is 1 (0.01-200) in terms of titanium to the external electron donor, preferably 1 (0.1-100), more preferably 1: (0.2 to 50);
the molar ratio of the compound A to the compound B in the external electron donor compound is 0.01-100, preferably 0.1-20, and more preferably 0.2-10; for the mode of entering the compound A and the compound B into the polymerization reaction kettle, before contacting with the olefin, the compound A and the compound B are mixed and then contacted with the olefin, so that the synergistic effect of the compound A and the compound B can be better exerted, and the compound A and the compound B have better activity and the effect of reducing agglomeration.
Preferably, R is C1～C20Is one or more of isopropanol, isobutanol, isoamyl alcohol, 2-ethyl-1-hexanol, dodecanol, octadecanol and the like.
Preferably, R is C6～C30An alkyl group containing an N element; the general formula (I) is one or more of N- (2-hydroxyethyl) dialkylamine, N, N-di (2-hydroxyethyl) alkylamine, N- (2-hydroxyethyl) dialkoxyalkylalkylamine, N, N-di (2-hydroxyethyl) alkoxyalkyl alkylamine and the like, and further, the general formula (I) is specifically one selected from N- (2-hydroxyethyl) didodecylamine, N, N-bis (2-hydroxyethyl) dodecylamine, N- (2-hydroxyethyl) dioctadecylamine, N, N-bis (2-hydroxyethyl) octadecylamine, N, N-bis (2-hydroxyethyl) octylamine, N, N-bis (2-hydroxyethyl) octadecylamine, N, N-bis (2-hydroxyethyl) decyloxypropylamine and the like.
Preferably, R3And R4Selected from hydrogen, halogen, substituted or unsubstituted C1～C10Alkyl radical, C1～C10Alkylene radical, C3～C10Cycloalkyl radical, C6～C10Aryl radical, C7～C10Alkylaryl or arylalkyl, and the like.
Preferably, R5And R6Selected from substituted or unsubstituted C1～C10Straight chain alkyl, C3～C10Branched alkyl, C3～C10Cycloalkyl radical, C6～C10Aryl radical, C7～C10Alkylaryl or C7～C10Aralkyl, and the like.
Preferably, the compound of the formula (III) is specifically selected from the group consisting of diethyl malonate, dipropyl malonate, diisopropyl malonate, dibutyl malonate, diisobutyl malonate, di-tert-butyl malonate, diethyl methyl malonate, dipropyl methyl malonate, diisopropyl methyl malonate, di-n-butyl methyl malonate, diisobutyl methyl malonate, di-tert-butyl methyl malonate, diethyl ethyl malonate, dipropyl ethyl malonate, diisopropyl ethyl malonate, di-n-butyl ethyl malonate, diisobutyl ethyl malonate, di-tert-butyl ethyl malonate, diethyl propyl malonate, dipropyl propyl malonate, diisopropyl propyl malonate, di-n-butyl propyl malonate, diisobutyl propyl malonate, di-tert-butyl propyl malonate, diethyl isopropyl malonate, diisopropyl isopropyl malonate, diethyl isopropyl malonate, diisopropyl malonate, diethyl malonate, isopropyl malonate, diisopropyl malonate, diethyl malonate, isopropyl malonate, diethyl malonate, and the like, Di-n-butyl isopropylmalonate, di-isobutyl isopropylmalonate, di-t-butyl isopropylmalonate, diethyl phenylmalonate, dipropyl phenylmalonate, diisopropyl phenylmalonate, di-n-butyl phenylmalonate, diisobutyl phenylmalonate, di-t-butyl phenylmalonate, diethyl benzylmalonate, dipropyl benzylmalonate, diisopropyl benzylmalonate, di-n-butyl benzylmalonate, diisobutyl benzylmalonate, di-t-butyl benzylmalonate and the like, diethyl dimethylmalonate, diethyl diethylmalonate, diethyl methylethylmalonate, diethyl methylbutylmalonate, diethyl methylisobutylkmalonate, diethyl methylpropylmalonate, diethyl methylisopropylmalonate, diethyl di-n-propylmalonate, diethyl di-n-butylmalonate, diethyl diisopropylmalonate, diethyl malonate, diethyl isopropylmalonate, and the like, Diethyl diisobutyl malonate, diethyl diallyl malonate, and the like.
