WO2008120795A1 - Composant catalytique solide pour une polymérisation d'oléfines, catalyseur de polymérisation, et procédé de production de polymère oléfinique le comprenant - Google Patents

Composant catalytique solide pour une polymérisation d'oléfines, catalyseur de polymérisation, et procédé de production de polymère oléfinique le comprenant Download PDF

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WO2008120795A1
WO2008120795A1 PCT/JP2008/056512 JP2008056512W WO2008120795A1 WO 2008120795 A1 WO2008120795 A1 WO 2008120795A1 JP 2008056512 W JP2008056512 W JP 2008056512W WO 2008120795 A1 WO2008120795 A1 WO 2008120795A1
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polymerization
methyl
malonate
group
acid
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PCT/JP2008/056512
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English (en)
Japanese (ja)
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Motoki Hosaka
Hiroyuki Kono
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Toho Catalyst Co., Ltd.
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Priority to JP2009507553A priority Critical patent/JP5340916B2/ja
Publication of WO2008120795A1 publication Critical patent/WO2008120795A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • Solid catalyst component for polymerization of olefins catalyst for polymerization and method for producing olefins polymer using the same
  • the present invention relates to a solid catalyst component and catalyst for polymerization of olefins which are high in activity and good in hydrogen activity, and can obtain high stereoregular polymer in high yield.
  • a solid catalyst component for alefin polymerization using a malonic acid ester compound instead of a conventional phthalic acid ester compound as an internal electron donating compound has also been developed.
  • No. 6 9 8 7 which is supported on halogenated M g and at least A solid catalyst component consisting of a titanium compound having a bond and a monoalkyl-substituted malonic acid diester such as jetyl 2-isopropyl malonate is disclosed.
  • Patent Document 3 WO 03/9504
  • a halogen-containing titanium compound, metallic magnesium, an alcohol, and a halogen having a weight of not less than 0.01 gram per 1 mol of the metallic magnesium are used.
  • a solid catalyst component comprising an alkoxy group-containing magnesium compound obtained by reacting a metal having a carbon atom and Z or a metal-containing compound, and a dialkyl-substituted malonic acid diester such as jetyl 2,2-dimethyl methacrylate Is disclosed.
  • melt polymer flowability melt flow rate
  • a high value is required, and therefore, many studies have been conducted to raise the melt flow rate of polymers.
  • Melt flow rate is highly dependent on the molecular weight of the polymer. It is common practice in the art to add hydrogen as a molecular weight regulator for the resulting polymer during the polymerization of propylene. At this time, when producing low molecular weight polymers, that is, usually adding a large amount of hydrogen to produce a high melt flow lay polymer, the pressure resistance of the reactor is limited due to its safety, There is also a limit to the amount of hydrogen that can be added. For this reason, In order to add more hydrogen, it is necessary to lower the partial pressure of the monomer to be polymerized, which leads to a decrease in productivity. In addition, the use of a large amount of hydrogen raises cost issues.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6 3-30 10 (Claims)
  • Patent Document 2 Special Table 2 Table 0 00-5 1 6 9 8 7 (claims)
  • Patent Document 3 WO 0 3/9 5504 (claims) That is, the present invention
  • the object is to solve the problems remaining in the prior art and to obtain a polymer having high hydrogen activity and high stereoregularity in a high yield, solid catalyst component for polymerization of olefins, polymerization It is an object of the present invention to provide a catalyst for use as well as a method for producing an olefin polymer using the same. Disclosure of the invention
  • the present invention provides a magnesium compound (a), a tetravalent titanium halogen compound (b) and the following general formula (1);
  • R 1 and R 2 each represent a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, a aryl group, an aryl group and a halogen atom 1 or 2 substituted carbon number Any of 1 to 10 linear or branched alkyl groups may be the same or different.
  • R 3 represents an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group, a bulyl group or an aryl group
  • R 4 represents an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, a farinole group, an aralchil group R 3 and R 4 are different in any of the groups.
  • the present invention provides a solid catalyst component for olefins polymerization prepared by contacting an electron donating compound (c) represented by
  • the present invention provides: (A) the above solid catalyst component,
  • R 5 represents an alkyl group having 1 to 4 carbon atoms
  • Q represents a hydrogen atom or a halogen atom
  • p is a real number of 0 ⁇ p ⁇ 3.
  • the present invention provides a catalyst for polymerization of olefins, which is characterized by being formed by an external electron donating compound.
  • the present invention also provides a method for producing an olefins polymer, which comprises polymerizing the olefins in the presence of the catalyst for olefins polymerization.
  • FIG. 1 is a flow chart showing the steps of preparing the polymerization catalyst of the present invention.
