Method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization and a process for propylene polymerization

Abstract

A method for producing a solid catalyst for olefin (co)polymerization includes bringing into contact with each other a magnesium compound, a tetravalent titanium halide compound, an organic compound represented the following general formula (1)
R.sup.1.sub.k(C.sub.6H.sub.4-k)(COOR.sup.2)(COOR.sup.3)(1) and
an organic compound represented the following general formula (2)
R.sup.4R.sup.5CC (COOR.sup.6)(COOR.sup.7)(2)
wherein R.sup.1 is a halogen atom or an alkyl group, R.sup.2 and R.sup.3 are a linear alkyl group, R.sup.4 and R.sup.5 are independently an atom or group selected from a hydrogen atom, halogen, a linear alkyl group, a branched alkyl group a vinyl group, a linear or branched alkenyl group, a cycloalkenyl group, an aromatic hydrocarbon group, and R.sup.6 and R.sup.7 are independently a linear alkyl group, a branched alkyl group, a vinyl group, a linear or branched alkenyl group a cycloalkyl group, a cycloalkenyl group, or an aromatic hydrocarbon group.

Claims

1. A method for producing an olefin polymerization catalyst component, the method comprising: bringing a magnesium compound, a tetravalent titanium halide compound, an organic compound represented the following general formula (1)
R.sup.1.sub.k(C.sub.6H.sub.4-k)(COOR.sup.2)(COOR.sup.3)(1) and an organic compound represented the following general formula (2)
R.sup.4R.sup.5CC(COOR.sup.6)(COOR.sup.7)(2) into contact with each other at the same step, wherein R.sup.1 is a halogen atom or an alkyl group having 1 to 8 carbon atoms, R.sup.2 and R.sup.3 are a linear alkyl group having 1 to 6 carbon atoms, provided that R.sup.2 and R.sup.3 are either identical or different, and k is an integer from 0 to 4, provided that a plurality of R.sup.1 are either identical or different when k is an integer from 2 to 4, and wherein R.sup.4 and R.sup.5 are independently an atom or group selected from a hydrogen atom, halogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 20 atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, provided that R.sup.4 and R.sup.5 optionally bond to each other to form a ring, and the number of carbon atoms of R.sup.5 is 2 or more when R.sup.4 is a hydrogen atom or a methyl group; and wherein R.sup.6 and R.sup.7 are independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 atoms.

2. A method for producing an olefin polymerization catalyst component according to the claim 1, the method comprising: a first step that brings a magnesium compound and a tetravalent titanium halide compound into contact with each other to make a reaction, followed by removing the reaction medium and optionally washing; a second step that brings a tetravalent titanium halide compound into contact with a product obtained by the first step to make a reaction, followed by removing the reaction medium and optionally washing; wherein compounds selected respectively from an organic compound represented by the following general formula (1) and an organic compound represented by the following general formula (2) are further added in at least either the first step and the second step.

3. A method for producing an olefin polymerization catalyst component according to the claim 2, the method further comprising: a third step that brings a an organic compound represented the following general formula (1) and an organic compound represented the following general formula (2) into contact with a product obtained by the second step to make a reaction, followed by removing the reaction medium and optionally washing.

4. An olefin polymerization catalyst includes (I) the solid catalyst component for olefin polymerization obtained by the method according to claim 1, (II) an organo aluminum compound represented by the following general formula (3),
R.sup.8.sub.pAlQ.sub.3-p(3) and (III) an external donor compound represented by the following general formula (4) or an external donor compound represented by the following general formula (5)
R.sup.9.sub.qSi(OR.sup.10).sub.4-q(4)
(R.sup.11R.sup.12N).sub.sSiR.sup.13.sub.4-s(5) wherein R.sup.8 is an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom or halogen atom; and p is an integer from 0 to 3; and wherein R.sup.9 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, provided that a plurality of R.sup.9 are either identical or different when a plurality of R.sup.9 are present; R.sup.10 is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, provided that a plurality of R.sup.10 are either identical or different when a plurality of R.sup.10 are present; and q is an integer from 0 to 3; R.sup.11 and R.sup.12 are a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, or an aralkyl group, a cycloalkyl group having 3 to 20 carbon atoms, or aryl group, provided that R.sup.11 and R.sup.12 are either identical or different, and optionally bond to each other to form a ring; R.sup.13 is a a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, or an aralkyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, or an aryloxy group, provided that a plurality of R.sup.13 are either identical or different when a plurality of R.sup.13 are present; and s is an integer from 0 to 3.

5. A process for propylene polymerization wherein propylene is contacted by a catalyst comprising the catalyst component according to claim 1, an organoaluminum compound, and an external electron donor compound.

