JP2010275382A - Method for producing propylene single polymer or propylene random copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily produce a propylene single polymer or a propylene random copolymer excellent in the balance of melt tension and fluidity. <P>SOLUTION: The method for producing a propylene single polymer or a propylene random copolymer comprises single polymerization of propylene or copolymerization of propylene with olefin (excluding propylene) in the presence of a solid catalyst that is obtained by bringing a solid catalyst component (A) containing a titanium atom, a magnesium atom and a halogen atom as essential components into contact with an organic aluminum compound (B) and an electron donor (C). The method is characterized in that: a hydrogenation catalyst (D) is further added while the residual polymerization activity of the solid catalyst is 5 to 45%; and the propylene single polymer or the propylene random copolymer shows a melt flow rate (MFR) of 1 to 20 (g/10 min) (measured in accordance with JIS K7210 at 230°C under a load of 2.16 Kgf). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a propylene homopolymer or a propylene random copolymer. More specifically, the present invention relates to a method for easily producing a propylene homopolymer or a propylene random copolymer having a high melt tension using a solid catalyst component and a hydrogenation catalyst.

Propylene homopolymers or propylene random copolymers are excellent in rigidity, transparency, heat resistance, chemical resistance, and the like, and are widely used in various molding fields. However, since melt tension is low, further improvement of melt tension has been desired for application to blow molding, sheet molding, laminate molding, foam molding, and the like. Generally, it is known that if the fluidity (MFR) of a propylene homopolymer or a propylene-based random copolymer is reduced, the melt tension increases. There is a unique MFR region. Therefore, it has been required to obtain a propylene homopolymer or a propylene random copolymer having an MFR optimum for each application and having a high melt tension.
On the other hand, a method for producing polypropylene using a solid catalyst component and a hydrogenation catalyst is known. For example, a method using a hydrogenation catalyst as one component of a solid catalyst component is known (see Patent Documents 1 to 4). In addition, a method for producing polypropylene by adding a hydrogenation catalyst at an initial stage of polymerization using a solid catalyst component is also known (see Patent Documents 5 to 7). Furthermore, a method for producing a polypropylene having a specific structure by coexisting a hydrogenation catalyst in the final stage in multistage polymerization is also known (see Patent Document 8).
However, the methods described in Patent Documents 1 to 7 use a hydrogenation catalyst as one component of the solid catalyst component or add it at the initial stage of polymerization, so that the polymerization activity is significantly reduced, and the final product is used. There is a concern about high molecular weight that can not withstand. Moreover, since the method described in Patent Document 8 adds a hydrogenation catalyst to the final stage of multistage polymerization, this method cannot be used in a production facility having only a single-stage reaction tank.

JP 63-289003 A JP-A-3-70710 Japanese Patent Laid-Open No. 4-110308 JP-A-4-222804 Japanese Patent Application Laid-Open No. 3-91511 JP-A-8-151408 JP-A-10-251314 JP 2004-175976 A

  In view of such circumstances, an object of the present invention is to easily produce a propylene homopolymer or a propylene-based random copolymer having an excellent balance between melt tension and fluidity.

That is, the present invention comprises a solid catalyst component (A) having a titanium atom, a magnesium atom and a halogen atom as essential components;
An organoaluminum compound (B);
An electron donor (C);
In the presence of a solid catalyst obtained by contacting the propylene with a propylene homopolymer or a copolymer of propylene and an olefin (excluding propylene). When the residual polymerization activity of the solid catalyst is 5 to 45% (the final polymerization activity of the solid catalyst is 100%),
Further adding a hydrogenation catalyst (D),
The melt flow rate (MFR) (measured at a temperature of 230 ° C. and a load of 2.16 kgf according to JIS K7210) of the propylene homopolymer or the propylene random copolymer is 1 to 20 (g / 10 min). The present invention relates to the manufacturing method.

According to the present invention, a propylene homopolymer or a propylene-based random copolymer having an excellent balance between melt tension and fluidity can be easily produced.

  Hereinafter, embodiments of the present invention will be described in detail.

