JP7424180B2 - Method for producing propylene polymer and branched propylene polymer - Google Patents

Description

The present invention relates to a method for producing a propylene polymer, and more specifically, a method for producing a propylene polymer that has excellent spreadability while maintaining melt tension necessary for molding, and a branched propylene polymer produced by the method. Relating to polymers.

In recent years, many studies have been conducted to improve the suitability of polypropylene for sheet molding, blow molding, thermoforming, foam molding, etc., which require materials with relatively high melt tension, by introducing a branched structure into polypropylene.
Recently, macromer copolymerization methods mainly using metallocene catalysts have been proposed. Branched polypropylene produced by the macromer copolymerization method has advantages such as less generation of gel due to crosslinking reaction, as compared to polypropylene in which a branched structure is introduced by irradiation with an electron beam or the like.
In such a macromer copolymerization method, for example, in the first polymerization step (macromer synthesis step), a propylene macromer having a vinyl structure at the end is produced using a specific catalyst and specific polymerization conditions, and in the second polymerization step (macromer synthesis step), a propylene macromer having a vinyl structure at the end is produced. A method has been proposed in which propylene and propylene macromer are copolymerized using a specific catalyst and specific polymerization conditions in the copolymerization step), and it has been shown that the resulting branched polypropylene has high melt strength and melt tension. (For example, see Patent Documents 1 and 2).

A single-stage polymerization method has also been proposed in which the macromer synthesis step and the macromer copolymerization step are carried out simultaneously using a specific metallocene catalyst, and the resulting branched polypropylene has been shown to exhibit improved melt strength. (For example, see Patent Document 3).
Furthermore, catalysts containing two specific metallocene compounds, specifically rac-SiMe ₂ [2-Me-4-Ph-lnd] ₂ ZrC1 ₂ and rac-SiMe ₂ [2-Me-4-Ph- A multistage polymerization method has been proposed using a catalyst that combines a metallocene compound such as ₂ HfC1 ₂ with silica supporting methylaluminoxane (MAO), and the resulting propylene polymer is relatively expensive. It has been reported that it exhibits melt tension (see Patent Document 4).

In addition, a method using a catalyst containing a specific metallocene compound and an ion-exchanged layered silicate has been devised, and the resulting propylene polymer has a wide molecular weight distribution, a large amount of branching, and a good melt tension. It has been reported (see Patent Document 5).
Furthermore, a method using a catalyst containing a plurality of specific metallocene compounds has been devised, and it has been reported that the resulting propylene polymer has good melt tension (see Patent Document 6).

Special Publication No. 2001-525460 Japanese Patent Application Publication No. 10-338717 Special Publication No. 2002-523575 Japanese Patent Application Publication No. 2001-64314 Japanese Patent Application Publication No. 2007-154121 Japanese Patent Application Publication No. 2009-57542

Propylene polymers with a branched structure obtained by conventionally proposed and devised macromer copolymerization methods have high melt tension and are highly suitable for sheet molding, blow molding, thermoforming, foam molding, etc. However, there is a problem that the spreadability is not excellent. In general, increasing fluidity improves spreadability, but melt tension tends to decrease. Therefore, when fluidity is increased to improve spreadability, there is a problem that melt tension becomes insufficient during sheet molding or extrusion molding.
Therefore, the present invention provides a method for producing a propylene polymer that has excellent spreadability while maintaining the melt tension necessary for molding, and a method for producing a propylene polymer that has excellent spreadability while maintaining the melt tension necessary for molding. The challenge is to provide the following.

As a result of extensive studies, the present inventors have found that the cause of the poor spreadability of branched propylene polymers with high melt tension produced by conventional methods is the structure of branched propylene, particularly the molecular weight distribution and branching distribution. They discovered that the above problems can be solved by controlling a non-conventional polymerization method, a hydrogen introduction method during polymerization, and the temperature dependence of melt tension.

The method for producing a propylene polymer of the present invention involves continuously producing a propylene polymer in the presence of a propylene polymerization catalyst containing the following components [A-1], component [A-2], component [B] and component [C]. In a method for producing a propylene polymer by polymerizing propylene,
It has a step of recovering the propylene-based polymer from the polymerization reactor while continuously introducing at least hydrogen and propylene into the polymerization reactor, and in the recovery step, the hydrogen and propylene are introduced at a flow rate at which the hydrogen and propylene are continuously introduced. keeping the ratio constant,
The ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer is 1.8 or more and 2.5 or less, and MT230°C is 3. It is characterized by being 6 g or more and 15.0 g or less.
Component [A-1]: A metallocene compound that forms a polymerization catalyst that produces a propylene homopolymer having a terminal vinyl ratio (Rv) of 0.5 or more when propylene homopolymerization is carried out at 70°C.
Here, the terminal vinyl ratio (Rv) is defined by the following formula.
Rv=(Mn/42)×[Vi]/1000
(In the formula, Mn is the number average molecular weight determined by GPC, and [Vi] is the number of terminal vinyl groups per 1000 monomers calculated by ¹ H-NMR.)
Component [A-2]: Metallocene compound represented by general formula (a2).

［一般式（ａ２）中、Ｅ^２１およびＥ^２２は、それぞれ独立して、シクロペンタジエニル基、インデニル基、フルオレニル基またはアズレニル基を表し、それぞれ置換基を有していてもよい（但し、置換基が窒素、酸素または硫黄を含有する炭素数４～１６の複素環基であることはない。）。Ｑ^２１は、炭素数１～２０の二価の炭化水素基、または炭素数１～２０の炭化水素基を有していてもよいシリレン基もしくはゲルミレン基を表し、Ｍ^２１は、ジルコニウムまたはハフニウムを表し、Ｘ^２１およびＹ^２１は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基を有するシリル基、炭素数１～２０のハロゲン化炭化水素基、アミノ基または炭素数１～２０のアルキルアミノ基を表す。］
成分［Ｂ］：成分［Ａ－１］及び成分［Ａ－２］と反応してイオン対を形成する化合物又はイオン交換性層状珪酸塩。
成分［Ｃ］：有機アルミニウム化合物。

[In general formula (a2), E ²¹ and E ²² each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent (however, The substituent is not a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.) Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: A compound or ion-exchangeable layered silicate that reacts with component [A-1] and component [A-2] to form an ion pair.
Component [C]: Organoaluminum compound.

In the method for producing a propylene polymer of the present invention, it is preferable that the component [A-1] is a compound represented by general formula (a1) from the viewpoint of producing a propylene polymer with a high terminal vinyl content. .

[In general formula (a1), R ¹¹ and R ¹² each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 30 carbon atoms that may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these; Or it represents a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

In the method for producing a propylene polymer of the present invention, the component [A-2] is a compound represented by the general formula (a3), and a high molecular weight propylene polymer is obtained by copolymerizing a terminal vinyl polymer. It is preferable from the point of view that it generates .

［一般式（ａ３）中、Ｒ^２１およびＲ^２２は、それぞれ独立して、炭素数１～６の炭化水素基である。Ｒ^２３およびＲ^２４は、それぞれ独立して、ハロゲン、ケイ素、酸素、硫黄、窒素、ホウ素、リン若しくはこれらから選択される複数のヘテロ元素を含有してもよい炭素数６～３０のアリール基を表す。Ｑ^２１は、炭素数１～２０の二価の炭化水素基、または炭素数１～２０の炭化水素基を有していてもよいシリレン基もしくはゲルミレン基を表し、Ｍ^２１は、ジルコニウムまたはハフニウムを表し、Ｘ^２１およびＹ^２１は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基を有するシリル基、炭素数１～２０のハロゲン化炭化水素基、アミノ基または炭素数１～２０のアルキルアミノ基を表す。］

[In general formula (a3), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. represent. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

The propylene polymer of the present invention is a branched propylene polymer having the following properties (A) to (E).
(A) The ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer is 1.8 or more and 2.5 or less.
(B) The MT230°C of the propylene polymer is 3.6 g or more and 15.0 g or less.
(C) The melt flow rate (MFR) measured at a temperature of 230° C. and a load of 2.16 kg is 3.0 g/10 minutes or more and 13.0 g/10 minutes or less.
(D) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Q value) obtained by gel permeation chromatography (GPC) is 3.8 or more and 4.5 or less.
(E) The maximum winding speed (MaxDraw) determined by the following measurement method and the melt flow rate (MFR) satisfy the relationship shown by the following formula (1').
(MaxDraw)≧62×log(MFR)+7...Formula (1')
<Maximum winding speed measurement method>
Using a melt tension tester, when extruding resin into a string under the following conditions and winding it around a roller, the winding speed was increased from 4.0 m/min to an acceleration of 5.4 cm/s ² . The winding speed immediately before the string-like material is cut is defined as the maximum winding speed (MaxDraw).
Capillary: diameter 2.1mm
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10mm/min Temperature: 210℃

According to the present invention, there is provided a method for producing a propylene polymer that has excellent spreadability while maintaining the melt tension necessary for molding, and a method for producing a propylene polymer that has excellent spreadability while maintaining the melt tension necessary for molding. can be provided.

FIG. 1 is a diagram illustrating the baseline and interval of a chromatogram in GPC. FIG. 2 is a diagram showing the relationship between the MFR and the maximum winding speed (MaxDraw) at 210° C. of propylene polymers of Examples and Comparative Examples.

