WO2008050883A1 - Procede destine a produire un copolymere bloc d'ethylene-propylene - Google Patents

Procede destine a produire un copolymere bloc d'ethylene-propylene Download PDF

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Publication number
WO2008050883A1
WO2008050883A1 PCT/JP2007/070974 JP2007070974W WO2008050883A1 WO 2008050883 A1 WO2008050883 A1 WO 2008050883A1 JP 2007070974 W JP2007070974 W JP 2007070974W WO 2008050883 A1 WO2008050883 A1 WO 2008050883A1
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Prior art keywords
bis
silane
ethylene
tris
methylamino
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PCT/JP2007/070974
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English (en)
Japanese (ja)
Inventor
Takefumi Yano
Motoki Hosaka
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Toho Catalyst Co., Ltd.
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Priority to JP2008541045A priority Critical patent/JP5235673B2/ja
Publication of WO2008050883A1 publication Critical patent/WO2008050883A1/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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Definitions

  • This HatsuTomo is ethylene.
  • Patent Document 1 Japanese Patent Laid-Open No. 63-1040 15 proposes to add various metal alkoxides during the copolymerization reaction, and has a low melt fluidity.
  • Japanese Patent Laid-Open No. 63-1040 15 proposes to add various metal alkoxides during the copolymerization reaction, and has a low melt fluidity.
  • further improvements were required to produce ethylene / propylene block copolymers with high melt flowability, high rigidity, and high impact resistance required in the recent market. .
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-1 20 3 8 8
  • the produced ethylene / propylene block copolymer is washed with liquefied propylene, and the concentration of chlorine atoms and chlorine atoms in the produced polymer are determined.
  • concentration By reducing the concentration, a method for improving rigidity, heat resistance, and impact resistance has been proposed.
  • this method requires the addition of new polymerization equipment, and it has been difficult to meet the current market demands for cost reduction.
  • the only way to obtain an ethylene-propylene block copolymer with a low price and excellent physical property balance as required by the market is to create a final product with physical properties in a direct ethylene / propylene block copolymerization reactor.
  • the method (hereinafter referred to as “straight weight method”) is attracting attention.
  • MFR melt fluidity
  • MFR value > 200 gZ l 0 min in
  • a large amount of hydrogen is required to obtain polypropylene with a low molecular weight, that is, a large MFR.
  • Patent Document 4 (WO 2 0 0 4— 1 6 6 6 2 publication) describes a compound represented by S i (OR 1 ) 3 (NR 2 R 3 ) as an olefin. It has been disclosed that by using it as a catalyst component for polymerization, a homopolypropylene having a high MFR and high stereoregularity can be produced with a small amount of hydrogenation, and has given some effect. However, this technology also has a large deactivation of the catalyst activity over time, and the polymerization activity in the second step and the subsequent steps is not sufficiently maintained, and the productivity of the ethylene / propylene block copolymer is not always sufficient. There is a need for further improvements.
  • the polypropylene part of the first step should be used in order to maintain the melt fluidity of the final product in the direct weight method. It is required to have a melt fluidity of at least an MFR value of> 200, and the rubber component must be at least 15 to 50% by weight in order to improve impact strength. MFR is required to be at least 30 or more. At the same time, it is necessary to control the molecular weight of the rubber component appropriately in order to maintain the surface characteristics of the product.
  • the manufacturing problems in the conventional manufacturing method are fundamentally solved, and in particular, the existing polymerization process has a high performance. Enables the production of block copolymers by direct polymerization, that is, maintains high catalytic activity for a long time without impairing the performance of the catalyst.
  • the first process (homopolymerization stage) and the subsequent second process (copolymerization) The catalyst activity is sufficiently high and excellent.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6 3-1 0 140 5
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 20 0 5-1 20 3 8 8
  • Patent Document 3 Japanese Patent Laid-Open No. 20 06-2220 8
  • Patent Document 4 WO 20 04-1 6 6 6 2
  • an object of the present invention is to provide a method for producing an ethylene / propylene block copolymer which makes it possible to produce an ethylene / propylene block copolymer having excellent characteristics at a low cost.
  • the present inventors have conducted intensive studies, and as a result, obtained from a solid catalyst component containing magnesium, titanium, halogen and an electron-donating compound, an organoaluminum compound, and an aminosilane compound having a specific structure.
  • ethylene / propylene block copolymerization was carried out using the formed catalyst, it was found that the problems of the prior art were solved, and the present invention was completed.
  • the present invention provides the following components (A), (B) and (C);
  • R 1 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 and p 3)
  • R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, cyclo An alkyl group and a derivative thereof, a bur group, a allyl group, and an aralkyl group, which may be the same or different
  • R 3 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, and Derivatives thereof, vinyl group, aralkyl group, aralkyl group, which may be the same or different
  • R 4 is a linear or branched alkyl group having 1 to 20 carbon atoms, sucrose alkyl group and derivatives thereof, vinyl group ,
  • An aryl group, an aralkyl group, which may be the same or different, R 3 and R 4 may combine to form a ring
  • n is 0 or an integer from 1 to 3
  • NR 3 R At least one of the four groups is a secondary amino group.