[Solid catalyst component (A)]
As the solid catalyst component (A) used in the present invention, a known polymerization catalyst used for olefin polymerization can be used, and a Ziegler-Natta catalyst (for example, JP-A 57-63310, JP-A 58- No. 83006, JP-A 61-78803, JP-A 7-216017, JP-A 10-212319, JP-A 62-158704, and JP-A 11-92518. ) Or metallocene catalysts (Japanese Patent Laid-Open No. 5-155930, Japanese Patent Laid-Open No. 9-143217, Japanese Patent Laid-Open No. 2002-293817, Japanese Patent Laid-Open No. 2003-171212, Japanese Patent Laid-Open No. 8-51044, Described in Japanese Laid-Open Patent Publication No. 2001-31720).

Examples of the method for preparing the solid catalyst component (A) containing a titanium atom, a magnesium atom, and a halogen atom include the following methods (1) to (5).
(1) A method of contacting a magnesium halide compound with a titanium compound.
(2) A method of contacting a magnesium halide compound, an electron donating compound, and a titanium compound.
(3) A method in which a magnesium halide compound and a titanium compound are dissolved in an electron donating solvent to obtain a solution, and then the carrier material is impregnated with the solution.
(4) A method of contacting a dialkoxymagnesium compound, a titanium halide compound, and an electron donating compound.
(5) A method of bringing a solid component containing a magnesium atom, a titanium atom and a hydrocarbon oxy group into contact with a halogenated compound, an electron donating compound and / or an organic acid halide.
Especially, the solid catalyst component obtained by the method of (5) is preferable, and it is more preferable that it is a solid catalyst component containing a phthalate ester compound as an electron donating compound.

When a metallocene catalyst is used as the olefin polymerization catalyst, the metallocene compound is preferably a metallocene compound represented by the following general formula [1].
_{Cp n MX 4-n [1} ]
Wherein Cp is a group selected from a substituted or unsubstituted cyclopentadienyl group, indenyl group or fluorenyl group, M is an element selected from zirconium and hafnium, X is a hydrogen atom, halogen atom, alkoxy group, amino A group selected from a group, an alkyl group having 1 to 10 carbon atoms, or an aryloxy group, and a plurality of Cp and X may be bonded to each other via a crosslinking group, and n represents an integer of 1 to 3).

[Organic aluminum compound (B)]
Examples of the organoaluminum compound (B) include trialkylaluminum, alkylaluminum halide, alkylaluminum hydride, aluminum alkoxide, alumoxane, and the like.

Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum.
Examples of the alkyl aluminum halide include diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, and the like.
Examples of the alkyl aluminum hydride include diethyl aluminum hydride, diisobutyl aluminum hydride and the like.
Examples of the aluminum alkoxide include diethylaluminum ethoxide and diethylaluminum phenoxide.
Examples of the alumoxane include methylalumoxane, ethylalumoxane, isobutylalumoxane, methylisobutylalumoxane, and the like.
These may be used alone or in combination of two or more.

  Among these, trialkylaluminum is preferable and triethylaluminum is more preferable.

[Electron Donor (C)]
As the electron donor (C), a silicon compound represented by the following general formula [2] is preferably used.
R ¹ _r Si (OR ² ) _4-r [2]
(Wherein R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a hetero atom, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, and r , if there are a plurality .R ¹ is an integer of 0 to 3, when good .R ² be different even multiple R ¹ is the same each have multiple, each of the plurality of R ² are the same Or different.)

Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ¹ include a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Cycloalkyl group, a C1-C20 cycloalkenyl group, a C1-C20 aryl group, etc. are mentioned.

Examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
Examples of the branched alkyl group having 1 to 20 carbon atoms include isopropyl group, sec-butyl group, tert-butyl group, tert-amyl group and the like.
Examples of the cycloalkyl group having 1 to 20 carbon atoms include a cyclopentyl group and a cyclohexyl group.
As a C1-C20 cycloalkenyl group, a cyclopentenyl group etc. are mentioned, for example.
Examples of the aryl group having 1 to 20 carbon atoms include a phenyl group and a tolyl group.

Examples of the group containing a hetero atom of R ¹ include a group containing an oxygen atom, a group containing a nitrogen atom, a group containing a sulfur atom, and a group containing a phosphorus atom. Specifically, dialkylamino groups such as dimethylamino group, methylethylamino group, diethylamino group, ethyl n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydro Indolyl group, perhydroisoindolyl group, perhydroquinolyl group, perhydroisoquinolyl group, perhydrocarbazolyl group, perhydroacridinyl group, furyl group, pyranyl group, perhydrofuryl group, thienyl group Among these, a substituent in which a hetero atom can be directly chemically bonded to a silicon atom of an alkoxysilicon compound is preferable.

Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ² include the same groups as those exemplified as the hydrocarbon group having 1 to 20 carbon atoms of R ¹ .

Preferable specific examples of the electron donor (C) include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyl. Dimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxy Silane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutyliso Tildimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl Isopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane , Phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butyl Ethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyl Diethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyl diet Xysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino ) (Perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane , (Perhydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimeth Shishiran, or (perhydroisoquinolino) (tert-butyl) dimethoxysilane include diethylamino triethoxy silane.
These may be used alone or in combination of two or more.

[Hydrogenation catalyst (D)]
The hydrogenation catalyst (D) is a catalyst having the ability to selectively hydrogenate olefinically unsaturated double bonds. Hydrogen present in the gas phase reactor reacts with olefins such as propylene and ethylene, and is removed as propane and ethane. Examples of the hydrogenation catalyst include known hydrogenation catalysts. For example, a compound containing a titanium atom, a platinum atom, a palladium atom, a palladium atom-chromium atom, a nickel atom, a ruthenium atom, specifically, (a) the metal, (b) an oxide of the metal, (c) Examples of the metal halide include (d) compounds obtained by supporting (i), (b), and (c) above on a porous carrier such as silica and alumina.

  Examples of the compound containing a nickel atom include bis (1,5-cyclooctadiene) nickel, bis (cyclopentadienyl) nickel, tetrakis (diethylphenylphosphonite) nickel, tetrakis (methyldiphenylphosphine) nickel, Examples include tetrakis (trifluorophosphine) nickel.

  Examples of the compound containing a titanium atom include a titanocene compound having at least one selected from the group consisting of a cyclopentadienyl group, an indenyl group, a fluorenyl group and derivatives thereof, a dialkylamino group, an alkoxy group, a phenoxy group. Group, aryloxy group, thioalkoxy group, thioaryloxy group, alkylamino group, arylamino group, alkylphosphino group, arylphosphino group, group represented by general formula [3] below, general formula [4 And a non-titanocene compound having at least one selected from the group consisting of derivatives thereof as a ligand.

R ³ ₃ P = N− [3]
(Wherein, R ³ represents a hydrogen atom, a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group, an amino group, three R ³ is optionally substituted by one or more identical to each other Or two or more of them may be bonded to each other and may form a ring.)

[４］




（式中、Ｒ⁴は、水素原子、ハロゲン原子、炭化水素基を表し、複数のＲ⁴は互いに同じであっても異なっていても良く、それら２つ以上が互いに結合していても良く、環を形成していても良い。）

[4]




(Wherein R ⁴ represents a hydrogen atom, a halogen atom, or a hydrocarbon group, and a plurality of R ⁴ may be the same or different from each other, and two or more of them may be bonded to each other; A ring may be formed.)

Examples of the compounds in which the above (a), (b), (c) and the like are supported on a porous carrier such as silica and alumina include, for example, Pd / Al ₂ O ₃ , Pd / SiO ₂ .Al ₂ O ₃ , Pd / SiO ₂ , Pt / Al ₂ O ₃ , and the like.

Among these, titanocene compounds are preferable. Examples of the titanocene compound include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) titanium fluoride, Bis (cyclopentadienyl) titanium chlorobromide, bis (cyclopentadienyl) titanium methoxy chloride, bis (cyclopentadienyl) titanium ethoxy chloride, bis (cyclopentadienyl) titanium phenoxychloride, bis (cyclopentadienyl) ) Titanium dimethoxide and the like.

  The hydrogenation catalyst (D) is preferably in a liquid or solvent-soluble state.

  The hydrogenation catalyst (D) can also be used in combination with a reducing agent. Examples of the reducing agent include organoaluminum compounds (B), organolithium compounds, organomagnesium compounds, and organozinc compounds. Among these, it is preferable to use in combination with the organoaluminum compound (B).