Preferably, the solid catalyst component comprises a reaction product of a titanium compound, a magnesium compound and the internal electron donor compound; the amounts of the titanium compound, the magnesium compound and the internal electron donor compound are not particularly limited, and may be respectively conventional amounts in the art.
Preferably, the magnesium compound is selected from one or more of magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcoholate of magnesium dihalide, derivative of magnesium dihalide with one halogen atom replaced by hydrocarbonoxy or halogenated hydrocarbonoxy in the molecular formula, and the like; preference is given to magnesium dihalides or alcoholates of magnesium dihalides. Specific examples thereof include one of magnesium dichloride, magnesium dibromide, magnesium diiodide, and alcohol hydrates thereof.
Preferably, the titanium-containing compound has the formula TiXm(OR2)4-mA compound of (1), wherein R2Is C1～C20X is halogen, m is more than or equal to 1 and less than or equal to 4; specifically, it is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, etc.
Preferably, the internal electron donor compound is selected from compounds containing O atoms, and the compounds containing O atoms are selected from one of ethers, esters, phenol ethers, phenol esters, ketones and the like; specifically, the compound is one selected from a benzoate compound, a phthalate compound, a1, 3-diether, a polybasic acid ester compound, a polyhydric alcohol/phenol ester compound and the like.
Preferably, the 1, 3-diether compound is specifically selected from the group consisting of 2-propyl-2-isopropyl-1, 3-dimethoxypropane, 2-propyl-2-butyl-1, 3-dimethoxypropane, 2-propyl-2-isobutyl-1, 3-dimethoxypropane, 2-propyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-butyl-2-isobutyl-1, 3-dimethoxypropane, 2-butyl-2-isopentyl-1, 3-dimethoxypropane, 2-isobutyl-2-pentyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopentyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-bis (2-methylbutyl) -1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-bis (2-ethylhexyl) -1, 3-dimethoxypropane, and 9, 9-bis (methoxymethyl) fluorene.
Preferably, the polybasic acid ester compound is specifically selected from a malonic acid ester compound, a succinic acid ester compound, a glutaric acid ester compound, and a phthalic acid ester compound. More preferably one or more selected from the group consisting of diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, diisooctyl phthalate, tetramethyldi-n-butyl phthalate, tetramethyldiisobutyl phthalate, di-n-butyl tetrabromophthalate, diisobutyl tetrabromophthalate, diethyl 2, 3-di-n-propylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-n-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-di-n-propylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-di-n-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate and the like.