  • Magnesium compound (a) used in the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “solid catalyst component (A)”) according to the present invention for polymerization of olefins
  • component (a) used in the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “solid catalyst component (A)”) according to the present invention for polymerization of olefins
  • component (a) used in the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “solid catalyst component (A)”) according to the present invention for polymerization of olefins
  • component (a) used in the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “solid catalyst component (A)” for polymerization of olefins
  • dihalogenated magnesium a mixture of magnesium dihalide and dioroleoxymagnesium, and dialkoxymagnesium are preferable, and dialkoxymagnesium is particularly preferable.
  • dialkoxy magnesium general formula M g (OR 1 °) ( OR 1 J) ( wherein, scale ⁇ Oyopi represents an alkyl group of ⁇ carbon atoms 1 0, their respective may be the same or different
  • the compounds represented by the above are preferred, and more specifically, dimethylmagnesium, methoxymagnesium, diproxoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like can be mentioned.
  • These dialkoxymagnesiums may be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound or the like. Further, the above dialoxy magnesium can be used alone or in combination of two or more.
  • the dialkoxymagnesium used for the preparation of the solid catalyst component (A) in the present invention is granular or powdery, and the shape may be amorphous or spherical.
  • the shape of the particle has a ratio (l Z w) of major axis diameter 1 to minor axis diameter w of 3 or more. And preferably 1 to 2, more preferably 1 to 1.5.
  • the average particle diameter of the above dialkoxymagnesium may be 1 to 200 / z m. Preferably it is 5 to 150 m. In the case of spherical dihydroxymagnesium, the average particle size is 1 to 100 m, preferably 5 to 50 ⁇ m, and more preferably 10 to 40 ⁇ m. Also, with regard to its particle size, it is desirable to use one with less fine and coarse powders and a narrow particle size distribution. Specifically, the particle size of 5; urn or less is 20% or less, preferably 10% or less. On the other hand, particles of 100 ⁇ m or more are 10% or less, preferably 5% or less. Further, its particle size distribution is shown as I n (D 90 / D 10) (where, D 90 is a particle size at 90% in cumulative particle size, D 10 is a particle size at 10% in cumulative particle size). Is 3 or less, preferably 2 or less.
  • the tetravalent titanium halogen compound (b) used for the preparation of the solid catalyst component (A) in the present invention has the general formula T i (OR 12 ) n X 4 _ n (wherein R 12 has 1 to 4 carbon atoms) And X is a halogen atom such as chlorine, bromine or iodine, and n is an integer of 0 ⁇ n ⁇ 4. It is selected from a titanium halide or alkoxy titanium halide group represented by Or one or more of the following compounds.
  • titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like as titanium halides, and mettitanium trichloride as alkoxy titanium halides, Acetoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethyl titanium titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di n-butoxy titanium dichloride Examples thereof include lead, trimethyl titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride. Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.
  • the electron donating compound (c) used for preparation of the solid catalyst component (A) in the present invention is a compound represented by the above general formula (1).
  • These compounds are dihalogen-substituted malonic acid diesters, alkyl and halogen-substituted malonic acid diesters, dialkyl-substituted malonic acid diesters, halogenated alkyl-substituted malonic acid diesters, etc. (hereinafter, also referred to as “substituted malonic acid diesters”). is there.
  • the halogen atom is a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, preferably a chlorine atom and a bromine atom.
  • R 1 is preferably a methyl group or an isopropyl group
  • R 1 is a methyl group and R 2 is a t-butyl group, or both R 1 and R 2 are preferably a isobutyl group.
  • R 3 which is an ester residue of carbonyl is a linear or branched alkyl group having 1 to 3 carbon atoms, specifically a methyl group, a ethyl group, a propyl group, An isopropyl group is preferred, and particularly preferred is a methyl group or an ethyl group.
  • R 4 is preferably an alkyl group having 2 to 20 carbon atoms, and is particularly preferably a linear or branched alkyl group having 2 to 8 carbon atoms, and more specifically an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group, a heptyl group, an octyl group, an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, an isohexyl group, an isoheptyl group and an isooctyl group are preferable.