Description

EXAMPLES

(1) The invention is further described below by way of examples. Note that the following examples are for illustration purposes only, and the invention is not limited to the following examples. In the examples and comparative examples, the sphericity of the dialkoxymagnesium particles, and the content of magnesium atoms, titanium atoms, halogen atoms, and the internal electron donor compound in the solid catalyst component were measured as described below.

(2) Content of Magnesium Atoms in Solid Catalyst Component

(3) The solid catalyst component from which the solvent component had been completely removed by heating (drying) under reduced pressure was weighed, and dissolved in a hydrochloric acid solution. After the addition of methyl orange (indicator) and a saturated ammonium chloride solution, the mixture was neutralized with aqueous ammonia, heated, cooled, and filtered to remove a precipitate (titanium hydroxide). A given amount of the filtrate was isolated preparatively, and heated. After the addition of a buffer and an EBT mixed indicator, magnesium atoms were titrated using an EDTA solution to determine the content of magnesium atoms in the solid catalyst component (EDTA titration method).

(4) Content of Titanium Atoms in Solid Catalyst Component

(5) The content of titanium atoms in the solid catalyst component was determined in accordance with the method (redox titration) specified in JIS M 8311-1997 (Method for determination of titanium in titanium ores).

(6) Content of Halogen Atoms in Solid Catalyst Component

(7) The solid catalyst component from which the solvent component had been completely removed by heating (drying) under reduced pressure was weighed, and treated with a mixture of sulfuric acid and purified water to obtain an aqueous solution. A given amount of the aqueous solution was isolated preparatively, and halogen atoms were titrated with a silver nitrate standard solution using an automatic titration device (COM-1500 manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content of halogen atoms in the solid catalyst component (silver nitrate titration method).

(8) Content of Internal Electron Donor Compound in Solid Catalyst Component

(9) The content of the internal electron donor compound (first internal electron donor compound, second internal electron donor compound, and third internal electron donor compound) in the solid catalyst component was determined using a gas chromatograph (GC-14B manufactured by Shimadzu Corporation) under the following conditions. The number of moles of each component (each internal electron donor compound) was calculated from the gas chromatography measurement results using a calibration curve that was drawn in advance using the measurement results at a known concentration.

(10) Measurement Conditions

(11) Column: packed column (2.6 (diameter)2.1 m, Silicone SE-30 10%, Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Ltd.) Detector: flame ionization detector (FID) Carrier gas: helium, flow rate: 40 ml/min Measurement temperature: vaporization chamber: 280 C., column: 225 C., detector: 280 C., or vaporization chamber: 265 C., column: 180 C., detector: 265 C.

Example 1

(12) Synthesis of Solid Catalyst Component (A1)

(13) (1) First Step

(14) A 500 ml round bottom flask equipped with a stirrer in which the internal atmosphere had been sufficiently replaced by nitrogen gas, was charged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565 mmol) of toluene to prepare a solution.

(15) A suspension prepared using 20 g (175 mmol) of spherical diethoxymagnesium (diameter=43 m), 80 ml (753 mmol) of toluene, and 4.0 ml (17.3 mmol) of di-n-propyl phthalate was added to the solution. The mixture was stirred at 5 C. for 1 hour, and heated to 110 C. 4.0 ml (17.2 mmol) of diethyl benzylidenemalonate was added stepwise to the mixture while heating the mixture. After reacting the mixture at 90 C. for 3 hours with stirring, the reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(16) After the addition of 187 ml of toluene (100 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated four times to wash the reaction product to obtain reaction product slurry including a solid component (I).

(17) (2) Second Step

(18) 170 ml of toluene and 30 ml (273 mmol) of titanium tetrachloride were added to the reaction product slurry including the solid component (I). The mixture was heated to 110 C., and reacted for 2 hours with stirring. After completion of the reaction, the supernatant liquid was removed. After the addition of 180 ml of toluene and 20 ml (182 mmol) of titanium tetrachloride, the mixture was heated to 80 C. After the addition of 0.5 ml (2.2 mmol) of di-n-propyl phthalate, the mixture was heated to 110 C., and reacted for 2 hours with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(19) After completion of the reaction, 187 ml of toluene (100 C.) was added to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated twice to wash the reaction product to obtain reaction product slurry including a solid component (II).

(20) (3) Third Step

(21) 170 ml (1600 mmol) of toluene was added to the reaction product slurry including the solid component (II) to adjust the concentration of titanium tetrachloride in the reaction mixture to 0.2 mass %, and the mixture was heated to 80 C. After the addition of 0.5 ml (2.2 mmol) of di-n-propyl phthalate, the mixture was reacted at 100 C. for 1 hour with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(22) After the addition of 150 ml of n-heptane (60 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 7 times to wash the reaction product to obtain a solid catalyst component (A1) for olefin polymerization.

(23) The solid catalyst component (A1) had a titanium atom content of 1.7 mass %, a total phthalic diester content of 14.6 mass %, and diethyl benzylidenemalonate content of 2.9 mass %.