The method for producing a propylene polymer of the present invention involves continuously producing a propylene polymer in the presence of a propylene polymerization catalyst containing the following components [A-1], component [A-2], component [B] and component [C]. In a method for producing a propylene polymer by polymerizing propylene,
It has a step of recovering the propylene-based polymer from the polymerization reactor while continuously introducing at least hydrogen and propylene into the polymerization reactor, and in the recovery step, the hydrogen and propylene are introduced at a flow rate at which the hydrogen and propylene are continuously introduced. keeping the ratio constant,
The ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer is 1.8 or more and 2.5 or less, and MT230°C is 3. It is characterized by being 6 g or more and 15.0 g or less.
Component [A-1]: A metallocene compound that forms a polymerization catalyst that produces a propylene homopolymer having a terminal vinyl ratio (Rv) of 0.5 or more when propylene homopolymerization is carried out at 70°C.
Here, the terminal vinyl ratio (Rv) is defined by the following formula.
Rv=(Mn/42)×[Vi]/1000
(In the formula, Mn is the number average molecular weight determined by GPC, and [Vi] is the number of terminal vinyl groups per 1000 monomers calculated by ¹ H-NMR.)
Component [A-2]: Metallocene compound represented by general formula (a2).

［一般式（ａ２）中、Ｅ^２１およびＥ^２２は、それぞれ独立して、シクロペンタジエニル基、インデニル基、フルオレニル基またはアズレニル基を表し、それぞれ置換基を有していてもよい（但し、置換基が窒素、酸素または硫黄を含有する炭素数４～１６の複素環基であることはない。）。Ｑ^２１は、炭素数１～２０の二価の炭化水素基、または炭素数１～２０の炭化水素基を有していてもよいシリレン基もしくはゲルミレン基を表し、Ｍ^２１は、ジルコニウムまたはハフニウムを表し、Ｘ^２１およびＹ^２１は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、炭素数１～２０の炭化水素基を有するシリル基、炭素数１～２０のハロゲン化炭化水素基、アミノ基または炭素数１～２０のアルキルアミノ基を表す。］
成分［Ｂ］：成分［Ａ－１］及び成分［Ａ－２］と反応してイオン対を形成する化合物又はイオン交換性層状珪酸塩。
成分［Ｃ］：有機アルミニウム化合物。

[In general formula (a2), E ²¹ and E ²² each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent (however, The substituent is not a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.) Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: A compound or ion-exchangeable layered silicate that reacts with component [A-1] and component [A-2] to form an ion pair.
Component [C]: Organoaluminum compound.

Hereinafter, the method for producing a propylene polymer of the present invention will be explained in detail for each item. In this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as the lower limit and upper limit.
Moreover, in this specification, "wtppm" means mass ppm, "wt%" means mass %, and "volppm" means volume ppm.

I. Catalyst Components of Propylene Polymerization Catalyst The propylene polymerization catalyst according to the present invention must contain at least component [A-1], component [A-2], component [B], and component [C]. .
1. Component [A-1]
Component [A-1] is a metallocene compound that forms a polymerization catalyst that produces a propylene homopolymer with a terminal vinyl ratio (Rv) of 0.5 or more when propylene homopolymerization is carried out at 70°C. .
Here, the terminal vinyl ratio (Rv) is defined by the following formula.
Rv=(Mn/42)×[Vi]/1000
(In the formula, Mn is the number average molecular weight determined by GPC, and [Vi] is the number of terminal vinyl groups per 1000 monomers calculated from ¹ H-NMR.)

The terminal structure of the propylene polymer will be explained below.
In the polymerization of propylene, a chain transfer reaction generally called β-hydrogen elimination occurs, and a polymer having a propyl-vinylidene structure (vinylidene structure) shown in structural formula (1-b) at the end is produced. Furthermore, when hydrogen is used, chain transfer usually occurs preferentially to hydrogen, producing a polymer having an i-butyl structure at the end as shown in structural formula (1-d).

Furthermore, when a catalyst containing a metallocene compound with a specific structure is used, a special chain transfer reaction called β-methyl elimination occurs, resulting in a 1-propenyl structure (vinyl structure) shown in structural formula (1-a). A polymer having terminals is produced (Reference document: Macromol. Rapid Commun. 2000, 21, 1103-1107).
Furthermore, the starting terminals after β-hydrogen elimination and β-methyl elimination are the n-propyl structure shown in structural formula (1-c) and the i-butyl structure shown in structural formula (1-d), respectively. Yes, with a saturated hydrocarbon end. That is, the starting end is always a saturated hydrocarbon end, and no unsaturated bond appears at both ends.
Furthermore, as for the terminal structure, it is thought that very rarely propylene is irregularly inserted, followed by β-hydrogen elimination, and a very small amount of the 1-butenyl terminal shown in structural formula (1-e) is generated.

Furthermore, polymers having structures shown in Structural Formulas (1-f) to Structural Formulas (1-j) at their ends may be produced.
Structural formula (1-f): i-butenyl structure, Structural formula (1-g): 2-butenyl structure are terminal structures extremely rarely produced by isomerization, and their amounts are based on the structure that is the main terminal structure. The number is minute compared to the number of formula (1-a), structural formula (1-b), structural formula (1-c), and structural formula (1-d).
Structural formula (1-h): The internal vinylidene structure is an olefin structure that is generated inside the polymer chain by further inserting propylene into the intermediate formed by further hydrogen elimination after the unsaturated end is generated. .

Among these terminal structures, polymers having the structures shown in Structural Formula (1-a) and Structural Formula (1-e) at their terminals can be macromers. Structural formula (1-a) and structural formula (1-e) are the same in that the two most terminal carbons have a vinyl structure, and there is no difference in their ability to copolymerize.

Component [A-1] of the present invention is a metallocene compound that forms a polymerization catalyst for producing a propylene macromer, and this is a metallocene compound that is a polymer whose terminal has a structural formula (1-a) or a structural formula (1-e). It can also be referred to as a metallocene compound that forms a catalyst that preferentially produces .

The metallocene compound capable of producing a macromer according to the present invention is a polymerization catalyst that produces a propylene homopolymer with a terminal vinyl ratio of 0.50 or more when propylene homopolymerization is carried out at 70°C. It is a metallocene compound that forms, preferably 0.65 or more, more preferably 0.75 or more, and ideally 1.0 (one end of all molecular chains has a vinyl structure). By using a metallocene compound that forms a polymerization catalyst that produces a propylene homopolymer with a higher percentage of vinyl terminals, a more efficient macromer synthesis process can be performed.

Furthermore, a polymer having a propyl-vinylidene structure (vinylidene structure) shown in structural formula (1-b) produced as a result of β-hydrogen elimination cannot be copolymerized. Therefore, when a metallocene compound forming a polymerization catalyst that produces a propylene homopolymer containing a large amount of vinylidene structure is used, the efficiency of producing branched polypropylene is reduced.

Therefore, in the metallocene compound capable of producing a macromer according to the present invention, the terminal vinylidene ratio of the propylene homopolymer produced when propylene homopolymerization is carried out at 70°C is preferably smaller than 0.1, more preferably 0.05. The metallocene compound is less than 0.01, more preferably less than 0.01, and ideally 0 (substantially no vinylidene structure exists).

[Evaluation method of terminal vinyl ratio (Rv)]
Here, the propylene polymerization conditions for determining the terminal vinyl content of component [A-1] will be described in detail.
After replacing the inside of the 3L autoclave tank with propylene, 2.86 mL of a heptane solution of triisobutylaluminum (143.4 mg/mL) was introduced, 240 mL of hydrogen was introduced, 750 g of liquefied propylene was introduced, and the temperature was raised to 70°C. . Thereafter, the catalyst is pumped into a polymerization tank, and polymerization is carried out at 70° C. for 1 hour. Finally, unreacted propylene is quickly purged and polymerization is stopped to obtain a propylene polymer.

The terminal vinyl ratio (Rv) and the ^terminal vinylidene ratio (Rvd) are determined by the number average molecular weight ( It is calculated using the following formula as the ratio of polymer chains having each terminal to the total number of polymer chains obtained from Mn).
Rv=(Mn/42)×[Vi]/1000
Rvd=(Mn/42)×[Vd]/1000
(However, Mn is the number average molecular weight determined by GPC.)

[Measurement method of number average molecular weight (Mn)]
In the present invention, the number average molecular weight (Mn) is measured by gel permeation chromatography (GPC).
Note that the baseline and interval of the obtained chromatogram are determined as shown in FIG.
Conversion from retention capacity to molecular weight is performed using a standard polystyrene calibration curve prepared in advance.
The standard polystyrene used is the following brand manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in o-dichlorobenzene (containing 0.5 mg/mL BHT) so that each concentration is 0.5 mg/mL.
The calibration curve uses a cubic equation obtained by approximation using the least squares method. The following numerical value is used for the viscosity formula [η]=K×M ^α used for conversion to molecular weight.
PS: K=1.38×10 ⁻⁴ α=0.7
PP:K=1.03× ^10-4 α=0.78
Note that the GPC measurement conditions are as follows.
Equipment: WATERS GPC (ALC/GPC 150C)
Detector: FOXBORO MIRAN1AIR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M/S (3 columns)
Mobile phase solvent: ο-dichlorobenzene Measurement temperature: 140°C
Flow rate: 1.0ml/min Injection volume: 0.2ml
Preparation of Sample A 1 mg/mL solution of the sample is prepared using o-dichlorobenzene (containing 0.5 mg/mL BHT), and dissolved at 140° C. for about 1 hour.