  The hydrogenation catalyst (D) is polymerized when the residual polymerization activity of the solid catalyst obtained by contacting the solid catalyst component (A), the organoaluminum compound (B) and the electron donor (C) is 5 to 45%. Is added to the system (the final polymerization activity of the solid catalyst is 100%). It is preferably added when the residual polymerization activity is 17 to 45%, more preferably when it is 17 to 43%.

The polymerization activity here is a value obtained by dividing the weight (g) of the produced propylene homopolymer or propylene random copolymer by the weight (g) of the solid catalyst component (A) used. Moreover, the residual polymerization activity of the solid catalyst at the time of hydrogenation catalyst (D) addition can be calculated | required as follows. The polymerization activity (I) is the polymerization activity of the solid catalyst when the hydrogenation catalyst (D) is added. The final polymerization activity is the polymerization activity of the solid catalyst when the hydrogenation catalyst (D) is added to complete the polymerization.
Residual polymerization activity (%) of solid catalyst upon addition of hydrogenation catalyst (D)
= (Final polymerization activity-polymerization activity (I)) / final polymerization activity × 100
Polymerization activity (I) at the time of hydrogenation catalyst (D) addition is polymerization activity at the time of hydrogenation catalyst (D) addition (I) = polymer production amount at the time of hydrogenation catalyst (D) addition (I) × final polymerization activity / 100.

The ratio of the number of moles of Al atoms contained in the reducing agent, especially the organoaluminum compound (B), and the number of moles of Ti atoms contained in the hydrogenation catalyst (D), particularly the titanocene compound (Ti / Al (mol / mol)) is 0.1 to 2.0, more preferably 0.15 to 1.8, and still more preferably 0.2 to 1.5.
When the Ti / Al molar ratio is less than 0.1, a sufficient hydrogen removal effect cannot be obtained, so that the desired high molecular weight product is not produced, and the resulting propylene homopolymer or propylene random copolymer melt tension. May be low. In addition, when the Ti / Al molar ratio exceeds 2.0, the polymerization activity is drastically decreased after the addition of the hydrogenation catalyst (D), and the desired high molecular weight component ratio is not generated, and the resulting propylene homopolymer Alternatively, the melt tension of the propylene random copolymer may be low.

  The hydrogenation catalyst (D) can be fed after being diluted with an inert organic solvent. At this time, the hydrogenation catalyst (D) may be previously contacted with a reducing agent. The above-mentioned inert organic solvent means that the solvent does not react with any participant in the hydrogenation reaction. Suitable solvents include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane and isomers thereof, and alicyclic hydrocarbons such as cyclohexane and cycloheptane, and derivatives thereof.

  The hydrogenation catalyst (D) used in the present invention preferably contains a titanocene compound, more preferably a compound obtained by bringing a titanocene compound and a reducing agent into contact, and the titanocene compound and the organoaluminum compound (B). More preferably, it is a compound obtained by contacting

The production method of the present invention is a method for producing a propylene homopolymer or a propylene random copolymer. Examples of olefins other than propylene used in the present invention include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene. Styrene, butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like, which are determined depending on the type of the desired polymer product. In the case of multistage polymerization, the same polymer may be produced at each stage, or polymers having different compositions may be produced.

The melt flow rate (MFR, JIS K7210, temperature 230 ° C., load 2.16 Kgf) of the propylene homopolymer or propylene random copolymer is 1 to 20 g / 10 min, preferably 1.5 to 15 g / 10 min. More preferably, it is in the range of 2 to 13 g / 10 min. Even if the melt flow rate is less than 1 g / 10 min or greater than 20 g / 10 min, moldability such as sheet molding, blow molding, foam molding, etc. is deteriorated.

The propylene homopolymer or the propylene random copolymer preferably has a bimodal molecular weight distribution curve measured by gel permeation chromatography (GPC). A bimodal molecular weight distribution curve means that the molecular weight distribution curve shows two maximum values or one maximum value and a broad shoulder. The ratio (Aw / An) of the weight average molecular chain length (Aw) to the number average molecular chain length (An) of the propylene homopolymer or propylene random copolymer of the present invention is preferably 17 to 35. More preferably, it is 18-33, More preferably, it is 19-31. When Aw / An is less than 17, the desired melt tension cannot be obtained. When Aw / An is greater than 35, the spread of the molecular weight distribution to the low molecular weight region often increases, and the melt flow rate (MFR) increases and the processing is increased. Sex worsens. The average molecular chain length is a value obtained by dividing the average molecular weight by a Q factor (a value obtained by dividing the molecular weight per monomer unit of the polymer by the extended chain length of the monomer unit).