(24) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(25) An autoclave (internal volume: 2.0 l) equipped with a stirrer in which the internal atmosphere had been completely replaced by nitrogen gas, was charged with 1.3 mmol of triethylaluminum, 0.22 mmol of diethylaminotriethoxysilane, and the solid catalyst component (A1) (2.6 mol on a titanium atom basis) to prepare a propylene polymerization catalyst (B1).

(26) The autoclave was charged with the propylene polymerization catalyst, and further charged with liquefied propylene (17 mol). The liquefied propylene was subjected to preliminary polymerization at 20 C. for 5 minutes under a pressure of 1.1 MPa, heated, and polymerized at 70 C. for 15 minutes under 3.2 MPa. Followed by addition of 5.5 l of hydrogen gas, the liquefied propylene was polymerized at 70 C. for 45 minutes under 3.2 MPa to obtain a polypropylene.

(27) The propylene polymerization activity per gram of the solid catalyst component, the melt flow rate (MFR) of the polymer, and the p-xylene-soluble content (XS) in the polymer were measured as described below. The results are shown in Table 1.

(28) Propylene Polymerization Activity

(29) The propylene polymerization activity per gram of solid catalyst component was calculated using the following expression.

(30) Propylene polymerization activity(g-PP/g-catalyst)=mass(g) of polypropylene/mass(g) of solid catalyst component included in olefin polymerization catalyst

(31) Melt Flow Rate (MFR) of Polymer

(32) The melt flow rate (MFR) (melt flow index) (g/10 min.) of the polymer was measured in accordance with ASTM D1238 (JIS K 7210)

(33) Xylene-Soluble Content (XS) in Polymer

(34) A flask equipped with a stirrer was charged with 4.0 g of the polymer (polypropylene) and 200 ml of p-xylene. The external temperature was increased to be equal to the boiling point (about 150 C.) of xylene, and the polymer was dissolved over 2 hours while maintaining p-xylene contained in the flask at a temperature (137 to 138 C.) under the condition of boiling point. The solution was cooled to 23 C. over 1 hour, and an insoluble component and a soluble component was separated by filtration. A solution of the soluble component was collected, and p-xylene was evaporated by heating (drying) under reduced pressure. The weight of the residue was calculated, and the relative ratio (mass %) with respect to the polymer (polypropylene) was calculated to determine the xylene-soluble content (XS).

(35) Evaluation of Flexural Modulus (FM)

(36) The polymer (polypropylene) was injection-molded to prepare a property measurement specimen. The specimen was conditioned in a temperature-controlled room maintained at 23 C. for 144 hours or more, and in accordance with JIS K 7171, the flexural modulus (FM) (MPa) was measured using the specimen provided that a liquid/powder exudate was not observed on the surface thereof.

(37) Note that the property measurement specimen was prepared as described below. 0.10 wt % of IRGANOX 1010 (manufactured by BASF), and 0.10 wt % of IRGAFOS 168 (manufactured by BASF), and 0.08 wt % of calcium stearate were added to the polymer (polypropylene), and the mixture was kneaded and granulated using a single-screw extruder to obtain pellets of the polymer(polypropylene). The pellets of the polymer (polypropylene) were introduced into an injection molding machine (mold temperature: 60 C., cylinder temperature: 230 C.), and injection-molded to prepare the property measurement specimen.

(38) Molecular Weight and Molecular Weight Distribution of Polymer

(39) The molecular weight and molecular weight distribution of the polymer were measured by gel permeation chromatography (GPC) (GPCHLC-8321 GPC/HT manufactured by Toso) under the following conditions. Molecular Weight Distribution of Polymer was evaluated by the ratio Mw/Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn)

(40) [Detection Condition]

(41) Solvent: o-dichlorobenzene (ODCB)+BHT0.1% Temperature: 140 C. (SEC) Column: GMHHR-H(20)1 and GMHHR-H(S)HT21 Sample concentration: 0.5 mg/ml(ODCB) Sample amount: 0.5 ml Carrier solvent flow rate: 1.0 ml/min

Example 2

(42) Synthesis of Solid Catalyst Component (A2)

(43) A solid catalyst component (A2) was prepared in the same manner as example 1, except that 0.6 ml (2.2 mmol) of di-n-butyl benzylidenemalonate was added to the flask instead of di-n-propyl phthalate at second step and third step.

(44) The solid catalyst component (A2) had a titanium atom content of 1.8 mass %, a total phthalic diester content of 14.0 mass %, and di-n-butyl benzylidenemalonate content of 2.8 mass %.

(45) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(46) A polymerization catalyst (B2) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (A2) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

Example 3

(47) Synthesis of Solid Catalyst Component (A3)

(48) A solid catalyst component (A3) was prepared in the same manner as example 1, except that 0.5 ml (2.2 mmol) of diethyl benzylidenemalonate was added to the flask instead of di-n-propyl phthalate at second step and third step.