[Method for measuring the number of unsaturated terminals]
Here, details of the method for measuring the number of terminal vinyl groups [Vi] and the number of terminal vinylidene groups [Vd] by ¹ H-NMR are as follows.
[Sample preparation and measurement conditions]
200 mg of the sample was combined with 2.4 ml of o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane, which is a reference material for chemical shift, into an NMR sample with an inner diameter of 10 mmφ. Pour into a tube and melt uniformly using a block heater at 150°C. The NMR measurement is performed using an AV400 NMR apparatus manufactured by Bruker Biospin Inc. equipped with a 10 mmφ cryoprobe.
¹ H-NMR is used to quantify unsaturated ends. The measurement conditions for ¹ H-NMR are a sample temperature of 120° C., a pulse angle of 4.5°, a pulse interval of 2 seconds, and a total number of 512 times. For chemical shifts, the proton signal of hexamethyldisiloxane is set at 0.09 ppm, and chemical shifts of signals due to other protons are based on this.

[How to calculate the number of unsaturated terminals]
In ¹ H-NMR, the proton signal of the 1-propenyl structure of structural formula (1-a) and the proton signal of the 1-butenyl structure of structural formula (1-e) are 5.08 to 4 in the ¹ H-NMR spectrum. The signals at .85 ppm and 5.86 to 5.69 ppm are overlapped and detected. Therefore, the number of terminal vinyl groups [Vi] is calculated as the total number of 1-propenyl structures and 1-butenyl structures, as the amount of unsaturated bonds per 1000 monomers, and using the signal intensity of the ¹ H-NMR spectrum, as follows: Obtain from the formula.
Structural formula (1-a) + Structural formula (1-e): [Vi]=Ivi×1000/Itotal
Further, the number of terminal vinylidene groups [Vd] is determined from the following formula using the signal intensity of ¹ H-NMR spectrum as the amount of unsaturated bonds per 1000 monomers.
Structural formula (1-b): [Vd]=Ivd×1000/Itotal
Here, Ivi and Ivd represent the characteristic values of the signals based on the structural formulas (1-a), (1-e), and (1-b), respectively, and are the amounts shown by the following formulas. be.
Ivi=(I _5.08~4.85 +I _5.86~5.69 )/3,
Ivd=(I _4.79~4.65 )/2,
I indicates the integrated intensity, and the subscript number of I indicates the range of chemical shift. For example, I _5.08-4.85 indicates the integrated intensity of the signal detected between 5.08 ppm and 4.85 ppm.
Further, Itotal is an amount expressed by the following formula.
Itotal=IC3+Ivi+Ivd+Iibu+Ivnl+Iivd
Here, Iibu, Ivnl, and Iivd are respectively structural formula (1-f): i-butenyl, structural formula (1-g): 2-butenyl, and structural formula (1-h): a signal based on an internal vinylidene structure. It represents a characteristic value and is a quantity expressed by the following formula.
Iibu=I _5.30~5.08 ,
Ivnl = (I _5.58~5.30 )/2,
Iivd=(I _4.85~4.79 )/2
IC3 represents a characteristic value of a signal based on propylene, and is an amount expressed by the following formula.
IC3 = 1/6 x Imain
Imain is the sum of the proton signals of the polymer main chain and saturated terminals detected at 4.00 to 0.00 ppm in the ¹ H-NMR spectrum.
In addition, peaks derived from other olefin structures that are by-produced in Itotal in a range other than the above, such as structural formula (1-i) internal trisubstituted olefin, structural formula (1-j) internal vinylene, etc., are detected in minute quantities. There is a possibility, but in that case, they will be excluded from the calculation.

Component [A-1] is a metallocene that forms a polymerization catalyst that produces a propylene homopolymer with a terminal vinyl ratio of 0.50 or more when propylene homopolymerization is carried out at 70°C. The compound is not particularly limited as long as it is a compound, and it can also be selected from compounds included in the general formula (a2) of component [A-2] described below. Examples of component [A-1] include bisindene complexes having a bulky heterocyclic group at the 2-position and an optionally substituted aryl group or a nitrogen-, oxygen- or sulfur-containing heterocyclic group at the 4-position. As one non-limiting preferred embodiment, the following structure can be mentioned.
Component [A-1] is preferably a metallocene compound represented by the following general formula (a1) from the viewpoint of producing a propylene polymer with a high terminal vinyl content.

[In general formula (a1), R ¹¹ and R ¹² each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 30 carbon atoms that may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these; Or it represents a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

The nitrogen-, oxygen- or sulfur-containing heterocyclic group having 4 to 16 carbon atoms in R ¹¹ and R ¹² above is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, a substituted 2-furfuryl group, more preferably a substituted 2-furfuryl group.
By setting R ¹¹ and R ¹² to groups selected from heterocyclic groups containing nitrogen, oxygen, or sulfur and having 4 to 16 carbon atoms, the terminal vinyl ratio (Rv) can be increased. By introducing a substituent of an appropriate size onto the group, the coordination field on the heterocycle and the transition metal, and the relative positional relationship with the growing polymer chain are made appropriate, thereby increasing the vinyl terminal ratio (Rv). can be made higher.
Substituents for the substituted 2-furyl group, substituted 2-thienyl group, and substituted 2-furfuryl group include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, and propyl group; Examples include halogen atoms such as fluorine atoms and chlorine atoms, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, and trialkylsilyl groups. Among these, methyl group and trimethylsilyl group are preferred, and methyl group is particularly preferred.
Furthermore, particularly preferred as R ¹¹ and R ¹² is a 5-methyl-2-furyl group. Moreover, it is preferable that R ¹¹ and R ¹² are the same.

The above R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. , or a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen, or sulfur.
In particular, by making R ¹³ and R ¹⁴ more bulky, a propylene polymer with higher stereoregularity, less heterobonds, and a higher vinyl terminal ratio can be obtained.
Therefore, R ¹³ and R ¹⁴ include one or more hydrocarbon groups having 1 to 6 carbon atoms or hydrocarbon groups having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. A silyl group having 1 to 6 carbon atoms, a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, or an aryl group which may have a halogen atom as a substituent is preferable, and specific examples of such R ¹³ and R ¹⁴ include 4-t -butylphenyl group, 2,3-dimethylphenyl group, 3,5-di-t-butylphenyl group, 4-chlorophenyl group, 4-trimethylsilylphenyl group, 1-naphthyl group, and 2-naphthyl group.
Further, R ¹³ and R ¹⁴ more preferably have one or more hydrocarbon groups having 1 to 6 carbon atoms, or hydrocarbon groups having 1 to 6 carbon atoms, within the range of 6 to 16 carbon atoms. A silyl group, a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, or a phenyl group having a halogen atom as a substituent. Moreover, the position to be substituted is preferably the 4-position on the phenyl group. Specific examples of such R ¹³ and R ¹⁴ are 4-t-butylphenyl group, 4-biphenylyl group, 4-chlorophenyl group, and 4-trimethylsilylphenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

The above X ¹¹ and Y ¹¹ are auxiliary ligands, and react with component [B] to produce an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, the types of ligands for X ¹¹ and Y ¹¹ are not limited, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Silyl group having a hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, amino group or alkylamino group having 1 to 20 carbon atoms represents.

The above Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, which connects two five-membered rings. represent. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ above include alkylene groups such as methylene, methylmethylene, dimethylmethylene, and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di(n - Alkylsilylene groups such as propyl)silylene, di(i-propyl)silylene, and di(cyclohexyl)silylene; (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene; arylsilylene groups such as diphenylsilylene; tetramethyl Alkyl oligosilylene group such as disilylene; germylene group; alkylgermylene group in which silicon of the above divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl)(aryl)germylene group ; Examples include an arylgermylene group. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferred, and an alkylsilylene group and an alkylgermylene group are particularly preferred.

Among the compounds represented by the above general formula (a1), preferred compounds are specifically exemplified below.
(1) dichloro[1,1'-dimethylsilylenebis{2-(2-furyl)-4-phenyl-indenyl}]hafnium,
(2) dichloro[1,1'-dimethylsilylenebis{2-(2-thienyl)-4-phenyl-indenyl}]hafnium,
(3) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(4) dichloro[1,1'-diphenylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(5) dichloro[1,1′-dimethylgermylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(6) dichloro[1,1′-dimethylgermylenebis{2-(5-methyl-2-thienyl)-4-phenyl-indenyl}]hafnium,
(7) dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(8) dichloro[1,1'-dimethylsilylenebis{2-(5-trimethylsilyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(9) dichloro[1,1′-dimethylsilylenebis{2-(5-phenyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(10) dichloro[1,1'-dimethylsilylenebis{2-(4,5-dimethyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(11) dichloro[1,1'-dimethylsilylenebis{2-(2-benzofuryl)-4-phenyl-indenyl}]hafnium,
(12) dichloro[1,1'-dimethylsilylenebis{2-(2-furfuryl)-4-phenyl-indenyl}]hafnium,
(13) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]hafnium,
(14) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}]hafnium,
(15) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}]hafnium,
(16) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-isopropyl-phenyl)-indenyl}]hafnium,
(17) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]hafnium,
(18) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]hafnium,
(19) dichloro[1,1'-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}]hafnium,
(20) dichloro[1,1′-dimethylsilylenebis(2-(2-furyl)-4-(2-naphthyl)-indenyl)]hafnium,
(21) dichloro[1,1′-dimethylsilylenebis(2-(2-furyl)-4-(2-phenanthryl)-indenyl)]hafnium,
(22) dichloro[1,1′-dimethylsilylenebis(2-(2-furyl)-4-(9-phenanthryl)-indenyl)]hafnium,
(23) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-biphenylyl)-indenyl}]hafnium,
(24) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}]hafnium,
(25) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}]hafnium,
(26) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthryl)-indenyl}]hafnium,
(27) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium,
(28) dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(1-naphthyl)-indenyl}]hafnium,
(29) dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-naphthyl)-indenyl}]hafnium,
(30) dichloro[1,1'-dimethylsilylenebis{(2-(5-t-butyl-2-furyl)-4-(2-phenanthryl)-indenyl)} hafnium,
(31) dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium,
(32) dichloro[1,1'-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2-(5-methyl-2-furyl)-4-phenyl-indenyl}] hafnium,
(33) Dichloro[1,1'-dimethylsilylene(2-methyl-4-phenyl-indenyl){2-(5-methyl-2-thienyl)-4-phenyl-indenyl}]hafnium, etc. can.