  • dihalogen-substituted malonic acid diesters include: dichloromalonic acid methinoleethyleole, dichloromalonic acid methyoleepropinore, dichloromalonic acid methylated / lebutinore, dichloromalonic acid methyolee isoptinole, dichloromalonic acid methylpentinole, dichloromalonic acid Methinolene neopentinole, Methyl dichloromalonate hexinol, Dichloromalonic acid methyl isohexyl, Dichloromalonic acid methinole heptyl, Dichloromalonic acid methinoleso heptyl, Dichloro malonate Methinoleocutinole, Dichloromalonic acid methino Resohokutinole, Dichloromalonic acid Etireno Propinolee, Dichloromalonic acid Etinole butyl, Dichloromeric acid Etin
  • alkyl and halogen-substituted malonic acid diesters include: methylated methylo malonate methylenoletinole; Chloromalonic acid ethino reisophoroctinole, etoleole bromomalonic acid methinolechinore, ethenole bromomalonic acid methinolepropionore, ethenole bromomalonic acid methinolebutinore, tet / rebromomalonic acid ethinolebuti / le, tethynolole malonic acid ethino oleo Cutinole, Isopropinole Chloromalonic Acid Methyl / Reetinole, Isopropylole Chloromalonic Acid Metinole Propinole, Isopro Nole Chloromalonic Acid Methoreptinole, Isopropi
  • dialkyl substituted malonic acid diester examples include methyl ethyl disisopropioleno malonate, methyl propyl diisopropyl malonate, methyl butyl diisopropyl benzoate, methyl isobutyl diisopropyl malonate, methyl pentyl diisopropyl malonate, diisopropyl malonic acid Methyl neopentyl, methyl isopropyl methyl benzoate, methyl isohexyl methyl isohexyl, methyl heptyl diisopropyl malonate, methyl heptyl diisopropyl malonate, methyl isoheptyl diisopropyl malonate, methyl octyl diisopropyl malonate, methyl iso malocyl disiso malonate, diisopropyl malon Acid ethyl propyl, isopropyl
  • Examples thereof include oral acid ethylisoheptyl, isopropyl isopentyl oxalic acid ethyloxyl, isopropyl isopentyl oxalic acid ethyli sylotil and the like.
  • halogenated alkyl-substituted malonic acid diester examples include methyl butyl bis (chloromethyl) malonate, bis (bromomethyl) malonic acid methinolebutinol, bis (chloroethinole) malinol methylolate maltoate / bis, bis (bromoethyl) malonate methyl butyl, bis Examples thereof include (3-Cro-mon-one-n-propyl) malonate methy / lebutyl, and bis (3-promo n-propinole) methyl butyl malonate.
  • methyl isopyl bromo malonate, butylated methyl malonate is methyl bromo malonate, methyl butyro malonate butylated butyl malonate, butyl ethyl bromo malonate, methyl / iso butyl bromo malonate, methyl butyl diisopropy malonate, methyl butyl dibutyl malonate, Dibutyl butyl malo-butyl, methyl butyl di-butyl malonate, methyl di-butyl mono-butyro methyl ether, di-butyl mono-butyl methyl diisobutyro malonate, methyl butyl di-isopentyl malonate, methyl butyl isopropyl iso-butyl malonate, isopropyl isopentyl Butyl methyl malonate, t
  • butyl of the ester residue is n-butyl or isobutyl.
  • diethoxy magnesium is used for the magnesium compound (a) and the alkyl group of the ester residue of R 3 and R 4 is used as the electron donor compound (c).
  • an alkyl group of a different ester residue other than the acetyl group is used, in the process of contacting each component and preparing the solid catalyst component, an etoxy group of jetoxymagnesium and one kind of electron donating compound ( Exchange with the ester residue of c) takes place, and three or more kinds of malonic acid ester compounds, including the electron donor compound (c) contained in the solid catalyst component, are finally obtained.
  • the esters contained in the solid catalyst component are dimethyl diisobutyl malonate and diisobutyl
  • the esters contained in the solid catalyst component are dimethyl diisobutyl malonate and diisobutyl
  • malonate methyloleate ethyl methyl diisobutyl malonate n-butynore, diisobutyl malonate n-butyl and n-butyl diisobutyl malonate.
  • the substituted malonic acid diester represented by the general formula (1) when used as the electron donating compound used for the preparation of the solid catalyst component, high activity and activity against hydrogen can be obtained. It is possible to obtain a good high stereoregular polymer in a high yield.
  • the preparation of the solid catalyst component (A) is carried out at a boiling point of 50 to 150 ° C. It is preferable to carry out the suspension contact in the hydrocarbon solvent (d) of As a hydrocarbon solvent having a boiling point of 50 to 150 ° C., toluene, xylene, diethylbenzene, hexane, heptane, octane, cyclohexane and the like are preferably used. These may be used alone or in combination of two or more. When a hydrocarbon solvent having a boiling point of 50 to 150 ° C.
  • the solid catalyst component (A) of the present invention can be prepared by contacting the above-mentioned magnesium compound (a), tetravalent titanium halogen compound (b) and electron donating compound (c). More specifically, the magnesium compound (a) is suspended in a tetravalent titanium halide compound (b) or a hydrocarbon solvent (d), and further an electron donor compound (c) and no or tetravalent one.
  • a method of contacting a titanium halogen compound (b) to obtain a solid catalyst component there is a method of contacting a titanium halogen compound (b) to obtain a solid catalyst component.
  • a solid catalyst component having a spherical shape and a sharp particle size distribution by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, a solution using a spray device.