  • the present invention provides a process for producing an ethylene / propylene block copolymer characterized by comprising steps.
  • the catalyst used in the method for producing an ethylene / propylene block copolymer of the present invention has high functionality such as high stereoregularity, high hydrogen response, high catalytic activity, and maintenance of catalytic activity at the same time. Enables the production of inexpensive ethylene / propylene block copolymers by direct weight method.
  • FIG. 1 is a flowchart showing the steps for preparing the polymerization catalyst of the present invention.
  • the catalyst component (A) (hereinafter sometimes referred to as “component (A) j”) of the present invention contains magnesium, titanium, halogen and an electron donor compound,
  • Magnesium compounds include dihalogenated magnesium, dialkylmagnesium, halogenated ammonium / killed magnesium, dialkoxymagnesium, diallyloxymagnesium, halogenated alkoxymagnesium, or fatty acid magnesium.
  • dihalogenated magnesium a mixture of magnesium dihalide and dialkoxymagnesium, dialkoxymagnesium is preferable, particularly dialkoxymagnesium is preferable, and dialkoxymagnesium is preferably dimethoxy Magnesium, Diethoxymagnesium, Dipropoxymagnesium, Dibutoxymagnesium, Ethoxymethoxymagnesium, Etoxyp Examples include ropoxymagnesium and butoxyethoxymagnesium, and methoxymagnesium is particularly preferable.
  • dialkoxymagnesiums may be obtained by reacting metal magnesium with alcohol in the presence of a halogen-containing organic metal or the like.
  • the above dialkoxymagnesium can be used alone or in combination of two or more.
  • dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape may be indefinite or spherical.
  • dialkoxymagnesium when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the resulting polymer powder during the polymerization operation is improved.
  • Problems such as clogging of the filter in the resulting polymer separation apparatus are solved.
  • the spherical dialkoxymagnesium does not necessarily have a true spherical shape, and an oval shape or a potato shape can also be used.
  • the shape of the particles is such that the ratio of the major axis diameter L to the minor axis diameter W (L / W) is 3 or less, preferably: It is -2, More preferably, it is 1-1.5.
  • the above-mentioned dialkoxymagnesium having an average particle size of! ⁇ 200 / im can be used. Preferably, it is 5 to 15 ° ⁇ m.
  • the average particle size is 1 to 100 ⁇ m, preferably 5 to 50 ⁇ , and more preferably 10 to 40 ⁇ m.
  • the particle size it is preferable to use a particle having a small particle size distribution and a small particle size distribution.
  • the particle size of 5 m or less is 20% or less, and preferably 10% or less.
  • the particle size of 100 ⁇ m or more is 10% or less, preferably 5% or less.
  • the particle size distribution is expressed as D 90 / D 10 (where D 9 ° is the integrated particle size at 90 ⁇ 1 ⁇ 2, and D 10 is the integrated particle size at 10%). Less than, preferably less than 2.
  • the production method of the above spherical dialkoxymagnesium is disclosed in, for example, JP-A-58-4132, JP-A-62-51633, JP-A-3-74341, JP-A-4-74. Examples are 368 39 1 and JP-A-8-73388.
  • the tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b) j”) used for the preparation of component (A) in the present invention is represented by the general formula T i (OR 5 ) n X 4 n ( In the formula, R 5 represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ⁇ n 4.
  • titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide as titanium halides, methoxytitanium trichloride and ethoxytitanium trichloride as alkoxytitanium halides, Propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, di edoxy titanium dichloride, dipropoxy titanium dichloride, gen n-butoxy titanium dichloride, trimethoxy titanium chloride And triethoxy titanium chloride, tripropoxy titanium chloride, tri_ ⁇ -butoxy titanium chloride and the like.
  • 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 used for the preparation of the solid catalyst component (c) in the present invention is an organic compound containing an oxygen atom or a nitrogen atom.
  • component (c) is an organic compound containing an oxygen atom or a nitrogen atom.
  • organic compound containing an oxygen atom or a nitrogen atom for example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, alkyl compounds, nitriles, isocyanates, Si 1 0-C bonds Or an organic silicon compound containing a Si i N—C bond.
  • alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methylenoatenore, etinoreethenore, propinoatenore, butinore Etherol, amyl etherol, diphenyl ether, 9, 9-bis (methoxymethyl) fluorene, 2—iso-propynole 2—iso-pentyl-1,3-dimethoxypropane and other ethers, methyl formate, ethyl acetate , Vinyl acetate, Propinole acetate, Octinore acetate, Cyclohexyl acetate , Ethyl propionate, Ethyl butyrate, Ethyl benzoate, Propyl benzoate, Butyl benzoate, Octyl benzoate, Cyclohexyl benzoyl benzoate, p
  • Amines such as amamine, ethylamine, tributylamine, piperidine, aniline, pyridine, olefins such as olefinic acid amide and stearic acid amide, acetonitryl, benzonitrile, Ditolyls such as riltritolyl, isocyanates such as methyl isocyanate, acetyl isocyanate, phenol Organosilicon compounds containing Si 1 O—C bonds, such as rualkoxysilanes, alkenylalkoxysilanes, phenylalkinorea norecoxysilanes, cycloanolquinolalkoxysilanes, alkyl alkylalkylalkoxysilanes, bis (alkylamino) Dialkyloxysilanes, bis (cycloalkylamino) dialkoxysilanes, alkyl (alkylamino) dialkoxysilanes, dialky
  • esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid diester derivatives are particularly preferable.