Preferably, the polyol/phenol forming ester is specifically selected from the group consisting of 1, 3-diol ester compounds and 1, 2-diphenol ester compounds, more preferably from the group consisting of 2, 4-pentanediol dibenzoate, 2, 4-pentanediol di-p-n-propyl benzoate, 2, 4-pentanediol di-p-isopropyl benzoate, 2, 4-pentanediol di-p-isobutyl benzoate, 2, 4-pentanediol di-p-n-butyl benzoate, 2, 4-pentanediol di-p-tert-butyl benzoate, 3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methyl benzoate, 3, 5-heptanediol di-p-ethyl benzoate, 3, 5-heptanediol di-p-n-propyl benzoate, 3, 5-heptanediol di-p-isopropyl benzoate, 3, 5-heptanediol di-p-isobutyl benzoate, 3, 5-heptanediol di-p-n-butylbenzoate, 3, 5-heptanediol di-p-tert-butylbenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol di-p-methylbenzoate, 4-ethyl-3, 5-heptanediol di-p-ethylbenzoate, 4-ethyl-3, 5-heptanediol di-p-propylbenzoate, 4-ethyl-3, 5-heptanediol di-p-butylbenzoate, 4-ethyl-3, 5-heptanediol di-p-tert-butylbenzoate, 4-propyl-1, 2-diphenol dibenzoate, 1, 2-diphenol di-p-n-propylbenzoate, 1, 2-diphenophenol di-p-isopropyl benzoate, 1, 2-diphenophenol di-p-isobutyl benzoate, 1, 2-diphenophenol di-p-n-butyl benzoate, 1, 2-diphenophenol di-p-tert-butyl benzoate, 4-tert-butyl-1, 2-diphenophenol di-p-n-propyl benzoate, 4, 5-dipropyl-1, 2-diphenophenol di-p-isopropyl benzoate, 4-ethyl-1, 2-diphenophenol di-p-isobutyl benzoate, 4-isopropyl-1, 2-diphenophenol di-p-n-butyl benzoate, 4-isopentyl-1, 2-diphenophenol di-p-tert-butyl benzoate, 2-ethyl-1, 2-diphenophenol di-p-n-propyl benzoate, 4-isobutyl-5-ethyl-1, 2-diphenol di-p-isopropyl benzoate, 4-tertiary butyl-5-ethyl-1, 2-diphenol di-p-isobutyl benzoate and the like.
Preferably, the solid catalyst component can also be a prepolymerized catalyst composition comprising a prepolymer prepared by prepolymerizing at least one of the above catalyst compositions with an olefin, wherein the prepolymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
The "prepolymerized catalyst" (e.g. CN110938160A) refers to a catalyst which has undergone a polymerization step with a lower degree of conversion; the prepolymerization can be carried out using the same alpha-olefin as the olefin used for the polymerization, wherein the olefin to be subjected to the prepolymerization is preferably propylene; in particular, it is particularly preferred to carry out the prepolymerization with propylene or a mixture thereof with one or more alpha-olefins in an amount of up to 20 mol%; preferably, the degree of conversion of the prepolymerized catalyst component is from about 0.2 to 500g polymer/g solid catalyst component; the prepolymerization process can be carried out in a liquid or a gas phase at-20 to 80 ℃, preferably at 0 to 50 ℃; the pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation.
Use of a catalyst composition for the polymerization of olefins, said catalyst composition being suitable for use in a process for the polymerization of olefins, in particular in a gas-phase polymerization process.
The olefin has the general formula CH2Wherein R is hydrogen or C1～C12An alkyl or aryl group of (a); preferably the olefin is propylene; the olefin polymerization process of the present invention is particularly suitable for being carried out in a gas phase polymerization process; the specific gas phase polymerization process includes fluidized bed process such as Unipol propylene polymerization process, vertical stirring kettle process such as Novolen propylene polymerization process, horizontal stirring kettle process such as Innovene and Horizone propylene polymerization process, and multi-zone circulating loop process such as Spherizone process, especially Unipol, Novolen and Innovene processes, because of the functions of the catalyst combination provided by the present invention, the possibility of agglomeration or implosion is greatly reduced, and the continuous operation of the apparatus is improvedTime of (d).
Therefore, the catalyst composition for olefin polymerization and the application thereof adopt the structure, the compound A containing hydroxyl groups and the compound B are jointly used as an external electron donor to be matched with the existing solid catalyst, so that the external electron donor has high activity and high directionality, the content of powder blocks in gas phase polymerization is reduced, and the running stability of the device is improved.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The present invention will be further described with reference to examples, in which various chemicals and reagents are commercially available unless otherwise specified.
Example 1
The solid catalyst CS-1, triethylaluminum, compound a isopropyl alcohol, compound B D-dornor, and propylene were charged into a reactor of a gas-phase fluidized bed to react, wherein compound a and compound B were mixed and then charged into the fluidized bed, the polymerization temperature was 70 ℃, the reaction pressure was 2.9MPa, the hydrogen concentration was 1000ppm, TEA/propylene was 130ppm, TEA/(a + B) was 10mol/mol, a/B was 1, the reaction time was 1 hour, and the propylene polymerization results are shown in table 1.