  • a solid catalyst component having a spherical shape and a sharp particle size distribution by forming particles by spray drying of the suspension, so-called spray drying method.
  • the contact of each component is carried out with stirring in a container equipped with a stirrer under an inert gas atmosphere and under the condition where water and the like are removed.
  • the contact temperature may be a relatively low temperature range around room temperature when simply contacting and stirring and mixing, or dispersing or suspending and modifying it, but the reaction may be carried out after contact and the product
  • the temperature range of 40 to 130 D C is preferred when obtaining.
  • the reaction temperature is less than 40 ° C., the reaction does not proceed sufficiently, and as a result, the performance of the prepared solid catalyst component becomes insufficient, and the temperature exceeds 130 ° C. As the evaporation of the solvent used becomes remarkable, the control of the reaction becomes difficult.
  • the reaction time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more.
  • the process in the double parenthesis ( ⁇ ) can be further improved by repeating the process several times as necessary.
  • the component (b) or the component (d) used in the step in ⁇ may be a new addition or a residue of the previous step.
  • the product obtained in each contacting step can be washed with a hydrocarbon compound which is liquid at normal temperature.
  • dialkoxymagnesium as a magnesium compound (a) is used as a hydrocarbon solvent (d) at a boiling point of 50 to 150 as toluene.
  • this suspension is brought into contact with titanium tetrachloride as the tetravalent titanium halogen compound (b), and then the reaction is carried out.
  • one or two or more kinds of dialkyl-substituted malonic acid diesters may be used as an anionic compound (c), Contact at 20 to 130 ° C.
  • the solid reaction product (1) is washed with a liquid hydrocarbon compound at a normal temperature (intermediate washing), and then the tetravalent titanium halogen compound (b) is again added thereto in the presence of an aromatic hydrocarbon compound.
  • the reaction is carried out by contacting at 0 to 100 ° C. to obtain a solid reaction product (2). If necessary, the intermediate washing and reaction treatment may be repeated several more times.
  • the solid reaction product (2) is then washed (final wash) with a hydrocarbon compound liquid at room temperature to obtain a solid catalyst component (A).
  • Preferred conditions for the above treatment or washing are as follows.
  • Low temperature aging reaction -20 to 70 ° C, preferably 1 to 60 ° C, more preferably 0 to 30, 1 minute to 6 hours, preferably 5 minutes to 4 hours, particularly preferably 1 0 minutes to 3 hours.
  • Reaction treatment 0 to: I 30, preferably 40 to: L 20 ° (:, particularly preferably 50 to: L 15 for 0.5 to 6 hours, preferably 0.5 to 5 hours Particularly preferably 1 to 4 hours.
  • the hydrocarbon compound used in the washing is preferably an aromatic compound or a saturated hydrocarbon compound which is liquid at normal temperature, and specifically, an aromatic hydrocarbon compound such as toluene, xylene, hydroxyethylbenzene or the like. Examples of compounds include hexane, heptane, cyclohexane and the like. Be Preferably, it is desirable to use an aromatic hydrocarbon compound in the intermediate cleaning and a saturated hydrocarbon compound in the final cleaning.
  • the ratio of the amount of each component used in preparation of the solid catalyst component (A) can not be generally defined because it varies depending on the preparation method, but for example, a tetravalent titanium halide compound (1 mole of magnesium compound (a) b) Force S O. 5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donor compound (c) is 0.1 to 1 to 10 mol.
  • the amount of the hydrocarbon solvent (d) is preferably 0.000 to 1 mol, more preferably 0.2 to 0.2 mol, and the hydrocarbon solvent (d) is preferably 0.01 to 500 mol, preferably 0.000 to 100 Mole, more preferably 0.000 to 5: 1 mole.
  • the content of titanium, magnesium, halogen atom and electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably 1.8 to 8 wt% of titanium, preferably 2.0 to 8.0 by weight 0/0, more preferably 2.0 to 6.0 wt 0/0, magnesium 1 0-7 0% by weight, more preferably 1 0 to 50 wt%, particularly preferably Is 15 to 40% by weight, more preferably 15 to 25% by weight, 20 to 90% by weight of halogen atoms, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight More preferably, it is 45 to 75% by weight, and the total of the electron donor compounds is 0.5 to 30% by weight, more preferably a total of 1 to 2% by weight, particularly preferably 2 to 20% by weight in total.
  • the titanium content is 3 to 8% by weight, and the magnesium content is 1 It is desirable that the content of the halogen atom is 45 to 75% by weight, and the content of the halogen-containing compound is 2 to 20% by weight.
  • organic aluminum compound (B) used when forming the catalyst for the olefins polymerization of the present invention a compound represented by the general formula R s n AIQ 3 p (wherein R 5 is An alkyl group having 1 to 4 carbon atoms is shown, Q is a hydrogen atom or a halogen atom, and p is a real number of 0 or p 3.
