• 专利附录
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    • 专利摘要:
    The present invention relates to a titanium compound (A) and an ester compound (B) having a titanium-halogen bond or a mixture of a titanium compound (A) and an ester compound (B) having a titanium-halogen bond at the same time. A solid catalyst component for olefin polymerization obtained by contact with a solid catalyst component precursor (C) containing a hydrocarbyloxy group. According to the present invention, an olefin polymer is produced which provides a solid catalyst component for olefin polymerization having excellent particle shape, exhibits excellent polymerization activity with respect to the solid catalyst component and is excellent in powder property.
    公开号:KR19990029380A
    申请号:KR1019980035512
    申请日:1998-08-31
    公开日:1999-04-26
    发明作者:신이찌 구마모또；에이지 나까이시；마꼬또 사또
    申请人:고사이 아끼오；스미또모 가가꾸 고오교오 가부시끼가이샤；
    IPC主号:
    专利说明:

    Solid catalyst component for olefin polymerization and catalyst for olefin polymerization, and method for producing olefin polymer
    The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a process for producing an olefin polymer. More specifically, the present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer, which are suitable for gas phase polymerization and slurry polymerization processes.
    The olefin polymers of the present invention include homopolymers of olefins and copolymers of olefins with other olefins.
    When the activity (polymerization amount per unit catalyst) of the catalyst used for the preparation of the olefin polymer is sufficiently high, it is not necessary to remove the catalyst residue from the polymer produced after the polymerization, and thus its usefulness can be simplified. Naturally, the value is extremely high industrially.
    On the other hand, it is desirable for the polymer or the like to adhere to the polymerization vessel as little as possible, since the polymer or the like adheres to the polymerization vessel, causing various problems in operation and reducing the operational efficacy. In view of operational stability and operational efficiency, it is preferable that the polymer powder has a high apparent density, a narrow particle size distribution, and excellent fluidity. In addition, since the presence or absence of the low molecular weight component in a polymer becomes a factor which controls transparency, impact resistance, and blocking property of a film, it is preferable to manufacture the olefin polymer containing a small amount of a low molecular weight component.
    Recently, in the field of catalysts for olefin polymerization, the polymerization activity has been significantly improved by the combination of magnesium compounds and titanium compounds (e.g., JP-B-46-34092, JP-B-47-41676, JP-B-55-23561, JP-B-57-24361). However, the olefin polymers produced by using such catalysts were not satisfactory in that they were in particle form and blocking properties.
    It has been disclosed that in the stereoregular polymerization of propylene, a highly crystalline polymer can be obtained with high activity using a catalyst obtained by treating with an oxygen-containing electron donor such as ester as an internal donor (e.g., JP-B -52-39431, 52-36786, 1-28049 and 3-43283). However, the olefin polymer obtained by carrying out the copolymerization of ethylene with an α-olefin using such a catalyst was not satisfactory in particle properties and blocking properties as described above.
    1 is a development view for better understanding of the present invention. This development is a representative example of an embodiment of the present invention, and the present invention is not limited to this example.
    An object of the present invention is to provide a solid catalyst component for olefin polymerization having excellent particle morphology, an olefin polymerization catalyst having a high polymerization activity for the catalyst, which does not require removal of catalyst residues, and a low molecular weight having excellent particle properties using the catalyst. It is to provide a method for producing an olefin polymer containing a small amount of components.
    The present inventors studied these problems with high intensity and completed the present invention.
    That is, the present invention provides an olefin obtained by simultaneously contacting a titanium compound (A) and an ester compound (B) having a titanium-halogen bond with the solid catalyst component precursor (C) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups. By contacting a solid catalyst component for polymerization and a mixture of a titanium compound (A) and an ester compound (B) having a titanium-halogen bond and a solid catalyst component precursor (C) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups It is to provide a solid catalyst component for olefin polymerization obtained. The present invention also provides a method for producing an olefin polymer comprising polymerizing an olefin using an olefin polymerization catalyst comprising the solid catalyst component (I) and an organoaluminum compound (II) for olefin polymerization and the catalyst for olefin polymerization. to provide.
    The invention will be explained in detail below.
    [Solid Catalyst Component for Olefin Polymerization]
    Solid catalyst component (I) for olefin polymerization of the present invention is a solid catalyst component precursor (C) containing a titanium compound (A) and an ester compound (B) having a titanium-halogen bond containing magnesium atoms, titanium atoms and hydrocarbyloxy groups (C). Or by contacting a mixture of a titanium compound (A) and an ester compound (B) having a titanium-halogen bond with a solid catalyst component precursor (C) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups It is a solid catalyst component for olefin polymerization obtained.
    As the titanium compound (A) having a titanium-halogen bond used in the present invention, a titanium compound having at least one Ti-Cl bond is preferable. In particular, titanium halides, titanium halide alkoxides, titanium halide amides, and the like can be cited, and titanium tetrachloride is particularly preferable in terms of polymerization activity.
    As the ester compound (B) used in the present invention, mono- or poly-atomic carboxylic acid esters are preferably used, examples of which are saturated or unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, aromatic carboxylic acids. Esters and the like. Specific examples thereof include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, n Butyl benzoate, isobutyl benzoate, methyl toluate, ethyl toluate, ethyl aniseate, diethyl succinate, di-n-butyl succinate, diisobutyl succinate, diethyl malonate, di-n- Butyl malonate, diisobutyl malonate, dimethyl maleate, di-n-butyl maleate, diisobutyl maleate, diethyl itaconate, di-n-butyl itaconate, diisobutyl itaconate, Monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate Phthalate, diisobutyl phthalate, di-n-octyl phthalate, diphenyl phthalate and the like.
    Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylate, maleate and the like, or aromatic carboxylic acid esters such as phthalate are preferred, aromatic carboxylates are more preferred, and diesters of phthalic acid are particularly preferred. .
    The solid catalyst component precursor (C) used in the present invention is a solid component containing magnesium atoms, titanium atoms and hydrocarbyloxy groups. In particular, in the presence of an organosilicon compound (1) having a Si-O bond, disclosed in JP-B-3-043283, the organomagnesium compound (3) is represented by the formula Ti (OR 1 ) a X 4-a (where R is 1 represents a hydrocarbon group having C 1-20 , X represents a halogen atom, a is a number satisfying 0a ≦ 4), and the solid product obtained by reducing the titanium compound (2) represented by 0a ≦ 4, and JP-B In the presence of an organosilicon compound (1) having a Si-O bond and a porous carrier (4), disclosed in 4-057685, the organomagnesium compound (3) is represented by the formula Ti (OR 1 ) a X 4-a (wherein The solid product obtained by reducing the titanium compound (2) represented by R 1 , X, a is the same as the above definition).
    Specific examples of R 1 in the titanium compound (2) represented by the above formula include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, amyl, iso-amyl, Alkyl group such as n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, aryl group such as phenyl group, cresyl group, xylyl group, naphthyl group, cyclohexyl group, cyclophene A cycloalkyl group such as a methyl group, an allyl group such as a propenyl group, and the like, and an aralkyl group such as a benzyl group.
    Of these groups, C 2-18 alkyl groups or C 6-18 aryl groups are preferred. In particular, a C 2-18 straight chain alkyl group is preferred. Titanium compounds having at least two different OR 1 groups can also be used.
    As a halogen atom represented by X, a chlorine atom, a bromine atom, and an iodine atom can be illustrated. In particular, the chlorine atom shows the preferable result.
    a is a number which satisfy | fills 0a <= 4, Preferably 2 <= a <= 4, More preferably, a = 4.
    In order to synthesize | combine a titanium compound (2), a well-known method can be used. For example, a method of reacting Ti (OR 1 ) 4 and TiX 4 at a predetermined ratio, and a method of reacting TiX 4 and a corresponding alcohol (eg, R 1 OH) and the like in a predetermined amount may be used.
    As organosilicon compound (1) which has a Si-O bond, the following compound is mentioned.
    Si (OR 3 ) b R4 4-b
    R 5 (R 6 2 SiO) c SiR 7 3 , or
    (R 8 2 SiO) d
    R 3 represents a C 1-20 hydrocarbon group, R 4 , R 5 , R 6 , R 7 and R 8 represent a C 1-20 hydrocarbon group or a hydrogen atom, b is a number satisfying 0b ≦ 4, c Represents an integer between 1 and 1000, and d represents an integer between 2 and 1000.
    Specific examples of the organosilicon compound include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-iso-propoxysilane, di -Iso-propoxy-di-iso-propylsilane, tetra-n-propoxysilane, di-n-propoxydi-n-propylsilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, Di-n-butoxydi-n-butylsilane, di-iso-butoxydi-iso-butylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxy Sisilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexa-n-propyldisiloxane, hexaisopropyldisiloxane, octaethyltrisiloxane, poly (dimethylsiloxane), poly (diphenylsiloxane) , Poly (methylhydrosiloxane), poly (phenylhydrosiloxane) and the like.
    Among these organosilicon compounds, alkoxysilane compounds represented by the formula Si (OR 3 ) b R 4 4-b are preferred, alkoxysilane compounds satisfying 1 ≦ b ≦ 4 are more preferred, and tetraalkoxy having b is 4 Particular preference is given to silane compounds.
    As the organomagnesium compound (3), any form of organomagnesium compound having a magnesium-carbon bond can be used. In particular, the Grignard compound represented by the formula R 9 MgX (R 9 represents a C 1-20 hydrocarbon group, X represents a halogen atom), or the formula R 10 R 11 Mg (R 10 and R 11 are C 1-20 A dialkyl magnesium compound or a diaryl magnesium compound represented by the above) is preferably used. R 10 and R 11 may be the same or different. Specific examples of R 9 to R 11 include a C 1-20 alkyl group, a C 20 or less aryl group, a C 20 or less aralkyl group, and a C 20 or less alkenyl group such as a methyl group, an ethyl group, an n-propyl group, and iso -Propyl group, n-butyl group, sec-butyl group, tert-butyl group, iso-amyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, phenyl group, benzyl group and the like. In particular, it is preferable to use the Grignard compound represented by R 9 MgX in the form of an ether solution in terms of catalyst performance.
    It is also possible to use an organometallic compound which dissolves the organomagnesium compound in a hydrocarbon and a hydrocarbon soluble complex of the organomagnesium compound. Examples of organometallic compounds include organic compounds of Li, Be, B, Al or Zn.