Among these, more preferred are:
(3) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(13) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]hafnium,
(16) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-isopropyl-phenyl)-indenyl}]hafnium,
(17) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]hafnium,
(18) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]hafnium,
(23) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-biphenylyl)-indenyl}]hafnium,
(25) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}]hafnium,
It is.

Also, particularly preferred are:
(13) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]hafnium,
(16) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-isopropyl-phenyl)-indenyl}]hafnium,
(17) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]hafnium,
(18) dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]hafnium,
It is.

2. Component [A-2]
Component [A-2] is a metallocene compound represented by the following general formula (a2).

[In general formula (a2), E ²¹ and E ²² each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent (however, The substituent is not a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.) Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

The above E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. However, the substituent is not a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur.
Among these, substituted cyclopentadienyl groups, substituted indenyl groups, and substituted azulenyl groups are preferred.
The substituent includes a hydrocarbon group having 1 to 6 carbon atoms, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Examples include aryl groups, halogen atoms, alkoxy groups, trialkylsilyl groups, and the like.
The hydrocarbon group having 1 to 6 carbon atoms may be the same as the hydrocarbon group having 1 to 6 carbon atoms in R ²¹ and R ²² in general formula (a3) described below. Further, the aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these may be represented by the general formula (a3) described below. may be the same as the aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or multiple hetero elements selected from these in R ²³ and R ²⁴ . Further, examples of the halogen atom include a fluorine atom and a chlorine atom, examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and examples of the trialkylsilyl group include a trimethylsilyl group. It will be done.

The above X ²¹ and Y ²¹ are auxiliary ligands, and react with component [B] as a co-catalyst to produce an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, the types of ligands for X ²¹ and Y ²¹ are not limited, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Silyl group having a hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, amino group or alkylamino group having 1 to 20 carbon atoms represents.

^Q21 is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via a carbon having 1 or 2 carbon atoms, or a carbon Represents either a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.

Specific examples of Q ²¹ above include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, dimethylsilylene, etc. Alkylsilylene groups such as (n-propyl)silylene, di(i-propyl)silylene, and di(cyclohexyl)silylene; (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene group such as tetramethyldisilylene; germylene group; alkylgermylene group in which silicon of the above divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; examples include arylgermylene group.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferred, and an alkylsilylene group and an alkylgermylene group are particularly preferred.
Furthermore, the above M ²¹ is zirconium or hafnium, preferably hafnium.

Component [A-2] is preferably a compound that forms a polymerization catalyst capable of copolymerizing a propylene monomer and a propylene macromer. Such a compound may also be a compound that forms a catalyst capable of simultaneously producing propylene macromers.
Component [A-2] is preferably a metallocene compound represented by the following general formula (a3) from the viewpoint of producing a propylene polymer with a high terminal vinyl content.

[In general formula (a3), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. represent. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

The above R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, etc. Preferably methyl , ethyl, n-propyl.

Further, R ²³ and R ²⁴ each independently have a carbon number of 6 to 30 and may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. , preferably an aryl group having 6 to 24 carbon atoms. Examples of such an aryl group include a phenyl group, a biphenylyl group, and a naphthyl group which may have a substituent. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4-(2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, and 3,5-dichloro-4-trimethylsilylphenyl.
In general formula (a3), Q ²¹ , M ²¹ , X ²¹ and Y ²¹ may be the same as Q ²¹ , M ²¹ , X ²¹ and Y ²¹ in general formula (a2), respectively.

Non-limiting examples of the metallocene compound represented by the above general formula (a3) include the following.
However, only representative exemplified compounds have been described to avoid a large number of complicated examples. Furthermore, although a compound in which the central metal is hafnium has been described, it is obvious that similar zirconium compounds can also be used, and that various ligands, crosslinking groups, or auxiliary ligands can be used as desired.
(1) dichloro{1,1'-dimethylsilylenebis(2-methyl-4-phenyl-4-hydroazulenyl)}hafnium,
(2) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium,
(3) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(4) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(5) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(3-chloro-4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(6) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(3-methyl-4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(7) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(3-chloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(8) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(9) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}]hafnium,
(10) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(2-naphthyl)-4-hydroazulenyl}]hafnium,
(11) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl}]hafnium,
(12) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(13) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(2-chloro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(14) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(9-phenanthryl)-4-hydroazulenyl}]hafnium,
(15) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium,
(16) dichloro[1,1'-dimethylsilylenebis{2-n-propyl-4-(3-chloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(17) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(3-chloro-4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(18) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(19) dichloro[1,1'-dimethylgermylenebis{2-methyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(20) dichloro[1,1'-dimethylgermylenebis{2-methyl-4-(4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(21) dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium,
(22) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl}]hafnium,
(23) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(24) dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(3,5-dichloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium, etc.

Among these, dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2- Methyl-4-(3-chloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(2-fluoro-4-biphenylyl)-4 -hydroazlenyl}] hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis {2-ethyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl- 4-(3,5-dichloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium.

Particularly preferably, dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl -4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(3-methyl-4-trimethylsilylphenyl)-4- hydroazulenyl}] hafnium, dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(3,5-dichloro-4-trimethylsilylphenyl)-4-hydroazulenyl}] Hafnium.

3. Component [B]
Component [B] is a compound or ion exchange layered silicate that reacts with component [A-1] and component [A-2] to form an ion pair.
Component [B] may be used alone or in combination of two or more. Preferred are ion exchange layered silicates.

3-1. Compounds that form ion pairs with component [A-1] and component [A-2] Compounds that react with component [A-1] and component [A-2] to form ion pairs include aluminum oxy compounds, Examples of the aluminum oxy compound include boron compounds, and specific examples of the aluminum oxy compound include compounds represented by the following general formulas (I) to (III).

In the above general formulas (I), (II), and (III), R ⁹¹ , R ¹⁰¹ and R ¹¹¹ are hydrogen atoms or hydrocarbon groups, preferably hydrocarbon groups having 1 to 10 carbon atoms, particularly preferably carbon atoms. Indicates a hydrocarbon group of numbers 1 to 6. Furthermore, the plurality of R ⁹¹ , R ¹⁰¹ and R ¹¹¹ may be the same or different. Further, p represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (I) and (II) are also called aluminoxane, and among these, methylaluminoxane or methylisobutylaluminoxane is preferred. It is also possible to use a plurality of the above aluminoxanes in combination within each group and between each group. The above aluminoxane can be prepared under various known conditions.
In the general formula (III), R ¹¹² represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. The compound represented by the general formula (III) is a mixture of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ¹¹² B(OH) ₂ in a ratio of 10:1 to It can be obtained by a reaction of 1:1 (molar ratio).
Examples of boron compounds include complexes of cations such as carbonium cations and ammonium cations and organic boron compounds such as triphenylboron, tris(3,5-difluorophenyl)boron, and tris(pentafluorophenyl)boron; Various organic boron compounds may be mentioned, such as tris(pentafluorophenyl)boron.

3-2. Ion exchange layered silicate Ion exchange layered silicate (hereinafter sometimes simply abbreviated as silicate) has a crystal structure in which layers formed by ionic bonds are stacked in parallel with each other due to bonding force. , refers to a silicate compound that has interlayer ions between its layers, and the contained interlayer ions are exchangeable.
Most silicates are naturally produced as main components of clay minerals. Generally, purification is performed by dispersing/swelling in water and using differences in sedimentation rate, etc. However, it is not necessary to completely remove impurities, and impurities other than ion-exchanged layered silicate (quartz) are purified. , cristobalite, etc.). Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, they may be more preferable than pure silicates, and such complexes are also included in the ion-exchanged layered silicate of component [B]. .
Furthermore, the silicates used in the present invention are not limited to naturally occurring ones, but may also be artificially synthesized ones.