  • the compounds represented by) can be used.
  • Specific examples of such organoaluminum compounds (B) include triethylaluminum, jetylaluminum chloride, tri-iso-butylaluminum, jetylaluminum bromide, and diethylaluminum hydride. One, two or more can be used.
  • triethyl aluminum and tri-iso-butyl aluminum are used.
  • component (C) As the external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) used when forming the catalyst for olefins polymerization of the present invention, a compound represented by the general formula (3):
  • R 6 , R 7 or R 8 is a hydrogen atom, carbon number 1 to 12 linear or branched alkyl groups, substituted or unsubstituted cycloalkyl groups, phenyl groups, aryl groups, aryl groups, or aryl groups, which may contain hetero atoms;
  • R 9 may be analkyl group having 1 to 4 carbon atoms, a cycloanolechil group, a phenyl group, a buryl group, an alliole group or an aralkyl group, which may contain a hetero atom, and may be the same or different
  • R 7 and R 8 may combine to form a cyclic group), and one or more selected from organic key compounds represented by and polyethers may be mentioned.
  • R 6 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms. Alkyl groups and cycloalkyl groups having 5 to 8 carbon atoms are preferred.
  • R 7 or R 8 is a linear or branched alkyl having 1 to 10 carbon atoms The group is preferably a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms, or a cycloalkenyl group having 5 to 8 carbon atoms.
  • R 7 and R 8 are preferably combined to form a ring (NR 7 R 8 ), preferably a perhydroquino lino group or a perhydroisoquino lino group.
  • R 9 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • organic silicon compounds include phenylalkoxysilane, ⁇ / lequinoleanolexoxisilane, phenylolenolequinoleoxylsilane, cycloanolekylalkoxysilane, silicoroleoleanolequino.
  • examples include realkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkyl (alkylamino) silane, alkylaminosilane and the like.
  • particularly preferred compounds are di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldime Toxisilane, di-n-butyl jetxilesilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyloxysilane, cyclohexylmethyl dimethyxsilane, cyclohexylemethyl jetoxysilane, cyclohexyle dimethyxsilane, cyclohexylexysilane, Zishik Oral pentyldimethoxysilane, dicyclopentyljetioxysilane, cyclopentylmethyldimethoxysilane, cyclo
  • the organic key compound (C) can be used singly or in combination of two or more.
  • the polyethers 1,3-diethers are preferred, and further, 9,9-bis (methoxymethyl) fluorene and 2-isopentyl-2-isopentyl-1, 3-dimethoxypropane are preferred.
  • These external electron donor compounds can be used alone or in combination of two or more.
  • the catalyst for the polymerization of olefins according to the present invention comprises the solid catalyst component (A) for polymerization of olefins described above, component (B) and component (C), and the polymerization of olefins in the presence of the catalyst Or perform copolymerization.
  • olefins examples include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- 1 1-pentene, biphenylhexane and the like, and these olefins can be used alone or in combination of two or more. .
  • ethylene, propylene and 1-butene are preferably used.
  • propylene is particularly preferred.
  • copolymerization with other olefins can also be carried out.
  • the olefins to be copolymerized are, for example, ethylene, 1-butene, 1-pentene, 4-methinole- 1-pentene, bininoleic acid hexene, etc. These olefins may be used alone or in combination of two or more. It can be used together.
  • ethylene and 1-butene are preferably used.
  • the organoaluminum compound (B) is contained in the solid catalyst component (A). It is used in an amount of 1 to 200 mol, preferably 5 to 100 mol, per 1 mol of titanium atoms.
  • the organic silicon compound (C) is used in an amount of 0.000 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the component (B). It is used in the range of
  • each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is brought into contact, and the solid catalyst component (A Contact is desirable.
  • the polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and olefin monomers such as propylene can be used in either a gas or liquid state.
  • Polymerization temperature is 200 ° C or less
  • Mashiku is less than 1 0 0 D C
  • the polymerization pressure is 1 OMP a, preferably less than or equal to 5 MP a.
  • either continuous polymerization or batch polymerization can be used.
  • the polymerization reaction may be carried out in one step or in two or more steps.
  • the contact sequence of each component and monomer is optional, but preferably the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an oxygen gas atmosphere, and then the olefins After contacting the solid catalyst component (A) for polymerization, olefin such as propylene and Z or one or more other olefins are contacted.
  • component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an oxygen gas atmosphere, and then the olefins After contacting the solid catalyst component (A) for polymerization, olefin such as propylene and Z or one or more other olefins are contacted.
  • the component (B) When prepolymerization is carried out by combining the component (C), the component (B) is first charged into a prepolymerized system set to an inert gas atmosphere or an oxygen gas atmosphere, and then the component (C) is brought into contact with Furthermore, after contacting the solid catalyst component (A) for olefins polymerization, it is preferable to contact olefins such as propylene and one or more other olefins.