(49) The solid catalyst component (A3) had a titanium atom content of 1.7 mass %, a total phthalic diester content of 18.5 mass %, and diethyl benzylidenemalonate content of 8.0 mass %.

(50) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(51) A polymerization catalyst (B3) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (A3) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

Example 4

(52) Synthesis of Solid Catalyst Component (A4)

(53) A solid catalyst component (A4) was prepared in the same manner as example 1, except that 4.4 ml (17.2 mmol) of di-n-propyl benzylidenemalonate was added stepwise to the mixture while heating the mixture instead of di-n-ethyl benzylidenemalonate at first step of heating procedure.

(54) The solid catalyst component (A4) had a titanium atom content of 1.7 mass %, a total phthalic diester content of 15.3 mass %, and di-n-propyl benzylidenemalonate content of 2.2 mass %.

(55) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(56) A polymerization catalyst (B4) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (A4) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

Example 5

(57) Synthesis of Solid Catalyst Component (A5)

(58) (1) First Step

(59) A 75 liter round bottom reactor equipped with a stirrer in which the internal atmosphere had been sufficiently replaced by nitrogen gas, was charged with 6.6 l (60 mol) of titanium tetrachloride and 13.2 l (12.4 mol) of toluene to prepare a solution.

(60) A suspension prepared using 3.3 kg (28.9 mol) of spherical diethoxymagnesium (diameter=43 m), 13.2 l (12.4 mol) of toluene, and 660 ml (2.9 mol) of di-n-propyl phthalate was added to the solution. The mixture was stirred at 5 C. for 1 hour, and heated to 110 C. 660 ml (2.9 mol) of diethyl benzylidenemalonate was added stepwise to the mixture while heating the mixture. After reacting the mixture at 90 C. for 3 hours with stirring, the reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(61) After the addition of 30.9 l of toluene (100 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated four times to wash the reaction product to obtain reaction product slurry including a solid component (I).

(62) (2) Second Step

(63) 28.1 l of toluene and 5.0 l (46 mol) of titanium tetrachloride were added to the reaction product slurry including the solid component (I). The mixture was heated to 110 C., and reacted for 2 hours with stirring. After completion of the reaction, the supernatant liquid was removed. After the addition of 29.7 l of toluene and 3.3 l (30 mol) of titanium tetrachloride, the mixture was heated to 80 C. After the addition of 83 ml (365 mmol) of di-n-propyl phthalate, the mixture was heated to 110 C., and reacted for 1 hour with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(64) After completion of the reaction, 30.9 l of toluene (100 C.) was added to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated twice to wash the reaction product to obtain reaction product slurry including a solid component (II).

(65) (3) Third Step

(66) 30.9 l (290 mol) of toluene was added to the reaction product slurry including the solid component (II) to adjust the concentration of titanium tetrachloride in the reaction mixture to 0.2 mass %, and the mixture was heated to 80 C. After the addition of 83 ml (365 mmol) of di-n-propyl phthalate, the mixture was reacted at 100 C. for 1 hour with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(67) After the addition of 24.9 l of n-heptane (60 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 7 times to wash the reaction product to obtain a solid catalyst component (A5) for olefin polymerization.

(68) The solid catalyst component (A5) had a titanium atom content of 1.5 mass %, a total phthalic diester content of 14.5 mass %, and diethyl benzylidenemalonate content of 2.2 mass %.

(69) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(70) A polymerization catalyst (B5) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (A5) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

(71) Preparation of Ethylene-Propylene Copolymerization Catalyst and Production of Impact Copolymer

(72) An autoclave (internal volume: 2.0 l) equipped with a stirrer in which the internal atmosphere had been completely replaced by nitrogen gas, was charged with 2.2 mmol of triethylaluminum, 0.22 mmol of diethylaminotriethoxysilane, and the solid catalyst component (A1) (0.37 mol on a titanium atom basis) to prepare an ethylene-propylene copolymerization catalyst.

(73) An autoclave equipped with a stirrer was charged with the ethylene-propylene copolymerization catalyst, and further charged with liquefied propylene (15 mol) and hydrogen gas (partial pressure: 0.20 MPa). The liquefied propylene was subjected to preliminary polymerization at 20 C. for 5 minutes, and subjected to first-step homopropylene polymerization (homopolymerization) at 70 C. for 60 minutes. The pressure inside the autoclave was then returned to normal pressure.

(74) Before starting copolymerization step, 0.70 MPa of propylene, 0.49 MPa of ethylene, and 0.010 MPa of hydrogen were added to the autoclave. The mixture was heated to 70 C., and reacted at 70 C. for 15 minutes under a pressure of 1.2 MPa while feeding ethylene, propylene, and hydrogen in a ratio of 1.6/2.4/0.015 (l/min) to obtain an ethylene-propylene copolymer. The polymerization results are shown in Table 2.