Specific examples of ion-exchanged layered silicates include layered silicates with a 1:1 type structure and a 2:1 type structure, which are described in Haruo Shiramizu, "Clay Mineralogy," Asakura Shoten (1988), etc. Can be mentioned.
The 1:1 type structure refers to a structure based on a stack of one layer of tetrahedral sheet and one layer of octahedral sheet as described in the above-mentioned "Clay Mineralogy" and the like.
The 2:1 type structure refers to a structure based on stacking, in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.
Specific examples of ion-exchanged layered silicates having a 1:1 type structure include kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite, and halloysite, and serpentine group silicates such as chrysotile, lizardite, and antigorite. Examples include salt.
Specific examples of ion-exchanged layered silicates having a 2:1 type structure include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, and stevensite, vermiculite group silicates such as vermiculite, and mica. , mica group silicates such as illite, sericite, and glauconite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite group. These may form a mixed layer.
Among these, those whose main component is an ion exchange layered silicate having a 2:1 type structure are preferred. More preferably, the main component is a smectite group silicate, and even more preferably, the main component is montmorillonite.
The type of interlayer cation (cation contained between the layers of the ion exchange layered silicate) is not particularly limited, but main components include alkali metals of Group 1 of the periodic table such as lithium and sodium, calcium, magnesium, etc. Alkaline earth metals of Group 2 of the periodic table, or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold are relatively easily available. It is preferable in some respects.

The ion exchange layered silicate may be used in a dry state or in a liquid slurry state.
There is no particular restriction on the shape of the ion-exchanged layered silicate; it may be a naturally occurring shape or an artificially synthesized shape, or the shape may be modified by operations such as crushing, granulation, and classification. A processed ion exchange layered silicate may also be used.
Among these, it is particularly preferable to use a granulated ion-exchanged phyllosilicate because it provides good polymer particle properties when the ion-exchanged phyllosilicate is used as a catalyst component.
For the treatment method of ion-exchanged layered silicate, the description in paragraphs 0042 to 0071 of JP-A-2009-299046 can be referred to.

Component [B] preferably used in the present invention is a chemically treated ion-exchanged layered silicate, and the atomic ratio of Al/Si is 0.01 to 0.25, preferably 0.03 to 0.24. preferably in the range of 0.05 to 0.23. The Al/Si atomic ratio appears to be an indicator of the acid treatment strength of the clay portion.
Aluminum and silicon in the ion-exchanged layered silicate are measured by creating a calibration curve using chemical analysis according to the JIS method, and quantifying it using fluorescent X-rays.

4. Component [C]
Component [C] used in the present invention is an organoaluminum compound, and preferably an organoaluminum compound represented by the following general formula (4) is used.
(AlR _n X _3-n ) _m ...General formula (IV)
[In the above general formula (IV), R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n is 1 to 3, and m is 1 to 2 Each represents an integer. ]
The organoaluminum compounds can be used alone or in combination.
Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, trinpropylaluminum, trinorbutylaluminum, triisobutylaluminum, trinahexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminium. Examples include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride, and the like. Among these, preferred are trialkylaluminum and alkylaluminum hydride where m=1 and n=3. More preferably, R is trialkylaluminum having 1 to 8 carbon atoms.

5. Preparation of Catalyst The olefin polymerization catalyst preferably used in the present invention contains the above component [A-1], component [A-2], component [B] and component [C]. These can be obtained by contacting them inside or outside the polymerization tank. The olefin polymerization catalyst may be prepolymerized in the presence of an olefin.
The amounts of component [A-1], component [A-2], component [B] and component [C] to be used are arbitrary.
For example, the total usage amount of component [A-1] and component [A-2] is preferably in the range of 0.1 μmol to 1000 μmol, more preferably 0.5 μmol to 500 μmol, per 1 g of component [B].
The amount of component [C] used is the molar ratio of aluminum in component [C] to the total transition metal of component [A-1] and component [A-2], preferably 0.01 to 5×10 ⁶ , more preferably in the range of 0.1 to 1×10 ⁴ .
The order in which the component [A-1], component [A-2], component [B], and component [C] are brought into contact is arbitrary; after bringing two of these components into contact, the remaining component is brought into contact. or the four components may be brought into contact at the same time. In these contacts, a solvent may be used to ensure sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of aliphatic saturated hydrocarbons and aromatic hydrocarbons include hexane, heptane, and toluene. Further, as the prepolymerized monomer, propylene can be used as a solvent.

6. Prepolymerization The olefin polymerization catalyst is preferably subjected to prepolymerization, which involves bringing olefins into contact and polymerizing a small amount. Prepolymerization can improve catalyst activity and reduce manufacturing costs.
The olefins used are not particularly limited, but include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc. For example, propylene is preferred.
Any method of feeding the olefin can be used, such as a method of introducing the olefin into the prepolymerization tank at a constant rate or maintaining a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization temperature and prepolymerization time are not particularly limited, but are preferably in the range of -20°C to 100°C and 5 minutes to 24 hours.
Further, regarding the amount of prepolymerization, the mass ratio of the prepolymerized polymer to component [B] is preferably 0.01 to 100, more preferably 0.1 to 50.
Moreover, component [C] can also be added at the time of preliminary polymerization.
It is also possible to use a method in which a polymer such as polyethylene or polypropylene, or a solid inorganic oxide such as silica or titania is allowed to coexist during or after the contact of each of the above components.
The catalyst may be dried after prepolymerization. There are no particular restrictions on the drying method, but examples include vacuum drying, heat drying, and drying by circulating dry gas, and these methods may be used alone or two or more methods may be used in combination. May be used. In the drying process, the catalyst may be stirred, vibrated, fluidized, or left still.

II. Polymerization method of propylene polymer 1. Polymerization method Propylene is continuously polymerized in the presence of a propylene polymerization catalyst containing component [A-1], component [A-2], component [B] and component [C].
Any polymerization mode can be adopted as long as propylene can efficiently contact the olefin polymerization catalyst containing the component [A-1], component [A-2], component [B], and component [C]. . Among these, the so-called bulk polymerization method, in which propylene is used as a solvent without substantially using an inert solvent, is preferred, and single-stage polymerization is preferred.

For example, the polymerization temperature for bulk polymerization is more preferably 40°C or higher, and even more preferably 50°C or higher. Further, the upper limit is preferably 80°C or lower, more preferably 75°C or lower. The polymerization pressure in bulk polymerization is preferably 1.0 MPa or more and 5.0 MPa or less, and the lower limit is more preferably 1.5 MPa or more, still more preferably 2.0 MPa or more. Moreover, the upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.

The polymerization may be homopolymerization of propylene, and in addition to the propylene monomer, α-olefin comonomers having 2 to 20 carbon atoms other than propylene, such as ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl- Copolymerization may also be carried out using one or more comonomers selected from 1-pentene and the like.

2. Step of recovering propylene polymer The production method of the present invention includes a step of recovering the propylene polymer from the polymerization reactor while continuously introducing at least hydrogen and propylene into the polymerization reactor. In the process, the hydrogen and propylene are continuously introduced at a constant flow rate ratio.
In other words, even after the propylene polymer has been polymerized and the propylene polymer has begun to be discharged from the polymerization reactor, the propylene polymer must be continuously introduced until the ratio of the introduced flow rate of hydrogen and propylene is kept constant. The method is characterized in that the propylene polymer is not recovered as a product, but the propylene polymer is recovered as a product after the flow rate ratio is kept constant.

[Introduction of propylene]
The method for continuously introducing propylene into the polymerization reactor is not particularly limited, but includes, for example, a method in which liquefied propylene is introduced from the top of the polymerization reactor using a pump. Additionally, an amount of liquefied propylene smaller than the amount fed from the upper part of the polymerization reactor may be fed in portions from the catalyst feed pipe or the hydrogen pipe.

[Introduction of hydrogen]
When hydrogen is continuously introduced into the polymerization reactor, hydrogen can be introduced into the gas phase, liquid phase, or both within the polymerization reactor. In the production method of the present invention, hydrogen is preferably introduced directly into liquefied propylene because it is easy to maintain a constant introduction flow rate ratio to propylene. At this time, the hydrogen can be introduced at any position vertically or horizontally in the propylene liquid in the polymerization reactor. The place where hydrogen is introduced is preferably such that, relative to the depth H of the propylene liquid in the polymerization reactor, the position of the propylene liquid surface is 0 (H ), when the lowest position of the propylene liquid is expressed as 1 (H), it is easier to keep the introduced flow rate ratio to propylene constant, and to set it in the range of 0.5 (H) to 1.0 (H). , is preferable from the viewpoint of efficient contact between hydrogen and the catalyst in liquefied propylene, and more preferably in the range of 0.6 (H) to 0.8 (H).

[Introduction flow rate ratio of hydrogen and propylene]
The production method of the present invention is characterized in that, in the step of recovering the propylene polymer from the polymerization reactor, the flow rate ratio of hydrogen and propylene at which they are continuously introduced is kept constant.
When the hydrogen introduction flow rate and the propylene introduction flow rate are expressed in terms of weight flow rate (for example, kg/hr), the introduction flow rate ratio of hydrogen and propylene (H2/C3) is a propylene type that has excellent spreadability considering its fluidity. From the viewpoint of producing a polymer, it is preferably 3.30 wtppm or more, more preferably 4.00 wtppm or more, even more preferably 4.50 wtppm or more, and preferably 7.00 wtppm or less, and 6.50 wtppm. It is more preferable that it is below.
Note that the hydrogen introduction flow rate and the propylene introduction flow rate may be appropriately selected depending on the scale of producing the propylene polymer, and are not particularly limited. From the viewpoint of efficiently recovering the desired product at a high production rate, the average value of the hydrogen introduction flow rate may be, for example, 0.050 kg/hr or more and 0.130 kg/hr or less, and 0.060 kg/hr or more and 0.00 kg/hr or more. It is preferably 120 kg/hr or less, and the average value of the propylene introduction flow rate may be, for example, 16.0 T/hr or more and 24.0 T/hr or less, and 18.0 T/hr or more and 22.0 T/hr or less. It is preferable.