The component produced after addition of the hydrogenation catalyst (D) in the propylene homopolymer or propylene random copolymer has an intrinsic viscosity [η] measured in 135 ° C. tetralin of 5.5 to 10 dl / g, preferably 5.8 to 9.0 dl / g, more preferably 6.0 to 8.5 dl / g, and the component is 15 to 65% by weight, preferably 17 to 63% by weight, more preferably 19 to 62% by weight. % (Propylene homopolymer or propylene random copolymer is 100% by weight).

  The production method of the present invention can be applied to both batch polymerization processes and continuous polymerization processes. For example, when a metallocene catalyst is used as a catalyst for propylene polymerization, the resulting olefin polymer is often obtained as having an unsaturated bond at the end. Therefore, it is possible that such hydrogen is gradually concentrated in the circulating olefin. Therefore, in such a case, the present invention can be applied as a technique for controlling the hydrogen concentration in a single-stage polymerization process.

  In addition, the production method of the present invention may be necessary even in multistage polymerization having a plurality of polymerization steps with different polymerization conditions. In the multistage polymerization, the polymerization may be performed by changing the polymerization conditions in one reactor, or the polymerization may be performed in a plurality of reactors connected in series with different polymerization conditions. When the downstream hydrogen concentration in one reactor is lower than that in the previous stage efficiently, or in multi-stage polymerization in multiple reactors, the hydrogen flowing together with the powder from the previous reactor into the subsequent reactor is efficiently The present invention can be applied to reduce this.

  Although the polymerization temperature varies depending on the type of monomer, the molecular weight of the product, etc., it is not higher than the melting point of the olefin polymer, preferably 10 ° C. or more lower than the melting point, more preferably room temperature to about 200 ° C., particularly preferably about 40 to 160 ° C. Most preferably, it is about 60-130 degreeC. In order to maintain the polymerization temperature within this range, the polymerization system is cooled by a cooler. In addition, the polymerization pressure is about atmospheric pressure to about 15 MPa, preferably about 0.2 to 7 MPa, and most preferably about 1 to 5 MPa.

  In the present invention, when applied to multistage polymerization, it is preferable that the hydrogen concentration in the gas phase part in the previous stage is 30% or less. Even if the hydrogen concentration is higher than 30%, there is no particular problem in carrying out the production method of the present invention. However, olefin hydride (propane, ethane) produced in the gas phase reactor by a large amount of hydrogen brought into the subsequent stage. Etc.) and the polymerization activity in the latter stage is lowered, so that it is not preferable that the concentration is too high.

  Prior to the polymerization step, a small amount of olefin may be polymerized (hereinafter referred to as prepolymerization) and used as a prepolymerization catalyst component. Examples of the prepolymerized olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, styrene, Examples include butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like. The amount of olefin to be prepolymerized is usually 0.1 to 200 g per gram of the solid catalyst component (A). Examples of the prepolymerization method include known methods. For example, the solid catalyst component (A) ) And the organoaluminum compound (B), and a method of supplying a small amount of olefin and using a solvent in a slurry state. Examples of the solvent used for the prepolymerization include inert saturated hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene, and liquid olefins. You may mix and use. The slurry concentration in the prepolymerization is usually 1 to 500 g, preferably 3 to 150 g, as the weight of the catalyst component contained per 1 L of the solvent.

  The amount of the organoaluminum compound (B) used in the prepolymerization is 0.1 to 700 mol, preferably 0.2 to 200 mol, per mol of transition metal atoms contained in the solid catalyst component (A). Preferably it is 0.2-100 mol. In the prepolymerization, an electron donor (C) such as an alkoxysilicon compound may coexist if necessary, and the amount of the electron donor (C) used is the transition metal atom 1 contained in the solid catalyst component (A). Preferably it is 0.01-400 mol per mol, More preferably, it is 0.02-200 mol, More preferably, it is 0.03-100 mol.

  The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. The prepolymerization time is usually 2 minutes to 15 hours.