(75) The propylene-based block copolymerization activity (ICP (impact copolymer) activity) (g-ICP/(g-cat)) was measured as described below to evaluate the sustainability of polymerization activity. The MFR of the homopolymer, the MFR of the ICP, the EPR content (rubber content) (wt %) in the propylene-based block copolymer, the ethylene content (wt %) in the EPR, the ethylene content (wt %) in the xylene-insoluble component, the flexural modulus (FM) (MPa), and the Izod impact strength (KJ/m.sup.2) were also measured. The results are shown in Table 2.

(76) ICP Polymerization Activity

(77) The propylene-based block copolymerization activity per gram of the solid catalyst component was calculated by the following expression.

(78) Propylene-based block copolymerization activity (g-ICP/g-catalyst)=(I(g)F(g)+J(g))/[{mass(g) of solid catalyst component in olefin polymerization catalyst((G(g)F(g)J(g))}/(G(g)F(g)))]

(79) Note that I is the mass (g) of the autoclave after completion of copolymerization, F is the mass (g) of the autoclave, G is the mass (g) of the autoclave after unreacted monomers had been removed after completion of PP homopolymerization, and J is the amount (g) of polymer removed after homopolymerization.
Homopolymerization Activity

(80) The homopolymerization activity per gram of solid catalyst component was calculated by the following expression.

(81) homopolymerization activity(g-PP/g-catalyst)=(G(g)F(g)/(mass(g) of solid catalyst component in olefin polymerization catalyst).

(82) EPR Content (Xylene-Soluble Content in ICP Polymer)

(83) A flask equipped with a stirrer was charged with 5.0 g of the copolymer (ICP propylene polymer) and 250 ml of p-xylene. The external temperature was increased to be equal to or higher than the boiling point of xylene (about 150 C.), and the polymer was dissolved over 2 hours while maintaining p-xylene contained in the flask at the boiling point (137 to 138 C.). The solution was cooled to 23 C. over 1 hour, and an insoluble component and a soluble component were separated by filtration. A solution of the soluble component was collected, and p-xylene was evaporated by heating (drying) under reduced pressure. The weight of the residue was calculated, and the relative ratio (mass %) relative to the polymer (propylene-based block copolymer) was calculated to determine the EPR content.

(84) Determination of Ethylene Content in EPR

(85) A small amount of EPR (xylene-soluble component) that was extracted with xylene when determining the EPR content (xylene-soluble content in the ICP polymer) was sampled, and hot-pressed in the shape of a film. The ethylene content in the EPR was calculated from the absorbance measured using a Fourier transform infrared spectrometer (FT-IR) (Avatar manufactured by Thermo Nicolet) based on a calibration curve drawn using a plurality of samples having a known ethylene content.

(86) Measurement wavelength: 720 cm.Math.1 and 1150 cm.Math.1

(87) Film thickness: 0.1 to 0.2 mm

(88) Ethylene Content in Xylene-Insoluble (XI) Component

(89) A small amount of the xylene-insoluble component obtained by extraction with xylene was sampled, and hot-pressed in the shape of a film, and the ethylene content in the xylene-insoluble component was calculated in the same manner as the ethylene content in the EPR.

(90) Melt Flow Rate (MFR) of Polymer

(91) The melt flow rate (MFR) (melt flow index) (g/10 min) of homopolypropylene and the ICP polymer was measured in accordance with ASTM 01238 (JIS K 7210).

(92) The Intrinsic Viscosity of EPR (I.V.-EPR)

(93) The intrinsic viscosity of EPR (I.V.-EPR) was calculated by using following formula (Huggins equation) from the reduced viscosity (nSP/c) measured in decalin at 135 C. by means of Ubbelohde-type viscometer;
SP/c=[]+K[].sup.2c
wherein, SP/c (dI/g) is reduced viscosity, [] (dI/g) is intrinsic viscosity, c(g/dI) is polymer concentration, and K is 0.35 (Huggins constant).
Flexural Modulus (FM) of Polymer

(94) The polymer was molded to prepare a property measurement specimen in accordance with JIS K 7171. The specimen was conditioned in a temperature-controlled room maintained at 23 C. for 144 hours or more, and the flexural modulus (FM) (MPa) was measured using the specimen provided that a liquid/powder exudate was not observed on the surface thereof. Note that the property measurement specimen was prepared as described below. 0.10 wt % of IRGANOX 1010 (manufactured by BASF), and 0.10 wt % of IRGAFOS 168 (manufactured by BASF) were added to the ethylene-propylene copolymer, and the mixture was kneaded and granulated using a single-screw extruder to obtain pellets of the ethylene-propylene copolymer. The pellets of the ethylene-propylene copolymer were introduced into an injection molding machine (mold temperature: 60 C., cylinder temperature: 230 C.), and injection-molded to prepare the property measurement specimen.