The branched propylene polymer produced in the present invention is produced by continuously combining hydrogen and propylene in the process of recovering the propylene polymer during continuous polymerization in the presence of a specific polymerization catalyst. By keeping the introduction flow rate ratio constant, a propylene polymer with excellent spreadability can be obtained while maintaining the melt tension necessary for molding. The details are described below.
If the hydrogen introduction flow rate relative to propylene fluctuates and the amplitude becomes large, specifically, what was polymerized when the hydrogen introduction flow rate was small and what was polymerized when it was large would mix.
In the method for producing a propylene polymer of the present invention, as described above, a propylene polymerization catalyst containing the component [A-1], component [A-2], component [B] and component [C] is used. As a result, a relatively low molecular weight macromer is produced from component [A-1], and this macromer is copolymerized by component [A-2], which produces a high molecular weight component, thereby producing a relatively high molecular weight polymer. generate. Therefore, the propylene polymer produced according to the present invention has a structure in which a branched structure is introduced even into a portion having a very high molecular weight.
For example, a polymer polymerized when the hydrogen introduction flow rate is small, that is, a polymer polymerized when the hydrogen concentration has decreased, has a higher molecular weight than the propylene polymer produced from component [A-2], which is a high molecular weight producing complex. Since the molecular weight is increased and the molecular weight distribution is broadened, the number of branches per molecule increases, resulting in an ultra-high molecular weight and highly branched component. Furthermore, in terms of propylene polymerization activity, component [A-1] is synergistically more activated by hydrogen than component [A-2]. On the other hand, when the amount of hydrogen decreases, the activation of component [A-1] becomes insufficient, and the proportion of component [A-2] becomes relatively large. As a result, the amount of this ultra-high molecular weight highly branched component increases relatively. Therefore, when the hydrogen introduction flow rate fluctuates and becomes small, the increase in the molecular weight of the propylene polymer produced from component [A-2] and the relative activation of component [A-2] synergistically increase the The molecular weight of the high-molecular weight, highly branched component becomes even higher, and the amount of the ultra-high molecular weight, highly branched component increases, resulting in a broadening of the molecular weight distribution and a change in the branching distribution. Furthermore, the ultra-high molecular weight highly branched component whose molecular weight is high and whose amount has increased is likely to cause oriented crystallization. Therefore, if a large amount of the above-mentioned ultra-high molecular weight highly branched components are contained, for example, when extrusion molding is performed, parts that are easy to crystallize and parts that are difficult to crystallize will be unevenly formed in the produced propylene polymer. Put it away. As a result, fluidity deteriorates, MaxDraw becomes too low, and spreadability deteriorates. Furthermore, if a large amount of ultra-high molecular weight, highly branched components such as those mentioned above are included, stress during molding will be concentrated in areas where non-uniformity occurs and crystals form quickly during extrusion foam molding. may be stretched unevenly, broken, or foamed.
On the other hand, for example, a polymer polymerized when the hydrogen introduction flow rate is large, that is, a polymer polymerized when the hydrogen concentration increases, has a narrow molecular weight distribution due to a decrease in the average molecular weight of the necessary ultra-high molecular weight highly branched component. In addition, the component whose molecular weight is reduced has a reduced number of branches per molecule. Furthermore, in terms of propylene polymerization activity, component [A-1] is synergistically activated by hydrogen to a greater extent than component [A-2]. Therefore, if there is a large amount of hydrogen, the amount of this ultra-high molecular weight highly branched component will be relatively reduced, resulting in a narrowing of the molecular weight distribution and a change in the branching distribution. Therefore, when the hydrogen introduction flow rate fluctuates and becomes large, the lowering of the molecular weight of the propylene polymer produced from component [A-2] and the relative activation of [A-1] synergistically increase the The molecular weight of the highly branched component becomes lower and its amount also decreases. As a result, although the spreadability becomes high, the fluidity becomes too high and the melt tension at 230° C. becomes too low.

For example, when hydrogen and propylene are introduced only before the start of polymerization, as in batch polymerization, the amount of hydrogen relative to propylene changes over time, causing the above-mentioned problems. Further, even in continuous polymerization, the step of recovering the polymer is an intermittent extraction step, so the amount of hydrogen relative to propylene changes over time, which can cause the above-mentioned problems.
In contrast, in the present invention, when continuously polymerizing a propylene-based polymer in the presence of a specific polymerization catalyst, in the step of recovering the propylene-based polymer, the introduction flow rate ratio of hydrogen and propylene to be continuously introduced is adjusted. By keeping it constant, it becomes possible to appropriate the average molecular weight, molecular weight distribution, branch distribution, and content of the ultra-high molecular weight highly branched component, making it difficult for oriented crystallization to occur. As a result, in the present invention, the ratio between the melt tension of the propylene polymer at high temperatures close to the temperature inside the molding machine and the melt tension at low temperatures during the cooling process of the molten resin is set to a specific range smaller than that in the past. Can be done. Specifically, the ratio of the propylene polymer's melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) is set to a specific range that is smaller than before. Can be done. As a result, in the present invention, it is possible to produce a propylene-based polymer that has excellent spreadability in relation to fluidity at a temperature intermediate between the high and low temperatures. The propylene polymer produced in this way, which has excellent spreadability in proportion to its fluidity, exhibits excellent spreadability even if its fluidity is low. It is possible to obtain a propylene-based polymer with excellent spreadability while maintaining the following properties.

In the present invention, keeping the introduction flow rate ratio of hydrogen and propylene constant means that the hydrogen introduction flow rate and the propylene introduction flow rate are expressed in weight flow rate (for example, kg/hr), and the introduction flow rate ratio of hydrogen and propylene is expressed as a weight flow rate (for example, kg/hr). A state in which the coefficient of variation (standard deviation/average value) of (H2/C3) is 0.020 or less can be set as a guideline.
Furthermore, keeping the introduction flow rate ratio of hydrogen and propylene constant is evaluated by the following method.
For the hydrogen introduction flow rate and the propylene introduction flow rate, read the instantaneous readings of the flowmeter to three significant digits at equal intervals, and use these to calculate the hydrogen and propylene introduction flow rates divided by the propylene introduction flow rate at each instant. The introduction flow rate ratio of propylene is (H2/C3). As the flowmeter, for example, a thermal type or Coriolis type flowmeter can be used. Further, the interval at which the indicated value of the flowmeter is read at equal intervals is, for example, 1 second to 10 minutes, or may be 30 seconds to 1 minute. The average value and standard deviation of the introduced flow rate ratio (H2/C3) at each moment read at the above-mentioned equal intervals are calculated. Further, the coefficient of variation is calculated as a value obtained by dividing this standard deviation by the average value. The coefficient of variation is a value that does not depend on the absolute value and has no unit.
The coefficient of variation (standard deviation/average value) of the introduction flow rate ratio (H2/C3) of hydrogen and propylene is set to be 0.020 or less, but preferably 0.018 or less, and 0.020 or less. 016 or less is more preferable.

[Hydrogen concentration]
In addition, in the production method of the present invention, the amount of propylene polymer produced per unit time is fixed, and the hydrogen concentration in the polymerization reactor is kept constant by keeping the introduction ratio of hydrogen and propylene constant. is preferable from the viewpoint of the effects of the present invention.
For example, in bulk polymerization, whether the hydrogen concentration in the polymerization reactor is constant can be confirmed by measuring the hydrogen concentration in the gas phase at equal intervals.
In the present invention, for example, the hydrogen concentration in the gas phase in bulk polymerization is preferably 50 volppm or more and 300 volppm or less from the viewpoint of producing a propylene polymer that has excellent spreadability in view of fluidity.
In addition, at this time, it is preferable that the fluctuation range of the hydrogen concentration has a coefficient of variation of 0.02 or less, which makes it easier to keep the MT190°C/MT230°C within the predetermined range, and to produce a propylene polymer that has excellent spreadability considering its fluidity. This is preferable from the point of view of
The hydrogen concentration in the gas phase in the polymerization reactor can be measured by sampling the gas at the following positions at equal intervals in the gas phase in the polymerization reactor. This is preferable because it can be understood. In the height direction of the polymerization reactor, the position of the propylene liquid surface is set at 0 from the top interface between the gas phase and the liquid phase during stirring toward the top of the ceiling of the polymerization reactor. (H'), when the top position of the ceiling of the polymerization reactor is expressed as 1 (H'), it is 0.2 (H') because it is not affected by air bubbles or liquid droplets from near the liquid surface. ) It is preferable to sample and measure the gas present in the range above 0.3 (H'), and it is further preferable to sample and measure the gas present in the range above 0.3 (H'). In addition, in order to avoid the influence of concentration changes due to propylene condensation on the ceiling, it is preferable to sample and measure gas that exists in a range below 0.9 (H'), and furthermore 0.8 (H'). ) It is preferable to sample and measure the gas present in the lower range.
The hydrogen concentration can be determined by performing gas chromatography measurements on the gas sampled at equal intervals. Examples of the intervals at which samples are taken at equal intervals include 1 second to 10 minutes, and may also be 30 seconds to 1 minute. The average value and standard deviation of the hydrogen concentration determined at the equal intervals are calculated. Further, the coefficient of variation is calculated as a value obtained by dividing this standard deviation by the average value.