The propylene homopolymer or propylene-based random copolymer obtained by the polymerization method of propylene, which is the production method of the present invention, is excellent in the balance between melt tension and fluidity, so that it does not impair excellent mechanical properties and processability. Is good. This excellent characteristic makes it particularly suitable for films, sheets, fibers, pipes, foams, hollow products and the like.

Hereinafter, the present invention will be described with reference to examples and comparative examples. The structure of the propylene homopolymer or the propylene random copolymer was measured and evaluated by the following method.
(1) Melt flow rate (MFR, unit: g / 10 minutes)
According to JIS K7210, the measurement was performed at a temperature of 230 ° C. and a load of 2.16 Kgf.
(2) Melt tension (MT, unit: g)
Measurement was performed under the following conditions using a melt tension measuring machine manufactured by Toyo Seiki Co., Ltd.
Orifice: L / D = 4 (D = 2mm)
Preheating: 10 minutes Measurement temperature: 190 ° C
Extrusion speed: 5.7 mm / min Drawing speed: 100 rpm
(3) Intrinsic viscosity ([η], unit: dl / g)
The measurement was performed in 135 ° C. tetralin using an Ubbelohde viscometer.
(4) Weight average molecular chain length (Aw) and number average molecular chain length (An)
Tosoh HLC8121GPC / HT GPC (gel permeation chromatography) was used under the following conditions.
Measurement temperature: 152 ° C
Solvent: Orthodichlorobenzene Solvent flow rate: 1 ml / min Column: TSKgel GMHHR-H (20) / HT × 3
Solution concentration: sample 5 mg / orthodichlorobenzene 5 ml
The average molecular chain length is a value obtained by dividing the average molecular weight by a Q factor (a value obtained by dividing the molecular weight per monomer unit of the polymer by the extended chain length of the monomer unit).
(5) Residual polymerization activity (%) of solid catalyst upon addition of hydrogenation catalyst (D)
It calculated | required by the following calculation formula (1). The polymerization activity (I) is the polymerization activity of the solid catalyst when the hydrogenation catalyst (D) is added.
(Final polymerization activity-polymerization activity (I)) / final polymerization activity × 100 Formula (1)
(6) Intrinsic viscosity ([η], unit: dl / g) of the component produced after addition of the hydrogenation catalyst (D)
It calculated | required by the following formula (2)-(4).
-Polymer production ratio (I) (wt%) at the time of hydrogenation catalyst (D) addition =
Polymerization activity when adding hydrogenation catalyst (D) (I) / final polymerization activity × 100 Formula (2)
-Polymer production rate after addition of hydrogenation catalyst (D) (II) (wt%) =
100- (I) ... Formula (3)
-Intrinsic viscosity of the component produced after addition of the hydrogenation catalyst (D) =
([Η] of final product− [η] × (I) / 100 of product before addition of hydrogenation catalyst (D))
) / ((II) / 100) (4)
Example 1

(1) Preparation of titanocene compound solution A flask with an internal volume of 100 mL was replaced with nitrogen. In this container, 40.2 μmol of dicyclopentadienyl titanium dichloride (manufactured by Kanto Chemical Co., Inc.) and 30 mL of heptane were added and stirred at room temperature, and 2.0 mmol of triethylaluminum was added to obtain a solution.

(2) Preparation of solid catalyst component (A) 800 L of hexane, 6.8 kg of diisobutyl phthalate, 350 kg of tetraethoxysilane and 38.8 kg of tetrabutoxytitanium were charged into a reactor equipped with a nitrogen-replaced stirrer and stirred. . Next, 900 L of a dibutyl ether solution of butyl magnesium chloride (concentration 2.1 mol / L) was dropped into the stirred mixture over 5 hours while maintaining the temperature of the reactor at 7 ° C. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 1 hour and then filtered. The obtained solid was repeatedly washed with 1100 L of toluene three times, and toluene was added so that the total volume of the slurry became 625 L. Then, the obtained slurry was heat-treated at 70 ° C. for 1 hour with stirring, and cooled to room temperature to obtain a solid substance slurry.
Composition analysis of a dry solid material obtained by drying a part of the slurry under reduced pressure revealed that the solid material was 2.1% by weight of titanium atoms, 38.9% by weight of ethoxy groups, and 3.3% of butoxy groups. 4% by weight (100% by weight of dry solid material). Moreover, the valence of the titanium atom in this solid substance was trivalent.