  • olefins such as propylene and one or more other olefins.
  • the reaction product obtained is washed four times with 200 ml of toluene at 90 ° C., 40 ml of titanium tetrachloride and 80 ml of toluene are newly added, and the temperature is raised to 10 ° C., 1
  • the reaction was allowed to stir with time.
  • the solid catalyst component was obtained by washing seven times with 200 ml of 40 n-heptane. The solid content in the solid catalyst component was separated, and the titanium content in the solid content was measured, which was 4.5% by weight.
  • the polymerization activity per 1 g of the solid catalyst component, the ratio of the boiling n-heptane insoluble portion in the produced polymer (HI), the value of the melt flow rate of the produced polymer (a) (MFR; Table 1 shows the “MI”.
  • polymerization activity formation polymer (g) / solid catalyst component (g)
  • the ratio of insoluble n-heptane insoluble matter (HI) in the formed polymer is the ratio of the polymer insoluble in n-heptane when this formed polymer is extracted with boiled n-heptane for 6 hours. (% By weight)
  • a solid catalyst component was prepared in the same manner as in Example 1 except that diisoptyrolemalonate cetyl n-butyl 5.25 ml was used instead of diisoputolemalonic acid n-butyl, and 5.4 ml was used. The formation and polymerization of the polymerization catalyst were conducted. As a result, the titanium content in the obtained solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that methyl ethyl disopropyl malonate 3.9 m 1 is used instead of n-butyl diisobutyl malonate 4.5 ml, and the formation and polymerization of a polymerization catalyst are further carried out. Did. As a result, the titanium content in the obtained solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that methyl n-butyl malonate 4,3 m 1 is used instead of methyl n-butyl malon dibutyl malonate 4.5 ml, and a polymerization catalyst is further formed. And polymerization The As a result, the titanium content in the obtained solid catalyst component was 4.3% by weight.
  • 0.1% by weight of dimethyl diisobutyl malonate, 0.1% by weight of methyl ethyl diisobutylmalonate, 0.1% by weight of methyl diisobutyl malonate in the catalyst are contained in the catalyst.
  • the solid catalyst was the same as in Example 1 except that methyl bis (3-chloro-n-propinole) malonate n-putinole 4. 9 ml was used instead of n-butyl diisoputinolemalonate 4.5 ml
  • the components were prepared, and the formation and polymerization of a polymerization catalyst were further performed. As a result, the titanium content in the obtained solid catalyst component was 3.9% by weight.
  • the polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that methyl n-butyl butylbromomalonate 3.7 m 1 is used instead of n-butyl isobutyl malonate 4.5 ml, and a polymerization catalyst is further formed. And polymerization. As a result, the titanium content in the solid catalyst component was 3.4% by weight. The polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that n -butyl butylbromomalonate 4.3 m 1 is used instead of n-butyl diisobutyl malonate 4.5 m I, and a polymerization catalyst is further formed. And polymerization. As a result, the titanium content in the solid catalyst component was 3.3% by weight. The polymerization results are shown in Table 1.
  • Example 8 Preparation of solid catalyst component in the same manner as in Example 1 except that methyl t-butylmethylmalonate n-butyl 4.3 m 1 was used instead of 4.55 ml of diisoputinolemalonic acid nethyl esterate Further, the formation and polymerization of a polymerization catalyst were performed. As a result, the titanium content in the solid catalyst component was 3.3% by weight. The polymerization results are shown in Table 1.
  • a solid catalyst component was prepared in the same manner as in Example 1 except that 4.5 ml of butylisobutyl malonate was used instead of 4.5 ml of diisoputolemelonic acid eth ⁇ / n-putinole, Furthermore, the formation and polymerization of a polymerization catalyst were carried out. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that instead of 4.5 ml of n-butyl diisobutyl malonate, a solid catalyst component is used in the same manner as in Example 1, further formation of a polymerization catalyst and It has been polymerized. As a result, the titanium content in the solid catalyst component was 4.4% by weight.
  • the polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that 5.4 ml of methyl t-butyl methyl malonate is used instead of 4.5 ml of n-butyl diisobutyl malonate, and a polymerization catalyst is further prepared. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
  • a solid catalyst was prepared in the same manner as in Example 1 except that di n-butyl phthalate 4.0 m 1 was used instead of n-butyl diisobutyl malonate 4.5 ml.
  • the catalyst components were prepared, and the formation and polymerization of a polymerization catalyst were performed. As a result, the titanium content in the solid catalyst component was 3.5% by weight.