Example 2
Solid catalyst CS-1, triethylaluminum TEA, compound a isopropyl alcohol, compound B D-doror, and propylene were charged into a reactor of a gas-phase fluidized bed to react, wherein compound a and compound B were charged into the fluidized bed, respectively, at a polymerization temperature of 70 ℃, a reaction pressure of 2.9MPa, a hydrogen concentration of 1000ppm, TEA/propylene of 130ppm, TEA/(a + B) of 10mol/mol, a/B of 1, a reaction time of 1 hour, and propylene polymerization results are shown in table 1.
Comparative example 1
The solid catalyst CS-1, triethylaluminum TEA, compound B D-doror, and propylene were charged into a gas-phase fluidized-bed reactor to carry out a reaction at a polymerization temperature of 70 ℃, a reaction pressure of 2.9MPa, a hydrogen concentration of 1000ppm, TEA/propylene of 130ppm, TEA/B of 10mol/mol, no compound a, a reaction time of 1 hour, and the polymerization results of propylene are shown in table 1.
Example 3
The solid catalyst NG, triethylaluminum, compound A A1, compound B C-doror and propylene were charged into a reactor of a gas-phase fluidized bed to react, compound a and compound B were mixed and then charged into the fluidized bed, the polymerization temperature was 70 ℃, the reaction pressure was 2.9MPa, the hydrogen concentration was 1000ppm, TEA/propylene was 130ppm, TEA/(a + B) was 10mol/mol, a/B was 0.3, the reaction time was 1 hour, and the propylene polymerization results are shown in table 1.
Example 4
A solid catalyst NG, triethylaluminum, a compound A A1, a compound B C-DONOR and propylene were added to a reactor of a gas-phase fluidized bed to react, wherein the compound A and the compound B were mixed and then fed into the fluidized bed, the polymerization temperature was 70 ℃, the reaction pressure was 2.9MPa, the hydrogen concentration was 1000ppm, TEA/propylene was 130ppm, TEA/(A + B) was 10mol/mol, A/B was 0.7, the reaction time was 1 hour, and the propylene polymerization results are shown in Table 1.
Comparative example 5
The solid catalyst NG, triethylaluminum, compound A A1, compound B C-doror and propylene were charged into a reactor of a gas-phase fluidized bed to react, wherein compound a and compound B were charged into the fluidized bed separately, the polymerization temperature was 70 ℃, the reaction pressure was 2.9MPa, the hydrogen concentration was 1000ppm, TEA/propylene was 130ppm, TEA/(a + B) was 10mol/mol, a/B was 0.7, the reaction time was 1 hour, and the propylene polymerization results are shown in table 1.
Comparative example 2
A solid catalyst, NG, triethylaluminum, compound B C-DONOR and propylene were charged into a reactor of a gas-phase fluidized bed to carry out a reaction at a polymerization temperature of 70 ℃ and a reaction pressure of 2.9MPa, a hydrogen concentration of 1000ppm, TEA/propylene of 130ppm, TEA/B of 10mol/mol, no compound A, a reaction time of 1 hour, and the polymerization results of propylene are shown in Table 1.
Example 6
The solid catalyst NG, triethylaluminum, compound A A1, compound B C-doror and propylene were charged into a reactor of a gas-phase fluidized bed to react, compound a and compound B were charged into the fluidized bed, respectively, at a polymerization temperature of 70 ℃, a reaction pressure of 2.9MPa, a hydrogen concentration of 1000ppm, TEA/propylene of 130ppm, TEA/(a + B) of 10mol/mol, a/B of 3, a reaction time of 1 hour, and the polymerization results of propylene are shown in table 1.