Process 1
After replacing a 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, the solid material slurry obtained above was charged in an amount containing 8 g of dry solid material, and the total volume of the slurry was 26.5 mL. The supernatant was withdrawn so that A mixture of titanium tetrachloride (16.0 mL) and dibutyl ether (0.8 mL) was added at 40 ° C., and a mixture of phthalic acid chloride (2.0 mL) and toluene (2.0 mL) was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction mixture was stirred at 115 ° C. for 4 hours. Thereafter, solid-liquid separation was performed at the same temperature to obtain a solid component.

Process 2
The solid component was washed 3 times with 40 mL of toluene at 115 ° C.
Process 3
Toluene was added to the washed solid component so that the volume of the slurry was 26.5 mL. Thereto was added a mixture of 0.8 mL of dibutyl ether, 0.45 mL of diisobutyl phthalate and 6.4 mL of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature to obtain a solid component.

Repeating Step 2 Repeating Step 3 in which the solid component was washed twice with 40 mL of toluene at 105 ° C. Toluene was added to the washed solid component so that the slurry volume was 26.5 mL to 105 ° C. . Thereto was added a mixture of dibutyl ether 0.8 mL and titanium tetrachloride 6.4 mL, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature to obtain a solid component.

Further repetition of step 2 The solid component was washed twice with 40 mL of toluene at 105 ° C.
Further repetition of step 3 To the washed solid component, toluene was added to 105 ° C. so that the slurry volume was 26.5 mL. Thereto was added a mixture of 0.8 mL of dibutyl ether and 6.4 mL of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature to obtain a solid component.

Process 4
The solid component was washed 6 times with 40 mL of toluene at 105 ° C. and 3 times with 40 mL of hexane at room temperature. This was dried under reduced pressure to obtain a solid catalyst component.

  In the solid catalyst component, titanium atom 1.6% by weight, ethoxy group 0.06% by weight, butoxy group 0.15% by weight, diethyl phthalate 7.6% by weight, ethyl normal butyl phthalate 0.8% by weight % And 2.5% by weight of diisobutyl phthalate were contained (the solid catalyst component was 100% by weight).