  • Specific examples of these phthalic acid diesters include dimethyl phthalate, jetyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, and di-iso-butyl phthalate.
  • Ethyl methyl phthalate Methyl phthalate iso-propyl, Ethyl phthalate (n-propyl), Ethyl phthalate (n-Butyl), Ethyl phthalate iso-Ptyl, Di-phthalate di-n-pentanol, Phthanolic acid Diiso-pentinoles, dinepentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, phthalic acid Bis (2-ethylhexyl), di-n-nonyl phthalate, iso-decyl phthalate, bis (2,2-dimethylheptyl phthalate) ), Phthalic acid n- butyl (an IS 0 - Kishinore to - hexyl) phthalate n- heptyl (2
  • one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are alkyl groups having 1 to 5 carbon atoms, or chlorine atoms, bromine atoms and fluorine atoms. Examples thereof include those substituted with halogen atoms such as atoms.
  • the solid catalyst component prepared using the phthalate ester derivative as an electron-donating compound can further improve the effect of hydrogen amount on the melt flow rate, that is, the hydrogen response. Hydrogen added during polymerization Even in the same amount or a small amount, the melt flow rate of the polymer can be improved.
  • esters it is also preferable to use a combination of two or more of the above esters.
  • the total number of carbon atoms of the alkyl group of the ester used is 4 or more compared to that of other esters, the esters are combined. This is desirable.
  • component (d) a hydrocarbon compound (hereinafter sometimes referred to simply as “component (d)”).
  • component (d) a hydrocarbon compound (hereinafter sometimes referred to simply as “component (d)”.
  • component (d) include boiling points of toluene, xylene, ethylbenzene, hexane, heptane, octane, etc.
  • Hydrocarbon compounds at 0 are preferably used. These may be used alone or in combination of two or more.
  • a suspension is formed from component (a), component (c) and hydrocarbon compound (d) having a boiling point of 5150 ° C.
  • the preparation method by making the mixed solution formed from (b) and component (d) contact this suspension liquid, and making it react after that can be mentioned.
  • polysiloxane (hereinafter sometimes simply referred to as “component (e)”).
  • component (e) polysiloxane
  • the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced.
  • Polysiloxane is a polymer that has a siloxane bond (one si-O bond) in the main chain. Both N'oiru are collectively 2 5 Viscosity at ° C has a 0.
  • chain polysiloxane dimethylpolysiloxane and methylphenylpolysiloxane are used.
  • partially hydrogenated polysiloxane methylhydrene polysiloxane having a hydrogenation rate of 10 to 80% is used.
  • cyclic polysiloxane Hexamethylcyclotrisiloxane, Octamethylcyclotetrasiloxane, Decamethylcyclopentanesiloxane, 2,4,6-Trimethylcyclotrisiloxane, 2,4,6,8-Tetramethylcyclotetrasiloxane, and modified polysiloxanes are high-grade.
  • the component (A) is formed by contacting the components (a), (b), and (c) and, if necessary, the component (d) or the component (e). The preparation method of component (A) is described.
  • the magnesium compound (a) is suspended in an alcohol, a halogenated hydrocarbon compound solvent, a tetravalent titanium halogen compound (b) or a hydrocarbon compound (d), and electron donating properties such as phthalic acid diester.
  • examples thereof include a method of obtaining component (A) by contacting compound (c) and / or a tetravalent titanium halogen compound (b).
  • a spherical magnesium compound by using a spherical magnesium compound, a spherical component (A) having a sharp particle size distribution can be obtained, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device.
  • spray-drying method in which the suspension is sprayed and dried By forming particles by the above, it is possible to obtain a component (A) having a spherical shape and a sharp particle size distribution.
  • the contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture is removed.
  • the contact temperature is the temperature at the time of contacting each component when contacting each component, and may be the same temperature as the reaction temperature or a different temperature.
  • the contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or is dispersed or suspended for denaturation treatment.
  • a temperature range of 4 ° C to 1300 ° C is preferable.
  • the temperature during the reaction is lower than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component.
  • the temperature exceeds 1300 ° C evaporation of the solvent used is evident. This makes it difficult to control the reaction.
  • the reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
  • a preferred method for preparing component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d).
  • Method of preparing component (A) by reacting, or suspending component (a) in component (d), then contacting component (c) and then contacting component (b) to react A method for preparing the component (A) can be mentioned. Also improving the performance of the final solid catalyst component by contacting component (b) or component (b) and component (c) again or multiple times with component (A) thus prepared. Can do. In this case, it is desirable to carry out in the presence of the hydrocarbon compound (d).