  • the polymerization results are shown in Table 2.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that instead of 4.55 ml of diisoputinolemalonate n-butyl, a solid catalyst component is used except for the formation of a polymerization catalyst. And polymerization. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
  • titanium tetrachloride 17 Om 1 is inserted into a round bottom flask equipped with a stirrer and having a volume of 1 1; Was dropped. Thereafter, the temperature was raised to 110 ° C., and methyl diisobutylmalonate n-butyl 4.Oml was added. Then, it was treated at 110 ° C. for 2 hours. After the supernatant was removed, 17 Om 1 of titanium tetrachloride was newly introduced, and reaction was carried out with stirring at 110 ° C. for 2 hours.
  • the solid catalyst component was obtained by washing 7 times with 20 O ml of n-heptane at 40 ° C.
  • the solid liquid in the solid catalyst component was separated, and the titanium content in the solid content was measured to be 3.0% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 4 except that dicyclopentylbis (ethyamino) silane 0.13 mmol was used instead of 0.13 mm o 1 of hexylmethyldimethoxysilane.
  • the polymerization results are shown in Table 1.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that 4.1 ml of isobutyl 2-isopropyl malonate is used instead of 4.5 ml of isobutyl malonate n-butyl, and a polymerization catalyst is further prepared. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
  • a solid catalyst component was prepared in the same manner as in Example 1 except that instead of 4.5 ml of diisoputolemale malonate ethylenoate n-butyl, 4.1 m 1 of 2-isopropylmalonic acid ethyl neopentyl was used. Further, formation and polymerization of a polymerization catalyst were performed. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
  • a solid catalyst component was prepared in the same manner as in Example 12 except that di n-butyl phthalate 4.0 ml was used instead of methyl n-butyl diisobutylmalonate 4.0 ml. As a result, the titanium content in the solid catalyst component was 2. 7% by weight.
  • a solid catalyst component was prepared in the same manner as in Example 13 except that di n-butyl phthalate 4.0 m 1 was used instead of n-butyl malonate diisobutyl malonate. As a result, the titanium content in the solid catalyst component was 2.9% by weight.
  • a solid catalyst component was prepared in the same manner as in Example 1, except that di n-butyl malonate 4.5 m 1 was used instead of 4.5 ml of diisoputolemalonic acid ethinole n-butynolole, Further, the formation and polymerization of a polymerization catalyst were performed. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 2.
  • a solid catalyst component was prepared in the same manner as in Example 1 except that 2-sopropylmalonic acid n-butyl 4.1 m 1 was used instead of diisobutyl sodium hexyl n-butyl 4.5 m 1. Further, formation of a polymerization catalyst and polymerization were conducted. As a result, the titanium content in the solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 2.
  • a solid catalyst component was prepared in the same manner as in Example 1, except that 5.4 ml of diisobutyl malonate malonate was used instead of 4.5 ml of diisoputinolemalonic acid eth ⁇ / n-butylate, Further, the formation and polymerization of a polymerization catalyst were performed. As a result, the titanium content in the solid catalyst component was 4.8% by weight. polymerization The results are shown in Table 2.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that dimethyl diisobutyl malonate 4.5 m 1 is used instead of diisoputolemale malonate n-butyrene 4.5 ml, and a polymerization catalyst is further formed. And polymerization. As a result, the titanium content in the solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 2.
  • a solid catalyst component is prepared in the same manner as in Example 1 except that methyl ethyl 2-isopropylmalonate 4.1 m 1 is used instead of diiso succino remalo acid ethylole n-butynore 4.5 m 1, and a polymerization catalyst is further prepared. Formation and polymerization. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 2.
  • the solid catalyst component was prepared in the same manner as in Example 1 except that methyl n-butyl 2-isopropylmalonate 4.1 ml was used in place of 4.5 ml of diisoputinolemalonate ethyl n-butynolate. Further, the formation and polymerization of a polymerization catalyst were performed. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2. Table 1

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Abstract

L'invention concerne un composant catalytique solide pour une polymérisation d'oléfines, qui est préparé en mettant en contact un dialcoxymagnésium (a), un halogénure (b) de titane tétravalent, et un composé donneur d'électrons (c) représenté par la formule générale R1R2C (COOR3)(COOR4). L'invention concerne également un catalyseur pour une polymérisation d'oléfines qui comprend le composant catalytique solide, un composé d'organoaluminium représenté par la formule générale R5pAlQ3-p, et un composé donneur d'électrons externe. Lorsqu'il est utilisé pour polymériser un composé oléfinique, le catalyseur a une activité élevée, et active de l'hydrogène de manière satisfaisante. Un polymère fortement stéréorégulier peut ainsi être obtenu à un rendement élevé.