    As the used porous carrier 4, known porous carriers can be used. Porous inorganic oxides, polystyrene, styrene-divinylbenzene copolymers, styrene-ethylene glycol dimethacrylate copolymers, polymethylacrylates, polys, such as SiO 2 , Al 2 O 3 , MgO, TiO 2 , ZrO 2, etc. Ethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, Organic porous copolymers such as polyethylene, polypropylene, and the like. Among them, styrene-divinylbenzene copolymer or acrylonitrile-divinylbenzene copolymer is preferably used.
    The porous carrier preferably has a volume (pore volume) of pores having a pore radius of 200 to 2000 mm 3, preferably 0.3 cc / g or more, more preferably 0.4 cc / g or more, and a pore radius of 35 to 75000 mm 3. The volume is preferably at least 35%, more preferably at least 40%. If the pore volume of the porous material is too small, the catalyst component is sometimes not effectively fixed. In addition, even when the pore volume of the porous carrier is 0.3 cc / g or more, the catalyst component is sometimes not effectively fixed unless such pores are sufficiently present in the range of the pore radius of 200 to 2000 mm 3.
    As a method of reducing a titanium compound with an organomagnesium compound, there is a method of adding an organomagnesium compound (3) to a mixture of a titanium compound (2) and an organosilicon compound (1), and a reverse method thereof. 4) may be present.
    The titanium compound (2) and the organosilicon compound (1) are preferably dissolved or diluted in a solvent suitable for use.
    Examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, octane, decane, aromatic hydrocarbons such as toluene, xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin, and diethyl ether, di-n-butyl Ether compounds such as ether, diisoamyl ether, tetrahydrofuran and the like.
    The reduction temperature is usually -50 to 70 ° C, preferably -30 to 50 ° C, more preferably -25 to 35 ° C.
    The dropping time is not particularly limited, but is usually 30 minutes to 6 hours. After the reduction is completed, the post reaction may be further carried out at a temperature of 20 to 120 ℃.
    The amount of the organosilicon compound (1) used is an atomic ratio Si / Ti of the silicon compound to the titanium atom in the titanium compound (2), usually 1 to 500, preferably 1 to 300, more preferably 3 to 100. to be.
    The amount of the organomagnesium compound (3) used is an atomic ratio (Ti + Si) / Mg of the sum of titanium and silicon atoms to magnesium atoms, usually 0.1 to 10, preferably 0.2 to 5.0, more preferably 0.5 to 2.0.
    The molar ratio of Mg / Ti in the solid catalyst component (I) is 1 to 51, preferably 2 to 31, more preferably, the amount of the titanium compound (2), the organosilicon compound (1) and the organomagnesium compound (3) is used. Can be determined to be in the range of 4 to 26.
    The solid product obtained by reduction is solid-liquid separated and washed several times with an inert hydrocarbon solvent such as hexane, heptane and the like.
    The obtained solid catalyst component precursor (C) contains trivalent titanium, magnesium and hydrocarbyloxy groups and generally exhibits amorphous or extremely low crystallinity.
    The solid catalyst component by simultaneously contacting a titanium compound (A) and an ester compound (B) having a titanium-halogen bond with the solid catalyst component precursor (C) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups obtained by the above method (I) is obtained. In particular, the method of adding the mixture obtained by mixing (A) and (B) beforehand to (C), the method of continuously adding and processing (A) and (B) to (C), (A) and (B) Adding to (C) and treating at the same time, and adding and treating these components in reverse.
    The solid catalyst component obtained by contacting (A) or (B) with (C) and subjecting the remaining (B) or (A) to contact treatment after an operation such as washing is not preferred, which is used for polymerization. If this is the case, the effect of improving the blocking properties and particle properties of the produced polymer is not sufficient.
    The method of adding and treating the mixture obtained by mixing (A) and (B) beforehand to (C) is preferable. The operation can be repeated two or more times and after this operation, (A) or (B) can be further contacted with the treated solid.
    The amount of titanium compound (A) used is usually 0.1 to 1000 millimoles, preferably 0.3 to 500 millimoles, more preferably 0.5 to 300 millimoles per gram of solid catalyst component precursor (C).
    In the contact treatment, all of the titanium compound (A) may be used at one time, but may be optionally divided and used several times.
    The amount of the ester compound (B) used is usually 0.1 to 1000 mmol, preferably 0.3 to 500 mmol, particularly preferably 0.5 to 300 mmol, per 1 g of the solid catalyst component precursor (C).
    In the contact treatment, all of the ester compound (B) may be used at once, but may be optionally divided and used several times.
    The molar ratio of the ester compound (B) to the titanium compound (A) is preferably 0.05 to 50, more preferably 0.1 to 10 when the (A), (B) and (C) are simultaneously subjected to contact treatment.
    Treatment of the solid catalyst component precursor (C) with the titanium compound (A) and the ester compound (B) may be carried out by any known method capable of contacting both components, such as a slurry method or a mechanical grinding means (e.g., a ball mill). Can be done. However, contacting both components in the presence of a diluent (slurry method) is preferable because a solid catalyst component having a narrow particle size distribution is obtained.
    In addition, after the treatment, the following treatment may be performed immediately, but the washing process may be repeated several times using a diluent to remove unreacted reagents.
    Diluents are preferably inert to the treated solid component and are aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like, alicyclic hydrocarbons such as benzene, toluene, xylene and the like, and 1,2-dichloroethane, monochlorobenzene and the like. Halogenated hydrocarbons can be used.