[Introduction of catalyst]
In the present invention, when at least hydrogen and propylene are continuously introduced into the polymerization reactor, it is preferable that the catalyst is also continuously introduced.
When the catalyst introduction flow rate is expressed as a weight flow rate (for example, kg/hr), the introduction flow rate ratio of catalyst and propylene (catalyst/C3) should be set to produce a propylene-based polymer with excellent spreadability considering its fluidity. Therefore, it is preferably used at 10 wtppm or more, more preferably 20 wtppm or more. Furthermore, the upper limit is preferably 200 wtppm or less, more preferably 100 wtppm or less.

[Recovery of propylene polymer]
In the process of recovering propylene-based polymer as a product, in order to reduce fluctuations in hydrogen and propylene due to recovery, the slurry liquid is continuously discharged from the polymerization reactor and introduced into a degassing tank, and then unreacted propylene is collected. After discharging the propylene polymer as a gas, it is preferable to extract the propylene polymer intermittently.
Furthermore, in order to reduce the influence of such fluctuations, the intervals at which the propylene polymer is intermittently extracted from the degassing tank are set at intervals of 5 seconds to 30 seconds, and further at intervals of 10 seconds to 20 seconds. This is preferable because it is difficult to change the amount of polymer slurry extracted.
In addition, the amount of propylene polymer recovered as a product should be 6.0T to 10.0T per hour, and furthermore, should be 7.0T to 9.0T to efficiently recover the desired product. This is preferable from the point of view of recovery.

[Polymer slurry concentration]
For example, in bulk continuous polymerization, by adjusting the amount of propylene introduced into the polymerization reactor and the amount of produced polymer and unreacted propylene recovered, the amount of polymer held in the polymerization reactor is kept constant (steady). condition).
At this time, the ratio of the amount of polymer to the weight of propylene in the polymerization reactor (polymer slurry concentration) also becomes constant.
It is preferable to adjust the polymer slurry concentration so that the hydrogen concentration does not vary slightly depending on the location in the propylene solution. In the production method of the present invention, the polymer slurry concentration is preferably 55 wt% or less, more preferably 50 wt% or less, and still more preferably 45 wt% or less.
Further, from the viewpoint of productivity, it is preferable to adjust the concentration of the polymer slurry. In the production method of the present invention, the polymer slurry concentration is preferably 30 wt% or more, more preferably 35 wt% or more, and still more preferably 40 wt% or more.

III. Propylene polymer 1. Melt Tension In the present invention, the ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer to be produced is 1.8 or more and 2.5 The following shall apply.
Since the branched propylene polymer produced by the method of the present invention has a controlled branch structure (branch amount, branch length, branch distribution), oriented crystallization is less likely to occur. As a result, the melt properties of the propylene polymer produced by the method of the present invention are significantly improved, and the melt tension at 230°C (MT230°C) and the melt tension at 190°C (MT190°C) of the propylene polymer are significantly improved. The ratio (MT190°C/MT230°C) can be set in a specific range smaller than that in the conventional case. As a result, in the present invention, it is possible to produce a propylene-based polymer that has excellent spreadability considering its fluidity at a temperature intermediate between the above-mentioned high temperature and low temperature.

The melt tension ratio (MT 190°C/MT 230°C) needs to be 2.5 or less, preferably 2.4 or less, more preferably 2.5 or less, from the viewpoint of excellent spreadability considering fluidity. 3 or less.
On the other hand, the melt tension ratio (MT190°C/MT230°C) is required to be 1.8 or more, preferably 1.9 or more, and more preferably is 2.0 or more.

When the melt tension ratio (MT190°C/MT230°C), which indicates the temperature dependence of the melt tension, becomes larger than the range of 1.8 to 2.5, for example, in extrusion foam molding, the molten resin is extruded from the die and the temperature increases. During the cooling molding process, the melt tension increases rapidly, resulting in deterioration of spreadability during the molding process. Further, there arises a problem that the appearance of the molded article deteriorates as a result.
When this melt tension ratio (MT 190° C./MT 230° C.) is 2.5 or less, a propylene polymer having excellent spreadability considering its fluidity can be produced.
In addition, if this melt tension ratio (MT190°C/MT230°C) is 1.8 or more, for example, in extrusion foam molding, the molten resin is extruded from the die and the temperature cools. As the melt tension increases during the process, the independence of the bubbles and the sagging of the sheet can be improved.

The propylene polymer produced in the present invention has a lower limit of MT230°C of 3.6 g or more in order to obtain a propylene polymer with excellent spreadability while maintaining the melt tension necessary for molding. Preferably it is 4.0 g or more. The upper limit of MT230°C is 15.0 g or less, preferably 14.0 g or less, and more preferably 13.0 g or less.

In addition, the propylene polymer produced in the present invention has a lower limit of 7.2 g or more at MT190°C in order to obtain a propylene polymer with excellent spreadability while maintaining the melt tension necessary for molding. The amount is preferably 8.0 g or more, more preferably 9.0 g or more. The upper limit of MT190°C is 37.5 g or less, preferably 25.0 g or less, more preferably 15.0 g or less.

The method for measuring the melt tension at 230°C (MT230°C) and the melt tension at 190°C (MT190°C) is as follows using a melt tension tester (for example, Capillograph 1B manufactured by Toyo Seiki Co., Ltd.) at resin temperatures of 230°C and 190°C. The tension detected by the pulley when the resin is extruded into a string under the following conditions and wound around a roller is defined as the melt tension (MT 230°C, MT 190°C).
Capillary: diameter 2.1mm
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10 mm/min Winding speed: 4.0 m/min If breakage occurs at winding speed: 4.0 m/min, melt tension cannot be evaluated.

2. Fluidity The propylene polymer produced in the present invention must have a melt flow rate (MFR) of 3.0 g/10 minutes or more when measured at a temperature of 230°C and a load of 2.16 kg, because the melt tension is too high. 13.0 g/10 minutes or less is preferable from the viewpoint that the melt tension does not become too low.
MFR is an index indicating fluidity during melting, and changes depending on the average molecular weight, molecular weight distribution, and branched structure of the polymer.
The propylene polymer produced in the present invention has a melt flow rate (MFR) measured at a temperature of 230°C and a load of 2.16 kg, more preferably 4.0 g/10 minutes or more, and even more preferably 5.0 g. /10 minutes or more. On the other hand, the propylene polymer produced in the present invention has an MFR of preferably 12.0 g/10 minutes or less, further preferably 11.0 g/10 minutes or less, even more preferably 10.0/10 minutes or less. be.
The melt flow rate (MFR) was measured in accordance with JIS K6921-2 "Plastics - Polypropylene (PP) materials for molding and extrusion - Part 2: How to make test pieces and how to determine their properties". Conditions: Values measured at 230°C and a load of 2.16 kgf.
The propylene polymer produced by the present invention has a specific molecular weight distribution and branched structure, so that the ratio of melt tension at high temperatures close to the temperature inside the molding machine and melt tension at low temperatures during the cooling process of the molten resin is low. Within a certain range, flowability and spreadability are improved.

3. Molecular weight distribution Mw/Mn
The ratio [Mw/Mn] between weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) is an index expressing the spread of molecular weight distribution, and the larger this value is, the higher the molecular weight. This means that the distribution is wide. The propylene polymer produced in the present invention preferably has a molecular weight of 3.8 or more and 4.5 or less.
Mw/Mn of the propylene polymer produced in the present invention is more preferably 3.9 or more, and even more preferably 4.0 or more.
Molecular weight distribution Mw/Mn can be measured by gel permeation chromatography (GPC) in the same manner as the number average molecular weight (Mn) described above.

4. Branched structure Branch distribution The propylene polymer produced by the present invention has the following characteristics in the molecular weight distribution curve obtained from the absolute molecular weight (Mabs) measurement by MALLS obtained by 3D-GPC.
The branching index g' (Mnabs) in number average molecular weight (Mnabs) is 0.95 or more and 1.0 or less, more preferably 0.97 or more and 1.0 or less, and even more preferably 1.0. ,
The branching index g' (Mwabs) in weight average molecular weight (Mwabs) is 0.90 or more and 0.95 or less,
It is preferable that g' (Mzabs) in the z average molecular weight (Mzabs) is 0.80 or more and 0.90 or less.
By setting the branch distribution of the branched propylene polymer of the present invention within the above range, the melt tension ratio and melt tension can be set within a specific range, and fluidity and spreadability are improved.

[Definition of branching index g']
g' is given by the ratio of the intrinsic viscosity [η]br of a polymer with a long chain branched structure to the intrinsic viscosity [η]lin of a linear polymer having the same molecular weight, that is, [η]br/[η]lin. , takes a value smaller than 1.0 if a long chain branched structure exists.
Definitions are described, for example, in "Developments in Polymer Characterization-4" (J.V. Dawkins ed. Applied Science Publishers, 1983) and are indicators known to those skilled in the art.
g' can be obtained as a function of the absolute molecular weight Mabs, for example, by using a 3D-GPC equipped with a light scatterometer and a viscometer as detectors as described below.