Example 7
Solid catalysts BCND-II-04, triethyl aluminum, compound A A2, compound B B1 and propylene were added to a reactor of a gas phase fluidized bed to react, wherein compound A and compound B were mixed and then fed into the fluidized bed, the polymerization temperature was 70 ℃, the reaction pressure was 2.9MPa, the hydrogen concentration was 1000ppm, TEA/propylene was 130ppm, TEA/(A + B) was 10mol/mol, A/B was 10, the reaction time was 1 hour, and the propylene polymerization results are shown in Table 1.
Example 8
Solid catalyst BCND-II-04, triethyl aluminum, compound A A2, compound B B1, and propylene were added to a reactor of a gas phase fluidized bed to react, wherein compound A and compound B were mixed and then fed into the fluidized bed, the polymerization temperature was 70 ℃, the reaction pressure was 2.9MPa, the hydrogen concentration was 1000ppm, TEA/propylene was 130ppm, TEA/(A + B) was 10mol/mol, A/B was 0.5, the reaction time was 1 hour, and the propylene polymerization results are shown in Table 1.
Comparative example 3
The solid catalyst BCND-II-04, triethylaluminum, compound B B1, and propylene were charged into a gas-phase fluidized-bed reactor to react at 70 ℃, a reaction pressure of 2.9MPa, a hydrogen concentration of 1000ppm, TEA/propylene of 130ppm, TEA/B of 10mol/mol, no compound a, and a reaction time of 1 hour, and the polymerization results of propylene are shown in table 1.
The test method comprises the following steps:
the polymer isotacticity index was determined by heptane extraction (6 hours of heptane boil extraction): a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours, and the ratio of the weight of the polymer (g) to 2, which was obtained by drying the residue to a constant weight, was defined as the isotactic index.
TABLE 1 propylene polymerization results
Figure BDA0003318522980000111
Solid catalyst CS-1 is a Yingkou Yangxiao group product; the solid catalysts NG and BCND-II-04 are products of Odada division of China petrochemical catalyst Limited company; C-DONOR and D-DONOR are methylcyclohexyldimethoxysilane and dicyclopentyldimethoxysilane, respectively, and A1 is N, N-bis (2-hydroxyethyl) alkylamine (product of I.C.I); a2 is N, N-dihydroxyethyldecyloxypropylamine (product of Shandong Lujing Co.); b1 is n-tetradecanoic acid isopropyl ester. By a >10 mesh particle is meant a powder that is above a 10 mesh screen when the polymer powder is sieved.
As can be seen from Table 1, with the presence of the appropriate compound A, the catalyst maintains high activity and orientation ability regardless of whether the compounds A and B are mixed before contacting propylene, and the amount of agglomeration (particles which do not pass through a 20-mesh sieve in the powder) is greatly reduced, and in addition, the synergistic effect is more exhibited after the compounds A and B are mixed in advance; the reduction in the amount of large particles premixed is more pronounced for the same A/B than for the same A/B, and more compound A is required for the same amount of large particles, but more compound A will result in a certain reduction in catalyst activity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.