    The amount of diluent used is usually 0.1 ml to 1000 ml per g of solid catalyst component precursor (C). Preferably from 1 ml to 100 ml per gram.
    Treatment and washing temperatures are usually from -50 to 150 ° C, preferably from 0 to 120 ° C.
    The treatment and washing time is not particularly limited but is preferably 0.5 to 6 hours.
    The solid catalyst component (I) obtained in this way can be used for polymerization in the form of a slurry, in the presence of a diluent, or for polymerization in the form of a flowable powder after appropriate drying.
    [Catalyst for Olefin Polymerization]
    The catalyst for olefin polymerization used in the present invention consists of the solid catalyst component (I) and the organoaluminum compound (II) obtained by the above method.
    Organoaluminum compound (II) has at least one Al-carbon bond in the molecule.
    Representative examples thereof are as follows.
    R 12 r AlY 3-r
    R 13 R 14 Al- (O-AlR 15 ) d R 16
    R 12 , R 13 , R 14 , R 15 and R 16 each independently represent a C 1-8 hydrocarbon group, and Y represents a halogen atom, a hydrogen atom or an alkoxy group. R represents a number defined by 2 ≦ r ≦ 3. d represents a number defined by 1 ≦ d ≦ 30.
    Specific examples of the organoaluminum compound include trialkylaluminum, diethylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, such as tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and the like. Dialkylaluminum hydrides such as dialkylaluminum halides, diethylaluminum hydrides, di-n-butylaluminum hydrides, diisobutylaluminum hydrides and the like, mixtures of trialkylaluminum and dialkylaluminum halides, tetraethyl Alkylalumoxanes such as dialumoxane, tetra-n-butyldialumoxane, tetra-iso-butyldialumoxane, polymethylalumoxane, polyethylalumoxane and the like.
    Among these organoaluminum compounds, Trialkyl aluminum; Mixtures of trialkylaluminum and dialkylaluminum halides; Or alkylalumoxane is preferred, and among them, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialum Oxane is preferred.
    The amount of the organoaluminum compound (II) to be used can usually be selected in a wide range of 1 to 1000 moles per mole of titanium atoms in the solid catalyst component (I), with a range of 5 to 600 moles being preferred.
    [Preliminary Polymerization]
    The solid catalyst component (I) of the present invention can be used by itself in the polymerization, and it can also be used for the main polymerization (hereinafter abbreviated as polymerization) after the prepolymerization is carried out before the polymerization. Prepolymerization is carried out by contacting the solid catalyst component (I) for olefin polymerization with the organoaluminum compound (II) and the olefin.
    Ethylene, propylene, butene-1, etc. are mentioned as an olefin. Prepolymerization can be either homopolymerization or copolymerization.
    In order to obtain a prepolymer having high crystallinity, a known electron donor and hydrogen can be coexisted. As the electron donor, an organic compound having a Si-OR bond (wherein R represents a C 1-20 hydrocarbon) is preferably used.
    In carrying out the prepolymerization of the solid catalyst component (I) of the present invention, it is preferable to make (I) into a slurry, and examples of the solvent used to make the slurry include aliphatic hydrocarbons (for example, butane, pentane, hexane, heptane). , Aromatic hydrocarbons (eg toluene, xylene) and the like.
    The slurry concentration is usually 0.001 to 0.5 g (solid) / ml (solvent), preferably 0.01 to 0.3 g (solid) / ml (solvent). It is preferable to use an organoaluminum compound so that the molar ratio of Al / Ti may be 0.1-100, especially 1-10.
    The prepolymerization temperature is usually -30 to 80 ° C, preferably -10 to 50 ° C.
    The amount of prepolymerization is usually 0.1 to 100 g, preferably 0.5 to 50 g per 1 g of the solid catalyst component (I).
    [Method for producing olefin polymer]
    In the present invention, a solid catalyst component or a prepolymerized solid catalyst component and an organoaluminum compound can be used to homopolymerize one olefin or to copolymerize two or more olefins.
    More detailed implementations of the polymerization are shown below.
    In order to supply the solid catalyst component and the organoaluminum compound to the polymerization vessel, there is no limitation except that the inert gas (eg, nitrogen, argon), hydrogen, olefin or the like is supplied under water-free conditions.
    The solid catalyst component and the organoaluminum compound may be fed after being fed or contacted respectively.
    The polymerization can be carried out by known methods such as conventional gas phase polymerization, slurry polymerization and the like.
    It is usually preferred to carry out the polymerization at a temperature lower than the point at which the polymer melts, preferably at 20 to 100 ° C., more preferably at 40 to 90 ° C., under a pressure in the range of atmospheric pressure to 40 kg / cm 2 . In addition, in the polymerization, hydrogen may be added as a molecular weight regulator for the polymerization for the purpose of controlling the melt fluidity of the final product. The polymerization can be carried out by a continuous method or a batch method.
    The olefins used in the polymerization have two or more carbon atoms, specific examples thereof include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1 and the like. do.
    In the present invention, homopolymerization of olefins or copolymerization of two or more olefins can be carried out. In particular, it is preferable to copolymerize ethylene and C 3 or more α-olefin 1 or 2 or more. In this case, an ethylene copolymer can be prepared by contacting a mixed state of ethylene and at least one α-olefin with a catalyst.
    Example
    The following examples illustrate the invention in detail below, but are not limited to this range.