PCT/JP2008/056512 2007-03-30 2008-03-26 Composant catalytique solide pour une polymérisation d'oléfines, catalyseur de polymérisation, et procédé de production de polymère oléfinique le comprenant WO2008120795A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012060361A1 (fr) 2010-11-04 2012-05-10 東邦チタニウム株式会社 Procédé de production d'un composant de catalyseur solide pour la polymérisation d'oléfines, catalyseur pour la polymérisation d'oléfines, et polymères d'oléfines
US8383540B2 (en) 2010-12-21 2013-02-26 Dow Global Technologies Llc Catalyst composition with halo-malonate internal electron donor and polymer from same
WO2016121549A1 (fr) * 2015-01-30 2016-08-04 東邦チタニウム株式会社 Procédé de production de catalyseur de polymérisation d'oléfine et procédé de production de polymère d'oléfine

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160625A (ja) * 1997-08-22 1999-03-02 Idemitsu Petrochem Co Ltd オレフィン重合用固体触媒成分、オレフィン重合用触 媒及びオレフィン重合体の製造方法
JP2000516988A (ja) * 1997-06-09 2000-12-19 モンテル テクノロジー カンパニー ビーブイ オレフィンの重合用成分および触媒
JP2000516987A (ja) * 1997-06-09 2000-12-19 モンテル テクノロジー カンパニー ビーブイ オレフィンの重合用成分および触媒
JP2002528606A (ja) * 1998-11-04 2002-09-03 モンテル テクノロジー カンパニー ビーブイ オレフィン重合用成分と触媒
JP2003327615A (ja) * 2002-05-10 2003-11-19 Idemitsu Petrochem Co Ltd オレフィン重合用固体触媒成分、オレフィン重合用触媒及びオレフィン重合体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000516988A (ja) * 1997-06-09 2000-12-19 モンテル テクノロジー カンパニー ビーブイ オレフィンの重合用成分および触媒
JP2000516987A (ja) * 1997-06-09 2000-12-19 モンテル テクノロジー カンパニー ビーブイ オレフィンの重合用成分および触媒
JPH1160625A (ja) * 1997-08-22 1999-03-02 Idemitsu Petrochem Co Ltd オレフィン重合用固体触媒成分、オレフィン重合用触 媒及びオレフィン重合体の製造方法
JP2002528606A (ja) * 1998-11-04 2002-09-03 モンテル テクノロジー カンパニー ビーブイ オレフィン重合用成分と触媒
JP2003327615A (ja) * 2002-05-10 2003-11-19 Idemitsu Petrochem Co Ltd オレフィン重合用固体触媒成分、オレフィン重合用触媒及びオレフィン重合体の製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012060361A1 (fr) 2010-11-04 2012-05-10 東邦チタニウム株式会社 Procédé de production d'un composant de catalyseur solide pour la polymérisation d'oléfines, catalyseur pour la polymérisation d'oléfines, et polymères d'oléfines
JP5797661B2 (ja) * 2010-11-04 2015-10-21 東邦チタニウム株式会社 オレフィン類重合用触媒およびオレフィン類重合体の製造方法
US8383540B2 (en) 2010-12-21 2013-02-26 Dow Global Technologies Llc Catalyst composition with halo-malonate internal electron donor and polymer from same
JP2014500385A (ja) * 2010-12-21 2014-01-09 ダウ グローバル テクノロジーズ エルエルシー ハロ−マロネート内部電子供与体を備える触媒組成物および同一物由来のポリマー
US8697827B2 (en) 2010-12-21 2014-04-15 W. R. Grace & Co.-Conn Catalyst composition with halo-malonate internal electron donor and polymer from same
WO2016121549A1 (fr) * 2015-01-30 2016-08-04 東邦チタニウム株式会社 Procédé de production de catalyseur de polymérisation d'oléfine et procédé de production de polymère d'oléfine
CN107207645A (zh) * 2015-01-30 2017-09-26 东邦钛株式会社 烯烃类聚合催化剂的制造方法和烯烃类聚合物的制造方法
KR20170109576A (ko) * 2015-01-30 2017-09-29 도호 티타늄 가부시키가이샤 올레핀류 중합 촉매의 제조 방법 및 올레핀류 중합체의 제조 방법
JPWO2016121549A1 (ja) * 2015-01-30 2017-11-09 東邦チタニウム株式会社 オレフィン類重合触媒の製造方法およびオレフィン類重合体の製造方法
US10392453B2 (en) 2015-01-30 2019-08-27 Toho Titanium Co., Ltd. Production method for olefin-polymerization catalyst and production method for olefin polymer
CN107207645B (zh) * 2015-01-30 2020-01-17 东邦钛株式会社 烯烃类聚合催化剂的制造方法和烯烃类聚合物的制造方法
KR102462715B1 (ko) 2015-01-30 2022-11-03 도호 티타늄 가부시키가이샤 올레핀류 중합 촉매의 제조 방법 및 올레핀류 중합체의 제조 방법

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