(95) Izod Impact Strength

(96) 0.10 wt % of IRGANOX 1010 (manufactured by BASF), and 0.10 wt % of IRGAFOS 168 (manufactured by BASF) were added to the ethylene-propylene copolymer, and the mixture was kneaded and granulated using a single-screw extruder to obtain pellets of the ethylene-propylene copolymer. The pellets of the ethylene-propylene copolymer were introduced into an injection molding machine (mold temperature: 60 C., cylinder temperature: 230 C.), and injection-molded to prepare a property measurement specimen. The specimen was conditioned in a temperature-controlled room maintained at 23 C. for 144 hours or more, and the Izod impact strength of the specimen was measured in accordance with JIS K 7110 (Method of Izod Impact Test For Rigid Plastics) using an Izod tester (Model A-121804405 manufactured by Toyo Seiki Seisaku-Sho, Ltd.).

(97) Shape of specimen: ISO 180/4A, thickness: 3.2 mm, width: 12.7 mm, length: 63.5 mm

(98) Shape of notch: type-A notch (radius: 0.25 mm) formed using a die provided with a notch

(99) Temperature: 23 C. and 30 C.

(100) Impact speed: 3.5 m/s

(101) Nominal pendulum energy: 0.5 J (23 C.) and 0.5 J (30 C.).

Example 6

(102) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(103) A polymerization catalyst (B6) was prepared and evaluated in the same manner as example 5, except that 0.22 mmol of diisopropyldimethoxysilane was used instead of 0.22 mmol of diethylaminotriethoxysilane and 7.0 l of hydrogen was added instead of 5.5 l of hydrogen. The polymerization results are shown in Table 1.

Example 7

(104) Preparation of Propylene Polymerization Catalyst and Poylmerization of Propylene

(105) A polymerization catalyst (B5) was prepared and evaluated in the same manner as example 5, except that polymerization was performed under 65 C. instead of 70 C. and 9.0 l of hydrogen was added instead of 5.5 l of hydrogen. The polymerization results are shown in Table 1.

Example 8

(106) Evaluation of Flexural Modulus (FM)

(107) With the same polymer obtained in the example 7, flexural modulus evaluation was performed in the same manner as example 1, except that 1,000 ppm of sodium benzoate was added as a nucleating agent instead of 800 ppm of Calcium Stearate before the extrusion process of the polymer. The results are shown in Table 1.

Comparative Example 1

(108) Synthesis of Solid Catalyst Component (a1)

(109) (1) First Step

(110) A 500 ml round bottom flask equipped with a stirrer in which the internal atmosphere had been sufficiently replaced by nitrogen gas, was charged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565 mmol) of toluene to prepare a solution.

(111) A suspension prepared using 20 g (175 mmol) of spherical diethoxymagnesium (diameter=43 m), 80 ml (753 mmol) of toluene, and 4.0 ml (17.3 mmol) of di-n-propyl phthalate was added to the solution. The mixture was stirred at 5 C. for 1 hour, and heated to 110 C. 4.0 ml (17.2 mmol) of di-n-propyl phthalate was added stepwise to the mixture while heating the mixture. After reacting the mixture at 90 C. for 3 hours with stirring, the reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(112) After the addition of 187 ml of toluene (100 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated four times to wash the reaction product to obtain reaction product slurry including a solid component (I).

(113) (2) Second Step

(114) 170 ml of toluene and 30 ml (273 mmol) of titanium tetrachloride were added to the reaction product slurry including the solid component (I). The mixture was heated to 110 C., and reacted for 2 hours with stirring. After completion of the reaction, the supernatant liquid was removed. After the addition of 180 ml of toluene and 20 ml (182 mmol) of titanium tetrachloride, the mixture was heated to 80 C. After the addition of 0.5 ml (2.2 mmol) of diethyl benzylidenemalonate, the mixture was heated to 110 C., and reacted for 2 hours with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(115) After completion of the reaction, 187 ml of toluene (100 C.) was added to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated twice to wash the reaction product to obtain reaction product slurry including a solid component (II).

(116) (3) Third Step

(117) 170 ml (1600 mmol) of toluene was added to the reaction product slurry including the solid component (II) to adjust the concentration of titanium tetrachloride in the reaction mixture to 0.2 mass %, and the mixture was heated to 80 C. After the addition of 0.5 ml (2.2 mmol) of diethyl benzylidenemalonate, the mixture was reacted at 100 C. for 1 hour with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(118) After the addition of 150 ml of n-heptane (60 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 7 times to wash the reaction product to obtain a solid catalyst component (a1) for olefin polymerization.