    In the Example, the property of a polymer is measured by the following method.
    (1) Content of α-olefin
    A calibration curve is made from the characteristic absorption of ethylene and α-olefin measured using an infrared spectrophotometer (1600 series, manufactured by Perkin Elmer), and the calibration curve is used to determine the content of the α-olefin. The content is expressed as short chain branch number (SCB) per 1000 C.
    (2) The outflow (FR) is measured according to ASTM D1238.
    (3) Adopt a flow rate ratio (FRR) as a measure of melt flowability. FRR is expressed as the ratio of runoff (FR) when a load of 21.60 kg is applied to the method for measuring runoff (FR) according to ASTM D1238.
    FRR = (flow rate when the load is 21.60 kg) ÷ (flow rate when the load is 2.160 kg)
    In general, it is known that the wider the molecular weight distribution of a polymer, the greater the FRR value.
    (4) The low molecular weight component amount is calculated as the content (CXS) of the portion of the total polymer extracted with cold xylene at 25 ° C.
    (5) In the composition analysis, Mg, Ti and Cl were analyzed by ICP emission analysis using Optima 3000 (manufactured by Perkin Elmer), and alcohol was analyzed by gas chromatograph GC-7A (manufactured by Shimadzu Corporation) (PEG 6000 10%, SHIMALITE TPA 60/80).
    Example 1
    (1) Synthesis of Solid Catalyst Component Precursor (C)
    The internal volume of 500 ml flask with stirrer and dropping funnel was replaced with nitrogen, followed by 160 ml of hexane, 44 ml (196.4 mol) of tetraethoxysilane and 4.4 ml (12.9 mol) of tetra-n-butoxy Fill with titanium and stir the mixture at 30 ° C. for 30 minutes. Subsequently, 100 ml of n-butylmagnesium chloride (2.1 mol / l of di-n-butyl ether solution) was added dropwise to the dropping funnel over 1 hour while maintaining the temperature of the flask at 5 ° C. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour, further stirred at 20 ° C. for 1 hour, then filtered, washed three times with 200 ml of hexane and dried under vacuum to give 31.2 g of A brown solid product (solid catalyst component precursor (C)) is obtained.
    The resulting solid product contains 16.5 wt% Mg, 1.91 wt% Ti, 36.4 wt% OEt (ethoxy group) and 2.93 wt% OBu (butoxy group).
    (2) Synthesis of Solid Catalyst Component (I)
    The internal volume 50 ml flask with stirrer and dropping funnel was replaced with nitrogen, followed by 17.5 ml of toluene, 3.5 ml (31.9 mol) of TiCl 4 and 4.3 ml (16.0 mol) of diisobutylphthalate (hereafter DIBP). Abbreviated), and the mixture is stirred at 70 ° C. for 1 hour. An internal volume 100 ml flask equipped with a stirrer and a dropping funnel was replaced with nitrogen, followed by filling with 17.5 ml of toluene and 7.00 g of the solid catalyst component precursor (C) synthesized in the above step (1), and the mixture was heated to 70 ° C. After holding for 30 minutes at, it is filled with the whole mixture of previously prepared TiCl 4 and DIBP, and the resulting mixture is stirred at 95 ° C. for 3 hours. After stirring, the mixture is solid-liquid separated and washed three times with 35 ml of toluene at 95 ° C., to which 35 ml of toluene is added again. After heating to 70 ° C., 3.5 ml (31.9 mmol) TiCl 4 are added and the mixture is stirred at 95 ° C. for 1 hour. After stirring, solid-liquid separation is carried out, and the resulting solid is washed 7 times at 95 ° C. with 35 ml of toluene, twice with 35 ml of hexane at room temperature and dried under vacuum to give a good powdery solid. Obtain catalyst component (I).
    The resulting solid product contains 2.0 wt% Ti.
    (3) polymerization
    The internal volume 3 liter autoclave with stirrer was completely dried and the pressure was reduced to pressure, then charged with 1.2 kg / cm 2 (partial pressure) of hydrogen, 600 g butane and 150 g 1-butene and the mixture was Heat to 70 ° C. Ethylene is then added to make the partial pressure 6.0 kg / cm 2 . 5.7 mmol of triethylaluminum and 17.5 mg of solid catalyst component (I) obtained in the above procedure (2) are charged by argon pressurization and polymerization is initiated. The polymerization is then carried out at 70 ° C. for 3 hours while the ethylene is continuously fed to keep the total pressure constant.
    After the completion of the polymerization, the unreacted monomer is removed and 99 g of polymer having good powderiness is obtained. The polymer does not attach to the inner wall of the autoclave and to the stirrer at all.
    The amount of polymer produced (polymerization activity) per catalyst is 1900 g polymer / g solid catalyst component / hour. This polymer contains a small amount of SCB of 15.2, FR of 0.59, FRR of 23.0 and 4.7% by weight of CXS, ie low molecular weight components.
    Example 2
    (1) Synthesis of Solid Catalyst Component (I)
    Synthesis was carried out in the same manner as in Example 1 (2), except that 2.3 ml (8.6 mmol) of di-n-butyl phthalate (hereinafter referred to as DNBP) as the ester compound was used instead of DIBP. Good solid catalyst component (I) is obtained.
    The resulting solid product contains 3.5 wt% Ti.