  • a preferred method for preparing component (A) in the present invention is to form a suspension from component (a), component (c), and hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. ) And component (d)
  • Examples of the preparation method include contact with a liquid and subsequent reaction.
  • Preferred methods for preparing component (A) in the present invention include the following methods.
  • a suspension is formed from the component (a), the component (c), and the hydrogenated hydrocarbon compound (d) having a boiling point of 50 to 150 ° C.
  • a mixed solution is formed from the component (c) and the hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the temperature of the obtained mixed solution is raised and the reaction process (first reaction process) is performed. After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the washed solid substance is used as a solid product.
  • the washed solid material is further brought into contact with a component (b) and a hydrocarbon compound (d) having a boiling point of 50 to 150 ° C at 120 to 100 ° C, and the temperature is raised. Then, a reaction treatment (secondary reaction treatment) is carried out, and after completion of the reaction, the operation of washing with a liquid hydrocarbon compound at room temperature can be repeated 1 to 10 times to obtain component (A).
  • a reaction treatment secondary reaction treatment
  • dialkoxymagnesium (a) is suspended in a hydrocarbon compound (d) having a boiling point of 50 to 150 ° C.
  • a reaction treatment is performed before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension.
  • one or more of the electron donating compounds (c) such as phthalic acid diester is used.
  • the solid catalyst component (A) is obtained by washing (2) with a hydrocarbon compound that is liquid at room temperature by decantation.
  • a tetravalent titanium halogen compound (a) per mole of the magnesium compound (a) b) is from 0 ⁇ 5 to 100 mol, preferably from 0.5 to 50 mol, more preferably from 1 to 10 mol, and the electron donating compound (c) is from 0.0 1 to 10 mol , Preferably 0.0 1 to 1 mol, more preferably 0.02 to 0.6 mol, a hydrocarbon compound
  • the titanium solid catalyst component (A) in the present invention, magnesium, a halogen atom, the content of the electron-donating compound is not particularly default, favored properly, titanium 0.5 to 8.0 wt 0/0, preferably from 1.0 to 8.0 by weight 0/0, more preferably 2.0 to 8.0 wt 0/0, magnesium 1 0-7 0 weight. / 0 , more preferably 10 to 50 weight. / 0 , particularly preferably 15 to 40% by weight, more preferably 15 to 25% by weight, and halogen atoms 20 to 90% by weight, more preferably 30 to 85% by weight.
  • the total amount of electron-donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight.
  • the total content is 2 to 20% by weight.
  • An organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention;
  • component (B) used in forming the olefin polymerization catalyst of the present invention.
  • R 1 is preferably an ethyl group or a isoptyl group
  • Q is a hydrogen atom, a chlorine atom, bromine or the like. Atoms are preferred, p is preferably 2 or 3, and 3 is particularly preferred.
  • organoaluminum compound (B) examples include trimethylaluminum, triethylaluminum, jetinoreluminium chloride, triisobutylaluminum, jetyla noreminum mouthmide, and jetylaluminum hydride.
  • Triethyl aluminum and triisobutyl aluminum are preferable.
  • component (C) j The compound (C) represented by the above general formula (2) used in forming the olefin-based polymerization catalyst of the present invention (hereinafter sometimes referred to as “component (C) j”) is used in the prior art. It is not an alkoxysilane compound, which is an electron-donating compound, but an aminosilane compound
  • examples of the cycloalkyl group derivative include an alkyl-substituted cyclopentyl group.
  • bis (alkylamino) dicyclopentylsilane bis (alkylamino) diisopropyl silane, bis (alkylamino) tert-butylsilane, bis (alkylamino) t-butylethylsilane, bis (alkylamino) t-butylmethylsilane, bis ( Alkylamino) Dicyclohexylsilane, Bis (alkylamino) Cyclohexylmethylsilane, Bis (alkylamino) Bis (Decahidronaphthyl) Silane, Bis (anolequinoleamino) Neck pliers ⁇ / Succumen hexenolesylan, Bis (Perch) Droit Soquinolino) (Alkylamino) Alkylsilane, Bis (Perhydroquinoline) (Alkylamino) Alkylsilane, Bis (Alkylamino) dicycl
  • Di-iso-propyl silane bis (alkylamino) di-tert-butyl silane, bis (alkylamino) tert-butylethyl silane, bis (alkylamino) tert-butylmethylsilane, bis (alkylamino) dicyclohexylsilane, bis (alkylamino) cyclo Hexylmethylsilane, bis (alkylamino) bis (decahido naphthyl) silane, bis (alkylamino) cyclopentylcyclohexylsilane, bis (perhydroisoquinoline) Arukiruamino) Ryo Rukirushiran, and a bis (Pahi Dorokino Li Roh) (Arukiruamino) alkyl Rushiran.