(3) Propylene polymerization After drying under reduced pressure, in a stainless steel autoclave with a stirrer having an internal volume of 3 liters substituted with argon and decompressed again, 4.4 mmol of triethylaluminum, 0.5 mmol of cyclohexylethyldimethoxysilane and (2) were prepared. After 7.0 mg of the solid catalyst component (A) was added, 1.77 MPa of hydrogen and 780 g of propylene were added, the autoclave internal temperature was raised to 70 ° C., and polymerization was performed for 20 minutes.
As a result of conducting the polymerization which is completed at this time in advance, the yield of propylene homopolymer per 1 g of the solid catalyst component (hereinafter referred to as PP / Cat) is 17,200 (g / g), and the obtained propylene homopolymer [Η] was 0.91 (dl / g).
After 20 minutes, half of the titanocene compound solution prepared in (1) was injected into the autoclave and polymerization was continued for 120 minutes. After completion of the polymerization, the unreacted monomer in the autoclave was purged, and the propylene homopolymer was recovered and dried under reduced pressure at 60 ° C. for 5 hours to obtain 196 g of propylene homopolymer powder. The polymerization results were PP / Cat = 28,000 (g / g) and [η] = 3.02 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Example 2
Polymerization similar to (3) of Example 1 was carried out except that the amount of the solid catalyst component (A) used was 5.2 mg, and the amount of the titanocene compound solution used was the total amount. 138 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 26,400 (g / g) and [η] = 3.25 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Example 3
Polymerization similar to (3) of Example 1 except that the amount of solid catalyst component (A) used was 6.4 mg, the amount of titanocene compound solution used was all, and the polymerization time after addition of the titanocene compound solution was 60 minutes. Went. 136 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 21,300 (g / g) and [η] = 2.26 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 1
Polymerization similar to (3) of Example 1 was carried out except that the amount of the solid catalyst component (A) used was 6.6 mg, and the amount of the titanocene compound solution used was 1/20. 266 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 40,400 (g / g) and [η] = 1.17 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 2
Polymerization similar to (3) of Example 1 was carried out except that the amount of the solid catalyst component (A) used was 5.7 mg and the amount of the titanocene compound solution was 1/10. 202 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 35,400 (g / g) and [η] = 1.76 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 3
Polymerization similar to (3) of Example 1 except that the amount of solid catalyst component (A) used was 7.1 mg, the amount of titanocene compound solution used was all, and the polymerization time after addition of the titanocene compound solution was 30 minutes. Went. 144 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 20,200 (g / g) and [η] = 1.53 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 4
The same as (3) of Example 1 except that the amount of the solid catalyst component (A) used was 9.3 mg, no titanocene compound solution was used, the amount of hydrogenation was 0.02 MPa, and the total polymerization time was 60 minutes. Polymerization was performed. 179 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 19,200 (g / g) and [η] = 3.30 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 5
The same as (3) of Example 1 except that the amount used of the solid catalyst component (A) was 10.0 mg, no titanocene compound solution was used, the amount of hydrogenation was 0.06 MPa, and the total polymerization time was 60 minutes. Polymerization was performed. 298 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 29,800 (g / g) and [η] = 2.13 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 6
The same as (3) of Example 1 except that the amount of the solid catalyst component (A) used was 9.1 mg, no titanocene compound solution was used, the amount of hydrogenation was 0.26 MPa, and the total polymerization time was 60 minutes. Polymerization was performed. 271 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 29,700 (g / g) and [η] = 1.53 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 7
The same as (3) of Example 1 except that the amount used of the solid catalyst component (A) was 8.2 mg, the amount of titanocene compound solution used was the total amount, added at the same time as the start of polymerization, and the total polymerization time was 140 minutes. Was polymerized. 161 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 19,600 (g / g) and [η] = 6.94 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 8
The same as (3) of Example 1 except that the amount of the solid catalyst component (A) used was 9.5 mg, the amount of the titanocene compound solution was the total amount, added at the same time as the start of polymerization, and the total polymerization time was 80 minutes. Was polymerized. 140 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 14,700 (g / g) and [η] = 6.25 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Comparative Example 9
Example 1 (3), except that the amount of solid catalyst component (A) used was 10.5 mg, the amount of titanocene compound solution used was the total amount, added at the same time as the start of polymerization, and the total polymerization time was 50 minutes. Was polymerized. 120 g of propylene homopolymer powder was obtained, and the polymerization results were PP / Cat = 11,500 (g / g) and [η] = 5.57 (dl / g). The polymerization results are shown in Table 1, and the structure of the propylene homopolymer is shown in Table 2.

Claims (4)

A solid catalyst component (A) having a titanium atom, a magnesium atom and a halogen atom as essential components;
An organoaluminum compound (B);
An electron donor (C);
In the presence of a solid catalyst obtained by contacting the propylene with a propylene homopolymer or a copolymer of propylene and an olefin (excluding propylene). When the residual polymerization activity of the solid catalyst is 5 to 45% (the final polymerization activity of the solid catalyst is 100%),
Further adding a hydrogenation catalyst (D),
The melt flow rate (MFR) (measured at a temperature of 230 ° C. and a load of 2.16 kgf according to JIS K7210) of the propylene homopolymer or the propylene random copolymer is 1 to 20 (g / 10 min). The manufacturing method characterized by the above-mentioned. The production method according to claim 1, wherein when the residual polymerization activity of the solid catalyst is 17 to 45% (the final polymerization activity of the solid catalyst is 100%), the hydrogenation catalyst (D) is further added. The hydrogenation catalyst (D) is a compound containing a titanium atom,
The ratio of the number of moles of Ti atoms contained in the hydrogenation catalyst (D) to the number of moles of Al atoms contained in the organoaluminum compound (B) (Ti / Al (mol / mol)) is 0.1-2. The production method according to claim 1 or 2, wherein the hydrogenation catalyst (D) is added so as to be in a range of 0.0. Propylene homopolymer or propylene random copolymer,
The molecular weight distribution curve measured by gel permeation chromatography (GPC) method is bimodal,
Aw / An is 17-35,
The intrinsic viscosity [η] of the component produced after the addition of the hydrogenation catalyst (D) is 5.5 to 10 dl / g, and the production rate thereof is 15 to 65% by weight.
The manufacturing method in any one of Claims 1-3.