    (2) polymerization
    The polymerization was carried out in the same manner as in Example 1 (3) using the solid catalyst component obtained in the above step (1) to obtain a polymer having excellent powderability. The polymer does not attach to the inner wall of the autoclave and to the stirrer at all.
    The polymerization activity is 1400 g polymer / g solid catalyst component / hour. This polymer contains a small amount of SCB of 13.3, FR of 0.49, FRR of 28.6 and 4.1% by weight of CXS, ie low molecular weight components.
    Example 3
    (1) Synthesis of Solid Catalyst Component (I)
    Synthesis was carried out in the same manner as in Example 1 (2), except that 2.6 ml (11.2 mmol) of diisopropyl phthalate (hereinafter, abbreviated as DIPP) was used as the ester compound, thereby obtaining a solid having excellent powderability. Obtain catalyst component (I).
    The resulting solid product contains 4.7 wt% Ti.
    (2) polymerization
    The polymerization was carried out in the same manner as in Example 1 (3) using the solid catalyst component obtained in the above step (1) to obtain a polymer having excellent powderability. The polymer does not attach to the inner wall of the autoclave and to the stirrer at all.
    The polymerization activity is 2600 g polymer / g solid catalyst component / hour. This polymer contains a small amount of SCB of 19.5, FR of 0.47, FRR of 19.8 and 8.8% by weight of CXS, ie low molecular weight components.
    Example 4
    (1) Synthesis of Solid Catalyst Component (I)
    Synthesis was carried out in the same manner as in Example 1 (2), except that 2.2 ml (9.6 mmol) of di-n-propyl phthalate (hereinafter abbreviated as DNPP) was used as an ester compound, Good solid catalyst component (I) is obtained.
    The resulting solid product contains 2.6 wt% Ti.
    (2) polymerization
    The polymerization was carried out in the same manner as in Example 1 (3) using the solid catalyst component obtained in the above step (1) to obtain a polymer having excellent powderability. The polymer does not attach to the inner wall of the autoclave and to the stirrer at all.
    The polymerization activity is 2100 g polymer / g solid catalyst component / hour. This polymer contains a small amount of SCB of 17.3, FR of 0.74, FRR of 24.7 and 7.2% by weight of CXS, ie low molecular weight components.
    Example 5
    (1) Synthesis of Solid Catalyst Component (I)
    Synthesis was carried out in the same manner as in Example 1 (2), except that 3.8 ml (9.6 mmol) of di (2-ethylhexyl) phthalate (hereinafter abbreviated as DEHP) were used as the ester compound, A solid catalyst component (I) having good properties is obtained.
    The resulting solid product contains 1.6 wt% Ti.
    (2) polymerization
    The polymerization was carried out in the same manner as in Example 1 (3) using the solid catalyst component obtained in the above step (1) to obtain a polymer having excellent powderability. The polymer does not attach to the inner wall of the autoclave and to the stirrer at all.
    The polymerization activity is 3500 g polymer / g solid catalyst component / hour. This polymer contains a small amount of SCB of 18.7, FR of 0.75, FRR of 27.6 and 6.2% by weight of CXS, ie low molecular weight components.
    Example 6
    (1) Synthesis of Solid Catalyst Component Precursor (C)
    An internal volume of 1000 ml flask equipped with a stirrer and a dropping funnel was replaced with nitrogen, and then dried at 80 ° C. for 5 hours at 51.0 g of styrene-divinylbenzene copolymer (average particle size of 37 μm and pore radius of 100 to The pore volume in the range of 5000 kPa is 1.05 cc / g), 250 ml heptane, 47.5 ml (228 mmol) tetraethoxysilane and 4.5 g (13.2 mmol) tetra-n-butoxytitanium, The mixture is stirred at 30 ° C. for 30 minutes.
    Subsequently, 114 ml of n-butylmagnesium chloride (2.1 mol / l of di-n-butyl ether solution) is added dropwise to the dropping funnel over 1 hour while maintaining the temperature of the flask at 5 ° C. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour, further stirred at 20 ° C. for 1 hour, then filtered, washed three times with 300 ml of hexane and dried under vacuum to give 85.2 g of brown color. A solid product (solid catalyst component precursor (C)) is obtained.
    The resulting solid product contains 5.9 wt% Mg, 0.42 wt% Ti, 9.8 wt% OEt and 0.6 wt% OBu.
    (2) Synthesis of Solid Catalyst Component (I)
    The internal volume 50 ml flask with stirrer and dropping funnel was replaced with nitrogen and then charged with 15.0 ml toluene, 1.5 ml (13.7 mmol) TiCl 4 and 0.94 ml (3.5 mmol) DIBP and the mixture was 70 Stir at 1 ° C. for 1 h. An internal volume 100 ml flask equipped with a stirrer and a dropping funnel was replaced with nitrogen, followed by filling with 30 ml of toluene and 7.80 g of the solid catalyst component precursor (C) synthesized in the above procedure (1), and the mixture was 70 After 30 min of treatment at C, it is filled with the entire mixture of TiCl 4 and DIBP prepared before, and the resulting mixture is stirred at 95 C for 3 hours. After stirring, solid-liquid separation is carried out, washed three times with 44 ml of toluene at 95 ° C., to which 44 ml of toluene is added again. After heating to 70 ° C., 4.4 ml (40 mmol) TiCl 4 are added and the mixture is stirred at 95 ° C. for 1 hour. After stirring, solid-liquid separation was carried out, washed 7 times with 44 ml of toluene at 95 ° C., twice with 44 ml of hexane at room temperature, and dried under vacuum to give a good powdery solid catalyst component (I) To obtain.