  • aminosilane compound examples include Tris (methylamino) methylsilane, Tris (methylamino) ethylsilane, Tris (methylamino) n —Probilsilane, Tris (methylamino) iso —Provirsilane, Tris (methylamino) n —Putylsilane, Tris (Methylamino) i SO—Ptylsilane, Tris (Methylamino) t — Butylsilane, Tris (Methylamino) Cyclopentylsilane, Tris (Methylamino) Cyclohexylsilane, Tris (Methylamino) Vinylsilane,
  • Tris (methylamino) (ethylamino) silane Tris (methylamino) (n-propylamino) Silane, Tris (methylamino) (is 0-propylamino) Silane, Tris (methylamino) (n-butylamino) Silane, Tris (Methylamino) (sec-Butylamino) Silane, Tris (Methylamino) (t-Ptylamino) Silane, Tris (Methylamino) (neo-Pentylamino) Silane, Tris (Methylamino) (Di-4-Methoxyphenylamino) ) Silane, Tris (methylamino) (Jetylamino) Silane, Tris (methylamino) (Gee iso-pylamine) Silane, Tris (methylamino) (Gee iso-butylamino) Silane, Tris (methylamino) (D
  • an organic key compound other than the component (C) (hereinafter referred to as “component”).
  • component (D) an organic key compound other than the component (C)
  • component (D) an organic key compound other than the component (C)
  • T-butyl (ethyl) dimethyoxysilane dicyclohexyldimethyoxysilane, cyclohexenole (methyl) dimethyetoxysilane, cyclopentyl (ethyl) dimethyoxysilane, cyclopentyl (cyclohexyl) dimethyoxysilane, 3-methylcyclohexyl (cyclopentyl) Nore) Dimethoxysilane, 4-Methylsix hexyl (Silph pentyl) Dimethyoxysilane, 3,5-Dimethy ⁇ / Cyclohexyl (Cyclopentinole) Dimethyoxysilane, Bis (jetylamino) dimethoxysilane, bis (di-n-propylamino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (d
  • the method for producing an ethylene / propylene block copolymer in the present invention comprises 5% by weight in the presence of a catalyst comprising the above components (A), (B) and (C), and optionally a component (D).
  • propylene and ethylene are polymerized in the presence to obtain a propylene copolymer having a total ethylene content of 3 to 60% by weight.
  • the use amount ratio of each component constituting the catalyst is not particularly limited as long as it does not affect the effect of the present invention, but the normal component (B) is the component. It is used in the range of 1 to 200,000 moles, preferably 50 to 100,000 moles per mole of titanium atom in (A).
  • Component (C) is in the range of 0.02 to: I 0 mol, preferably 0.01 to 2 mol, particularly preferably 0.05 to 0.5 mol, per mol of component (B).
  • component (D) is used in combination, 0.001 to 10 mol, preferably 0.001 to: per mol of component (B)! Mol, particularly preferably in the range of 0.001 to 0.5 mol, and 0.001 to 10 mol per mol of component (C), preferably 0.005 to 1 Mole is particularly preferably used in the range of 0.1 to 0.5 mol.
  • the order of contact of each component is arbitrary.
  • the organoaluminum compound (B) is charged into the polymerization system, and then the force for contacting the component (C), the components (C) and the component (D) mixed in advance. It is desirable to bring the solid catalyst component (A) into contact by bringing the component (C) and the component (D) into contact in any order.
  • the organoaluminum compound (B) is first charged into the polymerization system, while the component (A) and the component (C), or the component (C) and the component (D) are brought into contact with each other in advance.
  • component (A) and component (C) or component (C) and component (D) are charged into the polymerization system and contacted to form a catalyst.
  • component (A) and component (C) or component (C) and component (D) are charged into the polymerization system and contacted to form a catalyst.
  • the polymerization conditions in the first step are as follows: the copolymerization temperature is 200 ° C or less, preferably 150 ° C or less, more preferably 50 to 100 ° (:, the polymerization pressure is 10 MPa or less, preferably 6 MPa In the following, it is more preferably 0.1 to 5 MPa, and any of continuous polymerization method and batch polymerization method is possible Polymerization reaction is propane, butane, isobutane, pentane, hexane, heptane, octane, etc. Slurry polymerization or solution polymerization with an inert hydrocarbon solvent, bulk polymerization or vapor phase polymerization using liquid olefins as the medium is possible at the polymerization temperature. It may be multistage.
  • the first step is preferably propylene homopolymerization, and the polymerization is preferably bulk polymerization or gas phase polymerization.
  • ethylene may be contained in a trace amount, that is, 5% by weight or less. That is, when propylene and ethylene are polymerized, a mixture of propylene and ethylene may be supplied to the reaction vessel and used, or propylene and ethylene may be continuously supplied independently to the reaction vessel.
  • the ethylene content in the propylene and ethylene mixture is 5%. / 0 or less, preferably 3% by weight or less, and in the case of gas phase polymerization, 0 to 0.08 NL // min, preferably 0 to 0, per 1 NLZ of propylene based on the gas supply amount to the reaction vessel 0.05 NL / min.
  • the ethylene content in the intermediate polymer obtained in the first step is 5% by weight or less, preferably 3% by weight or less.