(119) The solid catalyst component (a1) had a titanium atom content of 1.7 mass %, a total phthalic diester content of 15.4 mass %, and diethyl benzylidenemalonate content of 4.0 mass %.

(120) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(121) A polymerization catalyst (b1) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (a1) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

Comparative Example 2

(122) Synthesis of Solid Catalyst Component (a2)

(123) A 500 ml round bottom flask equipped with a stirrer in which the internal atmosphere had been sufficiently replaced by nitrogen gas, was charged with 20 g of diethoxymagnesium (diameter=43 m), 110 ml of toluene, 40 ml of titanium tetrachloride. The mixture was heated to 60 C. After the addition of 8.2 ml (30.6 mmol) of diethyl diisopropylsuccinate, the mixture was heated to 100 C., and reacted for 2 hours with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(124) After completion of the reaction, 90 ml of toluene (100 C.) was added to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 6 times to wash the reaction product to obtain reaction product slurry including a solid component.

(125) 100 ml of toluene and 20 ml of titanium tetrachloride were added to the reaction product slurry including the solid component. The mixture was heated to 100 C., and reacted for 15 minutes with stirring. After completion of the reaction, the supernatant liquid was removed. This operation was repeated 3 times followed by the addition of 150 ml of n-heptane (40 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 6 times to wash the reaction product to obtain a solid catalyst component (a2) for olefin polymerization.

(126) The solid catalyst component (a2) had a titanium atom content of 2.2 mass %, and a diethyl diisopropylsuccinate content of 21.3 mass %.

(127) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(128) A polymerization catalyst (b2) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (a2) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

Comparative Example 3

(129) Synthesis of Solid Catalyst Component (a3)

(130) (1) First Step

(131) A 75 liter round bottom reactor equipped with a stirrer in which the internal atmosphere had been sufficiently replaced by nitrogen gas, was charged with 6.6 l (60 mol) of titanium tetrachloride and 13.2 l (12.4 mol) of toluene to prepare a solution.

(132) A suspension prepared using 3.3 kg (28.9 mol) of spherical diethoxymagnesium (diameter=61 m), 13.2 l (12.4 mol) of toluene, and 930 ml (4 mol) of di-n-propyl phthalate was added to the solution. The mixture was stirred at 5 C. for 1 hour, and heated to 110 C. 138 ml (480 mmol) of dimethyl di-isobutylmalonate was added stepwise to the mixture while heating the mixture. After reacting the mixture at 110 C. for 3 hours with stirring, the reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(133) After the addition of 30.9 l of toluene (100 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated four times to wash the reaction product to obtain reaction product slurry including a solid component (I).

(134) (2) Second Step

(135) 28.1 l of toluene and 5.0 l (46 mol) of titanium tetrachloride were added to the reaction product slurry including the solid component (I). The mixture was heated to 110 C., and reacted for 2 hours with stirring. After completion of the reaction, the supernatant liquid was removed. After the addition of 29.7 l of toluene and 3.3 l (30 mol) of titanium tetrachloride, the mixture was heated to 80 C. After the addition of 83 ml (365 mmol) of di-n-propyl phthalate, the mixture was heated to 110 C., and reacted for 1 hour with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(136) After completion of the reaction, 30.9 l of toluene (100 C.) was added to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated twice to wash the reaction product to obtain reaction product slurry including a solid component (II).

(137) (3) Third Step

(138) 30.9 l (290 mol) of toluene was added to the reaction product slurry including the solid component (II) to adjust the concentration of titanium tetrachloride in the reaction mixture to 0.2 mass %, and the mixture was heated to 80 C. After the addition of 83 ml (365 mmol) of di-n-propyl phthalate, the mixture was reacted at 100 C. for 1 hour with stirring. The resulting reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(139) After the addition of 24.9 l of n-heptane (60 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 7 times to wash the reaction product to obtain a solid catalyst component (a3) for olefin polymerization.

(140) The solid catalyst component (a3) had a titanium atom content of 1.9 mass %, a total phthalic diester content of 18.7 mass %, and dimethyl di-isobutylmalonate content of 1.2 mass %.

(141) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(142) A polymerization catalyst (b3) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (a3) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

Comparative Example 4

(143) Synthesis of Solid Catalyst Component (a4)

(144) (1) First Step

(145) A 75 liter round bottom reactor equipped with a stirrer in which the internal atmosphere had been sufficiently replaced by nitrogen gas, was charged with 6.6 l (60 mol) of titanium tetrachloride and 13.2 l (12.4 mol) of toluene to prepare a solution.