    The resulting solid product contains 0.77 wt% Ti.
    (3) polymerization
    Using the solid catalyst component obtained in the above step (2), polymerization was carried out in the same manner as in Example 1 (3) to obtain a polymer having excellent powderability. The polymer does not attach to the inner wall of the autoclave and to the stirrer at all.
    The polymerization activity is 1500 g polymer / g solid catalyst component / hour. This polymer contains a small amount of SCB of 17.0, FR of 0.94, FRR of 24.6 and 6.9% by weight of CXS, ie low molecular weight components.
    Comparative Example 1
    (1) Synthesis of Solid Catalyst Components
    An internal volume 500 ml flask with a stirrer is charged with 175 ml (1.27 mol Mg / l) heptane solution of n-butylethylmagnesium, and 75 g of tetrachlorosilane is added dropwise at room temperature. After dropping, the mixture is stirred at 60 ° C. for 2 hours, filtered, washed 7 times with 100 ml of heptane and dried under vacuum to give 18.0 g of white solid product.
    An internal volume 200 ml flask with a stirrer is charged with 1.82 g of a pre-prepared solid product and the mixture is slurried with 94 ml of heptane. To this was added 0.95 ml of TiCl 4 at room temperature and the resulting mixture was stirred at 90 ° C. for 1 hour, filtered, washed 5 times with 94 ml of heptane and dried under vacuum to give 1.66 g of solid product. .
    The resulting solid product contains 6.30 wt% Ti.
    (2) polymerization
    The 3 liter volumetric autoclave with stirrer was completely dried and the pressure was reduced in vacuo followed by filling with 1.0 kg / cm 2 (partial pressure) of hydrogen, 650 g butane and 100 g 1-butene, The mixture is heated to 70 ° C. Ethylene is then added to make the partial pressure 6.0 kg / cm 2 . 5.7 mmol of triethylaluminum and 14.2 mg of solid catalyst component (I) obtained in the above procedure (1) are charged by argon pressurization and polymerization is initiated. Subsequently, the polymerization is carried out at 70 ° C. for 2 hours while the ethylene is continuously supplied to keep the total pressure constant.
    After completion of the polymerization, the unreacted monomer is removed and 136 g of polymer are obtained.
    The polymerization activity is 4800 g polymer / g solid catalyst component / hour. This polymer has a SCB of 11.5, a FR of 0.56, a FRR of 34.6 and a CXS of 5.1% by weight, ie even if the content of α-olefins (SCB) is low, the content of CXS is high.
    Comparative Example 2
    The polymerization was carried out in the same manner as in Comparative Example 1 (2), except that 630 g of butane and 120 g of 1-butene were charged into the autoclave using the solid catalyst component obtained in Comparative Example 1 (1). do.
    The polymerization activity is 5200 g polymer / g solid catalyst component / hour. This polymer has an SCB of 16.3, an FR of 0.83, an FRR of 34.4 and 9.0 wt% of CXS, that is, even if the content of α-olefin (SCB) is low, the content of CXS is high.
    Comparative Example 3
    The polymerization was carried out in the same manner as in Comparative Example 1 (2), except that 610 g butane and 140 g 1-butene were charged into the autoclave using the solid catalyst component obtained in Comparative Example 1 (1). do.
    The polymerization activity is 5400 g polymer / g solid catalyst component / hour. This polymer has an SCB of 18.7, an FR of 0.86, an FRR of 34.0 and a 10.9% by weight of CXS, ie, a low content of α-olefin (SCB), but a high CXS content.
    Comparative Example 4
    (1) Synthesis of Solid Catalyst Components
    An internal volume 100 ml flask equipped with a stirrer and a dropping funnel was replaced with nitrogen, followed by filling with 35 ml of toluene and 7.00 g of the solid catalyst component precursor (C) synthesized in Example 1 (1), and the mixture was After treatment at 70 ° C. for 30 minutes, then 3.5 ml (31.9 mmol) of TiCl 4 are charged, the mixture is stirred for 2 hours, solid-liquid separation is performed and then at 95 ° C. with 35 ml of toluene 3 Wash twice and add 30.8 ml of toluene to it again. 4.2 ml (16.0 mmol) of DIBP are then added, the mixture is stirred at 95 ° C. for 1 hour, then solid-liquid separation is performed, washed three times at 95 ° C. with 35 ml of toluene, and 35.0 ml Toluene is added again. After heating to 70 ° C., 3.5 ml (31.9 mmol) TiCl 4 are added and the mixture is stirred at 95 ° C. for 1 hour. After stirring, solid-liquid separation is carried out, washed 7 times at 95 ° C. with 35 ml of toluene and twice at room temperature with 35 ml of hexane and dried under vacuum to give a solid catalyst component.
    The resulting solid product contains 4.1 wt% Ti.
    (2) polymerization
    The polymerization was carried out in the same manner as in Comparative Example 1 (3) using the solid catalyst component obtained in the above step (1).
    The polymerization activity is 7000 g polymer / g solid catalyst component / hour. This polymer has a SCB of 20.1, FR of 1.04, FRR of 26.0 and 10.9% by weight of CXS, that is, even if the content of α-olefin (SCB) is low, the content of CXS is high.