  • the unreacted monomer is usually separated from the solid polymer continuously with a bag filter device or the like.
  • the second step in the presence of the intermediate obtained in the first step, preferably ethylene 3-3 0 0 mole 0/0 for propylene Len 1 0 0 mole 0/0, and particularly preferably 5 to 2 0 0 mole 0/0 by polymerizing corresponding propylene and ethylene in whole E styrene content 3-6 0% by weight, preferably from 3 to 4 0% by weight, is properly especially preferred 1 0-4 0 weight 0 /
  • This is a process for obtaining an ethylene / propylene block copolymer of zero .
  • the copolymerization temperature, pressure and polymerization method in the second step are the same as those in the first step, but in the second step, propylene and ethylene are copolymerized in the presence of an intermediate. Is preferred.
  • propi For the polymerization of len and ethylene, a mixture of propylene and ethylene may be supplied to the reaction vessel and used, or propylene and ethylene may be supplied continuously to the reaction vessel independently. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight during polymerization.
  • the catalyst components (A) to (C) may be used in the polymerization tank used in the first step, and the second stage constituting the multistage polymerization tank.
  • the components (B), (C) and (D), the components (C) and (D), or the component (C) may be added to the polymerization tank in each stage. Additional supply may be provided.
  • an intermediate amount corresponding to 20 to 95% by weight, preferably 30 to 85% by weight of the total polymer is formed to obtain a specific amount of intermediate.
  • the second step by obtaining a copolymer containing a specific amount of total ethylene content and producing copolymers of various compositions, the properties such as elasticity, rigidity, surface properties and low temperature impact properties are different.
  • a polymer can be obtained.
  • the composition of propylene and ethylene in the first step and the second step, and the ratio of the polymer produced in the first step and the second step may be appropriately controlled according to the target polymer grade.
  • the amount of the intermediate polymer in the whole polymer is controlled within the above numerical range
  • the total ethylene content in the copolymer is controlled within the above numerical range.
  • the average polymerization rate and average in the apparatus When staying
  • a method for estimating the amount of polymer produced by the product between the two a method for controlling the amount of propylene supplied in the first step and the amount of propylene and ethylene supplied in the second step, the feed gas composition and outlet of the reactor
  • One example is a method in which the composition is quantitatively analyzed continuously and the composition is automatically controlled.
  • known electron donating compounds such as alcohols, oxygen gas or ketones are added to the polymerization system in order to prevent gel formation in the final product. can do.
  • alcohols include ethyl alcohol, isopropyl alcohol and the like, and the amount used is 0.01 to: L 0 mol, preferably 0.1 to 2 mol, relative to 1 mol of component (B).
  • first step and second step also referred to as “main polymerization” in combination of the first step and the second step
  • first step and second step also referred to as “main polymerization” in combination of the first step and the second step
  • catalytic activity “stereoregularity”
  • stereophilicity In order to further improve the particle properties and the like to be generated, it is desirable to perform prepolymerization.
  • monomers such as olefins or styrene similar to the main polymerization can be used.
  • component (A), component (B) and / or component (C) are contacted in the presence of olefins, and 0.001 to 100 g of polyolefin per component (A) lg is reserved.
  • the catalyst is polymerized and contacted with component (B) and / or component (C) to form a catalyst.
  • component (D) is used in combination, component (A), component (B) and component (D) are brought into contact with each other in the presence of olefins during the pre-polymerization, and component (C) is used during the main polymerization. That's right.
  • the order of contacting the respective components and monomers is arbitrary.
  • the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene.
  • the component (C) and the component (D) are brought into contact with each other, and then the component (A) Is then contacted with olefins such as propylene and / or one or more other olefins.
  • the prepolymerization temperature is optional and is not particularly limited, but preferably 10 ° C. It is in the range of ⁇ 70 ° C., more preferably in the range of 0 ° C. ⁇ 50 ° C.
  • catalytic activity generated polymer (E) gZ solid catalyst component gZ 1 hour.
  • the polymerization activity of the catalyst in the homo PP part is shown in Table 1 as the first step (homo stage) polymerization activity.
  • melt fluidity (MFR) of the obtained homo-PP part and the obtained ethylene / propylene block copolymer was measured according to the method of AS TM D 1 238.
  • the melt fluidity of the obtained ethylene / propylene block copolymer (ICP) is expressed as ICP (MFR).
  • Block rate (%) is autocrape weight (F) g, after the homo PP polymerization stage is finished, and after unreacted monomer is removed Autoclave weight (G) g, copolymerization 60 minutes after anocrepe weight
  • Homopolymer g (G-F) g
  • Block rate after 20 minutes (%) (K—G) g / (K-F) g X 1 00
  • the content of ethylene-propylene rubber component (hereinafter referred to as EPR) in the block copolymer was measured by the following method.
  • EPR ethylene-propylene rubber component
  • the solid part was taken in a beaker, 500 ml of acetone was added thereto, and the mixture was stirred at room temperature for 15 minutes. The solid was filtered and dried, and the weight was measured (this weight is designated as B). In addition, the solvent was distilled off from the separated liquid phase portion, and the solid was dried and weighed (this weight is C).