Claims (7)

1. A catalyst composition for olefin polymerization, comprising the following components:
(1) a solid catalyst component comprising magnesium, titanium, halogen and an electron donor compound containing a lone pair of electron elements such as oxygen, nitrogen, sulfur, phosphorus, etc.;
(2) alkylaluminidesThe general formula of the alkyl aluminum compound is AlR1 nX3-nN is more than 1 and less than or equal to 3; wherein R is1Is hydrogen or C1～C20X is halogen;
(3) an external electron donor compound, wherein the external electron donor compound comprises a compound A and a compound B;
the compound A is a compound containing hydroxyl groups, the general formula of the compound A is ROH (I), and R is C1～C60Substituted or unsubstituted hydrocarbyl of (a);
the compound B is one of organic siloxane compound, malonate compound or monocarboxylic ester compound, and the like, wherein the general formula of the organic siloxane compound is (R)1)aSi(OR2)4-a(Ⅱ)，0≤a≤3，R1Selected from halogen, hydrogen atom, C substituted or not by oxygen, sulfur, nitrogen, or the like1～C10Alkyl radical, C1～C10Alkylene radical, C3～C10Cycloalkyl radical, C6～C10Aryl radical, C7～C10One or more of alkylaryl or arylalkyl, and the like; r2Is selected from C1-C20One or more of alkyl, cycloalkyl, aryl, haloalkyl, amino, or the like;
the general formula of the malonate type compound is R3R4C(COOR5)(COOR6)(Ⅲ)，R3、R4、R5And R6All are substituted or unsubstituted C1-C20A hydrocarbon group of (a);
the monocarboxylic ester compound has the general formula R7COOR8(Ⅳ)，R7And R8Selected from substituted or unsubstituted C1～C10Straight chain alkyl, C3～C15Branched alkyl radical, C3～C15Cycloalkyl radical, C6～C20Aryl radical, C7～C20Alkylaryl or arylalkyl, and the like.
2. The catalyst composition for olefin polymerization according to claim 1, characterized in that: the content of the magnesium in the solid catalyst component is 8 wt% -24 wt%, and the content of the titanium is 0.5 wt% -8 wt%;
the molar ratio of the solid catalyst component to the aluminum alkyl compound is as follows: the aluminum is 1 (5-1000), and the molar ratio of the solid catalyst component to the external electron donor compound is 1 (0.01-200) in terms of titanium to the external electron donor;
the molar ratio of the compound A to the compound B in the external electron donor compound is 0.01-100 (mol/mol).
3. The catalyst composition for olefin polymerization according to claim 1, characterized in that: r is C1～C20Is one or more of isopropanol, isobutanol, isoamyl alcohol, 2-ethyl-1-hexanol, dodecanol, octadecanol and the like.
4. The catalyst composition for olefin polymerization according to claim 1, characterized in that: r is C6～C30An alkyl group containing an N element; the general formula (I) is one or more of N- (2-hydroxyethyl) dialkylamine, N, N-di (2-hydroxyethyl) alkylamine, N- (2-hydroxyethyl) dialkoxyalkylalkylamine, N, N-di (2-hydroxyethyl) alkoxyalkylamine and the like.
5. The catalyst composition for olefin polymerization according to claim 1, characterized in that: the internal electron donor compound is selected from compounds containing O atoms, and the compounds containing O atoms are one of ethers, esters, phenol ethers, phenol esters, ketones and the like.
6. The catalyst composition for olefin polymerization according to claim 1, characterized in that: the external electron donor component, compound A and compound B, are mixed and then enter a polymerization reactor to contact with olefin.
7. Use of a catalyst composition according to claims 1-6 for the polymerization of olefins, characterized in that: the catalyst composition is suitable for use in olefin polymerization processes, particularly in gas phase polymerization processes.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120302708A1 (en) * 2011-05-27 2012-11-29 Xianzhi Xia Magnesium halide adducts, catalyst components and catalysts comprising the same, and preparation processes thereof
JP2013028705A (en) * 2011-07-28 2013-02-07 Toho Titanium Co Ltd Solid catalyst component for olefin polymerization, method for producing the same, olefin polymerization catalyst, and method for producing olefin polymer
CN104513330A (en) * 2013-09-30 2015-04-15 中国石油化工股份有限公司 Catalyst system used in olefin polymerization and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120302708A1 (en) * 2011-05-27 2012-11-29 Xianzhi Xia Magnesium halide adducts, catalyst components and catalysts comprising the same, and preparation processes thereof
JP2013028705A (en) * 2011-07-28 2013-02-07 Toho Titanium Co Ltd Solid catalyst component for olefin polymerization, method for producing the same, olefin polymerization catalyst, and method for producing olefin polymer
CN104513330A (en) * 2013-09-30 2015-04-15 中国石油化工股份有限公司 Catalyst system used in olefin polymerization and application thereof

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