(146) A suspension prepared using 3.3 kg (28.9 mol) of spherical diethoxymagnesium (diameter=43 m), 13.2 l (12.4 mol) of toluene, and 660 ml (2.9 mol) of di-n-butylphthalate was added to the solution. The mixture was stirred at 5 C. for 1 hour, and heated to 110 C. 660 ml (2.9 mol) of di-n-butylphthalate was added stepwise to the mixture while heating the mixture. After reacting the mixture at 90 C. for 3 hours with stirring, the reaction mixture was allowed to stand, and the supernatant liquid was removed to obtain reaction product slurry.

(147) After the addition of 30.9 l of toluene (100 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated four times to wash the reaction product to obtain reaction product slurry including a solid component (I).

(148) (2) Second Step

(149) 28.1 l of toluene and 5.0 l (46 mol) of titanium tetrachloride were added to the reaction product slurry including the solid component (I). The mixture was heated to 110 C., and reacted for 2 hours with stirring. After completion of the reaction, the supernatant liquid was removed.

(150) After the addition of 24.9 l of n-heptane (60 C.) to the reaction product slurry, the mixture was stirred and allowed to stand, and the supernatant liquid was removed. This operation was repeated 7 times to wash the reaction product to obtain a solid catalyst component (a4) for olefin polymerization.

(151) The solid catalyst component (a4) had a titanium atom content of 2.8 mass % and a total phthalic diester content of 17.3 mass %.

(152) Preparation of Propylene Polymerization Catalyst and Polymerization of Propylene

(153) A polymerization catalyst (b4) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (a4) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 1.

(154) Preparation of Ethylene-Propylene Copolymerization Catalyst and Production of Impact Copolymer

(155) A polymerization catalyst (b4) was prepared and evaluated in the same manner as example 1, except that the solid catalyst component (a4) was used instead of the solid catalyst (A1). The polymerization results are shown in Table 2.

(156) TABLE-US-00001 TABLE 1 homo polymerization of propylene Activity MFR XS FM GPC Example g-PP/g-cat g/10 min % MPa Mn Mw Mz Mw/Mn Mz/Mw Mz/Mn 1 24,900 150 1.1 1,910 19,869 178,281 1,830,807 9.0 10.3 92.1 2 17,200 130 1.0 1,930 22,668 205,371 2,515,820 9.1 12.3 111.0 3 16,100 160 0.9 1,920 20,361 205,377 2,623,564 10.1 12.8 128.9 4 20,500 150 1.1 1,930 17,036 145,993 1,255,413 8.6 8.6 73.7 5 23,700 88 0.7 1,940 25,084 237,064 2,968,164 9.5 12.5 118.3 6 28,100 33 0.7 1,930 22,369 297,974 3,070,934 13.3 10.3 137.3 7 19,400 260 1.0 2,020 14,793 178,210 2,436,394 12.0 13.7 164.7 8 2,470

(157) TABLE-US-00002 TABLE 2 homo polymerization of propylene Comparative Activity MFR XS FM GPC Example g-PP/g-cat g/10 min % MPa Mn Mw Mz Mw/Mn Mz/Mw Mz/Mn 1 18,500 170 1.0 1,880 22,143 193,724 1,765,352 8.7 9.1 79.7 2 14,800 31 1.2 1,840 20,673 374,306 4,085,509 18.1 10.9 197.6 3 15,300 180 1.1 1,900 23,231 168,634 1,899,428 7.3 11.3 81.8 4 39,000 110 1.2 1,830 21,414 193,465 2,201,669 9.0 11.4 102.8

(158) TABLE-US-00003 TABLE 3 ICP production Activity Homo ICP EPR Ethylene content I.V. Izod polymerization polymerization MFR content in EPR inXI EPR FM (30deg. C.) (23deg. C.) g-PP/g-catalyst. g-ICP/g-catalyst. g/10 min. wt % wt % wt % dL/g Mpa Kj/m.sup.2 Kj/m.sup.2 Example 9 35,300 1500 (15 min) 170(Homo) 5.0 42.5 1.1 5.5 1660 2.4 4.4 120(ICP) Comparative 43900 3000 (15 min) 180(Homo) 5.6 40.3 1.6 5.6 1600 2.7 4.5 Example 5 110(ICP)

(159) As is clear from the results shown in Table 1 and Table 3, the olefin polymerization catalysts respectively prepared using the solid catalyst components obtained in Examples 1 to 9 achieved producing homo polypropylene or propylene-based block copolymer with high isotacticity and broad molecular distribution. Therefore the flexural modulus of the resulting (co)polymer is improved.

(160) On the other hand, as is clear from the results shown in Table 2 and Table 3, polypropylene or propylene-based block copolymer produced with the solid catalyst components obtained in comparative Examples 1 to 5 showed an insufficient flexural modulus compared to the results of Examples 1 to 9.

INDUSTRIAL APPLICABILITY

(161) The embodiments of the invention thus provide a method for producing homo propylene that exhibits high stiffness and propylene-based block copolymer that exhibits rigidity and impact strength in a well-balanced manner.