  • the content (% by weight) of EPR in the block copolymer was calculated by the formula of C (g) X 100 / ⁇ B (g) + C (g) ⁇ .
  • Ethylene content in EPR and ethylene content in solid B in the P-xylene insoluble part were measured by 13 C-NMR. The ethylene contents (in EPR) and (in XI) are shown in Tables of Examples, respectively.
  • the intrinsic viscosity of EPR (77) is reduced using the Ubbelohde viscometer in 1 35 ° C decalin at three concentrations of 0.1, 0.2, and 0.5 g dl. Next, the intrinsic viscosity was determined by extrapolation by plotting the reduced viscosity against the concentration and extrapolating the concentration to zero.
  • the molar ratio of T i, TEA, and B EAD C (T i / TEA / BE AD C) in the solid catalyst solid component was set to 1 Z 6 0 0 1 2 0.
  • 4 L of hydrogen gas and 1.4 L of liquefied propylene were charged and prepolymerized at 20 ° C for 5 minutes, and then propylene was polymerized at 70 ° C for 1 hour, and unreacted monomer was removed. Released.
  • the operation of pressurizing 0.5 MPa of high-purity nitrogen gas and then releasing the pressure was repeated 5 times to make the reactor a nitrogen gas atmosphere.
  • the weight of the autoclave was measured, and the production amount (weight) of homo-PP was calculated.
  • the homo PP was extracted from the polymer extraction device under nitrogen gas so that the homo PP in the reactor was about 200 g. did.
  • the copolymer was continuously fed to the reactor so that the total pressure was 1.2 MPa and the copolymerization was conducted at 70 ° C for a maximum of 2 hours. Copolymerization reaction time 30 minutes, 60 minutes, 90 minutes, 120 Each batch was polymerized in minutes. After the completion of batch polymerization, the gas supply was stopped, the weight of the reactor was measured, and the block ratio was calculated from the weight of the copolymer produced as an evaluation of the amount of copolymer produced at each time.
  • the amount of polymer required for analysis was extracted, the composition of the copolymer was analyzed, and the change over time was observed.
  • the results are shown in Table 1.
  • a 500 ml round bottom flask equipped with a stirrer and thoroughly replaced with nitrogen gas was charged with 4.76 g of anhydrous magnesium chloride, 25 ml of decane and 2 3.4 ml of 2-ethylhexyl alcohol. And reacted at 30 ° C for 2 hours to obtain a homogeneous solution.
  • 1.1 g of phthalic anhydride was added to the homogeneous solution and reacted at 1300C for 1 hour.
  • the solution was then charged into a round bottom flask having a capacity of 500 ml, equipped with a stirrer and thoroughly substituted with nitrogen gas, and titanium tetrachloride maintained at 20 ° C. 200 m 1 The whole amount was dropped into the inside over 1 hour.
  • the mixed solution was heated to 110 ° C. over 4 hours, and 2.68 ml of diisobutyl phthalate was added thereto and reacted for 2 hours.
  • the liquid part is removed by filtration, and the remaining solid component is washed at 110 ° C until no free titanium compound is detected with decane and hexane, filtered and dried to obtain a powdery solid A catalyst component was obtained.
  • the titanium content in the solid catalyst component was measured and found to be 3.1% by weight.
  • Example 6 Synthesis of ethylene-propylene block copolymer> Except that bis (ethylamino) diisoprovirsilane obtained in Reference Example 2 was used in place of bis (ethylamino) dicyclopentylsilane, ethylene was used in the same manner as in Example 1. A propylene block copolymer was synthesized. The results are shown in Table 2.
  • the ethylene-propylene block copolymer was synthesized in the same manner as in Example 1 except that bis (ethylamino) t_ptylmethylsilane obtained in Reference Example 4 was used instead of bis (ethylamino) dicyclopentylsilane. Conducted for 2 hours. The results are shown in Table 2.
  • Ethylene-propylene block copolymer was synthesized in the same manner as in Example 1 except that cyclohexylmethyldimethoxysilane was used in place of bis (ethylamino) dicyclopentylsilane. The results are shown in Table 2.
  • Ethylene-propylene block copolymer was synthesized in the same manner as in Example 1 except that cetylaminotriethoxysilane was used instead of bis (ethynoleamino) dicyclopentylsilane. The results are shown in Table 2. Table 1
  • the ethylene / propylene block copolymer obtained by the method of the present invention has a block rate that increases with the ethylene / propylene block copolymerization time compared to the comparative example of the prior art, and the polymerization activity increases. Maintained for a long time.
  • the MFR of homopolypropylene under the same amount of hydrogen is more than seven times that of the comparative example, and it is clear that the chain transferability (hydrogen response) by hydrogen is extremely excellent.
  • Homopolypropylene has an extremely high stereoregularity because the value of XS (p-xylene soluble part), which is an evaluation of stereoregularity, is 1.5% by weight or less even when the MFR is large compared to the comparative example.