    Comparative Example 5
    (1) Synthesis of Solid Catalyst Components
    An internal volume 500 ml flask with stirrer and dropping funnel was replaced with nitrogen, followed by filling with 346 ml of toluene and 67.2 g of solid catalyst component precursor (C) synthesized in Example 1 (1), and the mixture was Heat to 95 ° C. Then 45 ml (168 mmol) of DIBP are added, the mixture is stirred for 30 minutes, then solid-liquid separation is performed and washed twice with 340 ml of toluene at 95 ° C., where 87 ml of toluene is added. Try again. Then it was charged with a mixture of 6.7 ml (39.3 mmol) di-n-butyl ether, 3.8 ml (14.2 mmol) DIBP and 134.4 ml (1.23 mmol) TiCl 4, the mixture was stirred at 95 ° C. for 3 hours and , Solid-liquid separation is performed, followed by washing twice with 340 ml of toluene at 95 ° C., to which 68 ml of toluene is added again. Subsequently, it was filled with a mixture of 6.7 ml (39.3 mmol) of di-n-butyl ether and 67.2 ml (612 mmol) of TiCl 4 , and the resulting mixture was stirred at 95 ° C. for 3 hours, followed by solid-liquid separation. It is performed, washed three times at 95 ° C. with 340 ml of toluene, two times at room temperature with 340 ml of hexane, and dried under vacuum to give a solid catalyst component.
    The resulting solid product contains 1.8 wt% Ti.
    (2) polymerization
    The polymerization was carried out in the same manner as in Example 1 (3), except that 600 g of butane and 100 g of 1-butene were charged into the autoclave using the solid catalyst component obtained in the above step (1). .
    The polymerization activity is 3500 g polymer / g solid catalyst component / hour. This polymer has a SCB of 20.8, a FR of 0.98, a FRR of 27.0 and a 12.9% by weight of CXS, i.e., even if the content of α-olefin (SCB) is low, the content of CXS is high.
    According to the present invention, there is provided a solid catalyst component for olefin polymerization having an excellent particle shape, and a catalyst for olefin polymerization composed of the catalyst component having a very high catalytic activity for the catalyst and eliminating the removal of catalyst residues. Thus, an olefin polymer having excellent particle properties and containing a small amount of a low molecular weight component can be produced.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] A titanium compound (A) and an ester compound (B) having a titanium-halogen bond or a mixture of a titanium compound (A) and an ester compound (B) having a titanium-halogen bond may be simultaneously used as a magnesium atom, a titanium atom and a hydrocarbyl. Solid catalyst component for olefin polymerization obtained by contact with a solid catalyst component precursor (C) containing an oxy group.
    [2" claim-type="Currently amended] A compound of formula Ti (OR 1 ) a X 4-a in which the solid catalyst component precursor (C) is an organomagnesium compound (3) in the presence of an organosilicon compound (1) having a Si-O bond Olefin polymerization, which is a solid product obtained by reducing the titanium compound (2) represented by R 1 represents a hydrocarbon group having C 1-20 , X represents a halogen atom, and a is a number satisfying 0a ≦ 4. Solid catalyst component.
    [3" claim-type="Currently amended] The compound Ti (OR 1 ) a X according to claim 1, wherein the solid catalyst component precursor (C) is an organomagnesium compound (1) having a Si-O bond and an organomagnesium compound (3) in the presence of a porous carrier (4). Obtained by reducing the titanium compound (2) represented by 4-a (wherein R 1 represents a hydrocarbon group having C 1-20 , X represents a halogen atom and a is a number satisfying 0a ≦ 4) Solid catalyst component for olefin polymerization which is a solid product.
    [4" claim-type="Currently amended] 4. The solid catalyst component for olefin polymerization according to claim 3, wherein the porous carrier (4) is an organic porous polymer.
    [5" claim-type="Currently amended] The solid catalyst component for olefin polymerization according to claim 1, wherein the ester compound (B) is an unsaturated aliphatic carboxylic acid ester or an aromatic carboxylic acid ester.
    [6" claim-type="Currently amended] The catalyst for olefin polymerization which consists of a catalyst component (I) for olefin polymerization of Claim 1, and an organoaluminum compound (II).
    [7" claim-type="Currently amended] A process for producing an olefin polymer comprising polymerizing olefins using the catalyst for olefin polymerization of claim 7.
    [8" claim-type="Currently amended] The method for producing an olefin polymer according to claim 7, wherein the olefin polymer is a copolymer of ethylene and at least one α-olefin having 3 or more carbon atoms.
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    同族专利:
    公开号 | 公开日
    CN1218814A|1999-06-09|
    JPH1180234A|1999-03-26|
    DE19839822A1|1999-03-04|
    US20010021687A1|2001-09-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-09-02|Priority to JP23676597A
    1997-09-02|Priority to JP97-236765
    1998-08-31|Application filed by 고사이 아끼오, 스미또모 가가꾸 고오교오 가부시끼가이샤
    1999-04-26|Publication of KR19990029380A
    优先权:
    申请号 | 申请日 | 专利标题
    JP23676597A|JPH1180234A|1997-09-02|1997-09-02|Solid catalyst component for olefin polymerization, olefin polymerization catalyst, and production of olefin polymer|
    JP97-236765|1997-09-02|
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