  • EPR produced by ethylene-propylene block copolymerization was easily controlled by the amount of hydrogen, and the MFR of the ethylene / propylene block copolymer having a high EPR content could be increased.
  • the method of the present invention based on these results made it possible to produce an ethylene / propylene block copolymer having high performance and low cost in direct polymerization.

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Abstract

L'invention concerne un copolymère bloc de propylène peu coûteux présentant un excellent équilibre entre les propriétés physiques et susceptible d'être produit par un procédé comportant : une première étape destinée à polymériser un composant monomère qui est principalement composé de propylène et peut contenir de l'éthylène dans une quantité de 5 % en poids ou moins en présence d'un catalyseur constitué de (A) un composant catalyseur solide comprenant du magnésium, du titane, un halogène et un composé donneur d'électrons, (B) un composé d'aluminium organique représenté par la formule : R1pAlQ3-p et (C) un composé aminosilane représenté par la formule : R2nSi(NR3R4)4-n, produisant ainsi un intermédiaire dans une quantité correspondant à entre 20 et 95 % en poids de la quantité totale du polymère produit par le procédé ; et une deuxième étape destinée à polymériser l'intermédiaire avec du propylène et de l'éthylène dans une quantité comprise entre 3 et 300 % en moles par rapport à 100 % en moles de propylène, produisant ainsi un copolymère de propylène présentant une teneur totale en éthylène comprise entre 5 et 50 % en poids.
PCT/JP2007/070974 2006-10-27 2007-10-23 Procede destine a produire un copolymere bloc d'ethylene-propylene WO2008050883A1 (fr)

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JP2010024454A (ja) * 2008-07-23 2010-02-04 Samsung Total Petrochemicals Co Ltd 高光沢性のポリプロピレン系樹脂
WO2010106888A1 (fr) * 2009-03-17 2010-09-23 東邦チタニウム株式会社 Composant de catalyseur solide et catalyseur pour la polymérisation d'oléfines, et procédé de production de polymères d'oléfine l'employant
JP2011256120A (ja) * 2010-06-07 2011-12-22 Toho Titanium Co Ltd オルガノアミノシラン化合物の製造方法
JP2012506147A (ja) * 2008-10-20 2012-03-08 ダウ コーニング コーポレーション Ｃｖｄ前駆体
WO2018207642A1 (fr) * 2017-05-10 2018-11-15 東邦チタニウム株式会社 CATALYSEUR DE POLYMÉRISATION D'OLÉFINES, PROCÉDÉ DE PRODUCTION D'UN POLYMÈRE D'OLÉFINES, ET COPOLYMÈRE PROPYLÈNE/α-OLÉFINE

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JP2005120332A (ja) * 2003-09-25 2005-05-12 Ube Ind Ltd α−オレフィンの重合又は共重合用触媒、その触媒成分及びα−オレフィンの重合方法
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JP2010024454A (ja) * 2008-07-23 2010-02-04 Samsung Total Petrochemicals Co Ltd 高光沢性のポリプロピレン系樹脂
US8772524B2 (en) 2008-10-20 2014-07-08 Dow Corning Corporation CVD precursors
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WO2010106888A1 (fr) * 2009-03-17 2010-09-23 東邦チタニウム株式会社 Composant de catalyseur solide et catalyseur pour la polymérisation d'oléfines, et procédé de production de polymères d'oléfine l'employant
JP5543430B2 (ja) * 2009-03-17 2014-07-09 東邦チタニウム株式会社 オレフィン類重合用固体触媒成分および触媒並びにこれを用いたオレフィン類重合体の製造方法
JP2011256120A (ja) * 2010-06-07 2011-12-22 Toho Titanium Co Ltd オルガノアミノシラン化合物の製造方法
WO2018207642A1 (fr) * 2017-05-10 2018-11-15 東邦チタニウム株式会社 CATALYSEUR DE POLYMÉRISATION D'OLÉFINES, PROCÉDÉ DE PRODUCTION D'UN POLYMÈRE D'OLÉFINES, ET COPOLYMÈRE PROPYLÈNE/α-OLÉFINE
KR20190140484A (ko) * 2017-05-10 2019-12-19 도호 티타늄 가부시키가이샤 올레핀류 중합용 촉매, 올레핀류 중합체의 제조 방법 및 프로필렌-α-올레핀 공중합체
JPWO2018207642A1 (ja) * 2017-05-10 2020-03-12 東邦チタニウム株式会社 オレフィン類重合用触媒、オレフィン類重合体の製造方法およびプロピレン−α−オレフィン共重合体
JP7145149B2 (ja) 2017-05-10 2022-09-30 東邦チタニウム株式会社 オレフィン類重合用触媒、オレフィン類重合体の製造方法およびプロピレン－α－オレフィン共重合体
KR102530372B1 (ko) 2017-05-10 2023-05-09 도호 티타늄 가부시키가이샤 올레핀류 중합용 촉매, 올레핀류 중합체의 제조 방법 및 프로필렌-α-올레핀 공중합체

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