[Method for measuring branched structure' by 3D-GPC]
In this specification, 3D-GPC refers to a GPC device to which three detectors are connected.
Three such detectors are a differential refractometer (RI), a viscosity detector (Viscometer) and a multi-angle laser light scattering detector (MALLS).
Alliance GPCV2000 manufactured by Waters is used as a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer).
Further, as a light scattering detector, a multi-angle laser light scattering detector (MALLS) DAWN-E manufactured by Wyatt Technology is used.
The detectors are connected in the order of MALLS, RI, and Viscometer.
The mobile phase solvent was 1,2,4-trichlorobenzene (to which the antioxidant Irganox 1076 manufactured by BASF Japan was added at a concentration of 0.5 mg/mL).
The flow rate was 1 mL/min, and the columns used were two GMHHR-H(S)HT manufactured by Tosoh Corporation connected in series.
The temperature of the column, sample injection section, and each detector was 140°C.
The sample concentration is 1 mg/mL, and the injection volume (sample loop volume) is 0.2175 mL.
To obtain the absolute molecular weight (Mabs) obtained from MALLS, the root mean square radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, use the data processing software ASTRA (version 4.73.04) included with MALLS. Then, perform calculations with reference to the following literature.
References:
1. Developments in polymer characterization, vol. 4. Essex: Applied Science; 1984. Chapter1.
2. Polymer, 45, 6495-6505 (2004)
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

[Calculation of branching index (g')]
The branching index g' is the ratio ([ η]br/[η]lin).
When a long chain branched structure is introduced into a polymer molecule, the radius of gyration becomes smaller compared to a linear polymer molecule of the same molecular weight. As the radius of gyration decreases, the intrinsic viscosity decreases, so as a long chain branched structure is introduced, the intrinsic viscosity of a branched polymer ([η] br) ([η]br/[η]lin) becomes smaller.
Therefore, when the branching index g' ([η]br/[η]lin) becomes a value smaller than 1.0, it means that it has a long chain branched structure.
Here, as the linear polymer for obtaining [η]lin, commercially available homopolypropylene (Novatec PP (registered trademark) grade name: FY6, manufactured by Nippon Polypropylene Co., Ltd.) is used. It is known as the Mark-Houwink-Sakurada equation that the logarithm of [η]lin of a linear polymer has a linear relationship with the logarithm of the molecular weight. You can extrapolate to get a numerical value.
In addition, if the branching index g' ([η]br/[η]lin) is calculated to be 1.0 or more, it will not theoretically be 1.0 or more, which is the value for a straight chain. Treated as 1.0.

[Control of each branching index (g') branch distribution at each molecular weight]
The values of the branching index g'(Mnabs), g'(Mwabs), and g'(Mzabs) representing the degree of branching in each average molecular weight Mnabs, Mwabs, and Mzabs are determined by the composition of multiple complexes on the catalyst, polymerization temperature, etc. It can be controlled by selecting the conditions or the polymerization mode or polymerization form such as continuous type. In the present invention, for example, when producing a propylene-based polymer with the same MFR, hydrogen is introduced continuously and the continuous introduction flow rate ratio of hydrogen and propylene is kept constant, thereby making it possible to initially A propylene polymer having a preferable branching distribution can be obtained compared to a propylene polymer produced by adding hydrogen.

5. Melt Spreadability The propylene polymer produced by the present invention has a controlled branch structure (branch amount, branch length, branch distribution), and therefore has improved melt properties. That is, by setting the ratio of the melt tension at 190° C. and 230° C. to a specific range while having a high melt tension at 230° C., the melt spreadability can be improved, and the spreadability is excellent considering the fluidity.
Melt spreadability can be evaluated by the maximum winding speed (MaxDraw) measured by the following method.
Using a melt tension tester (for example, Capillograph 1B manufactured by Toyo Seiki Co., Ltd.), extrude the resin into a string under the following conditions and gradually increase the winding speed to 4.0 m/min as it is wound around a roller. (acceleration: 5.4 cm/s ² ), the winding speed immediately before the string-like material is cut is defined as the maximum winding speed (MaxDraw).
Capillary: 2.1mm diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10mm/min Temperature: 210℃
Note that a larger MaxDraw means better spreadability.

By controlling the branching components and distribution, the propylene polymer produced by the present invention can have a large MaxDraw at 210°C while maintaining high melt tension at 230°C, and has good melt tension and melt spreadability. The balance has been improved.
In the propylene polymer produced in the present invention, the maximum winding speed (MaxDraw) at 210°C is preferably 70 m/min or more, more preferably 72 m/min when MT230°C is 3.6 g or more and less than 5.8 g. /min or more, more preferably 77 m/min or more.
In the propylene polymer produced in the present invention, the maximum winding speed (MaxDraw) at 210°C is preferably 60 m/min or more, more preferably 62 m/min when MT230°C is 5.8 g or more and less than 7.5 g. /min or more, more preferably 64 m/min or more.
In the propylene polymer produced in the present invention, the maximum winding speed (MaxDraw) at 210°C is preferably 52 m/min or more, more preferably 54 m/min when MT230°C is 7.5 g or more and less than 10.5 g. /min or more, more preferably 56 m/min or more.
In the propylene polymer produced in the present invention, the maximum winding speed (MaxDraw) at 210°C is preferably 42 m/min or more, more preferably 46 m/min when MT230°C is 10.5 g or more and 15.0 g or less. /min or more, more preferably 50 m/min or more.

The propylene polymer produced according to the present invention has excellent spreadability considering its fluidity.
The propylene polymer produced in the present invention has a relationship between the maximum winding speed (MaxDraw) (unit: m/min) and MFR (unit: g/10 min) as shown by the following formula (1'). It is preferable to satisfy the relationship shown in the following formula (1) from the viewpoint of durability, and it is more preferable to satisfy the relationship expressed by the following formula (1).
(MaxDraw)≧62×log(MFR)+7 ...Formula (1')
(MaxDraw)≧62×log(MFR)+10...Formula (1)
In general, increasing fluidity improves spreadability, but melt tension decreases.If you increase fluidity to improve spreadability, there is a problem that the melt tension becomes insufficient. It is desired that the propylene polymer has both high melt tension and excellent spreadability. Formula (1) shows that the propylene-based polymer produced by the present invention has excellent spreadability in proportion to its fluidity, compared to conventional propylene-based polymers. That is, in order to distinguish the propylene-based polymer of the present invention from conventional ones, the maximum winding speed (MaxDraw) is considered to be a function that has a positive correlation with the increase in fluidity (MFR), and the function is The parameters are set to show that the maximum winding speed (MaxDraw) of the propylene polymer produced by the present invention is larger in terms of fluidity than the maximum winding speed (MaxDraw) defined by the function. Specifically, based on the data of the example and the comparative example, assuming the values of the maximum winding speed (MaxDraw) and fluidity (MFR) that distinguish the example and the comparative example of the prior art, the maximum winding speed is The parameters of the relational expression established between (MaxDraw) and liquidity (MFR) are determined by the least squares method.
The propylene-based polymer produced in the present invention is produced by keeping the flow rate ratio of hydrogen and propylene constant during continuous polymerization of the propylene-based polymer in the presence of a specific polymerization catalyst. Since the tension ratio (MT 190° C./MT 230° C.) and the melt tension value are selected to fall within a specific range, equations (1′) and (1) can be satisfied.
The propylene polymer produced by the present invention, which has excellent spreadability in proportion to its fluidity, exhibits excellent spreadability even if its fluidity is low. It is possible to obtain a propylene-based polymer with excellent spreadability while maintaining the following properties.

The propylene polymer of the present invention obtained as described above is a branched propylene polymer having the following properties (A) to (E).
(A) The ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer is 1.8 or more and 2.5 or less.
(B) The MT230°C of the propylene polymer is 3.6 g or more and 15.0 g or less.
(C) The melt flow rate (MFR) measured at a temperature of 230° C. and a load of 2.16 kg is 3.0 g/10 minutes or more and 13.0 g/10 minutes or less.
(D) The ratio (Q value) of weight average molecular weight (Mw) to number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) is 3.8 or more and 4.5 or less.
(E) The maximum winding speed (MaxDraw) determined by the following measurement method and the melt flow rate (MFR) satisfy the relationship shown by the following formula (1').
(MaxDraw)≧62×log(MFR)+7...Formula (1')
<Maximum winding speed measurement method>
Using a melt tension tester, when extruding resin into a string under the following conditions and winding it up on a roller, the winding speed was increased from 4.0 m/min to an acceleration of 5.4 cm/s ² . The winding speed immediately before the string-like material is cut is defined as the maximum winding speed (MaxDraw).
Capillary: diameter 2.1mm
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10mm/min Temperature: 210℃

The propylene polymer of the present invention is a branched propylene polymer having the above-mentioned properties (A) to (E), but preferably has the properties described above for the propylene-based polymer produced according to the present invention. The numerical range of the characteristic may be the same as above.
The propylene polymer of the present invention may further have characteristic (F).
Characteristic (F): In the molecular weight distribution curve obtained by 3D-GPC,
The branching index g' (Mnabs) in number average molecular weight (Mnabs) is 0.90 or more and 1.00 or less,
The branching index g' (Mwabs) in weight average molecular weight (Mwabs) is 0.90 or more and 0.95 or less,
g' (Mzabs) in z average molecular weight (Mzabs) is 0.80 or more and 0.90 or less.

5. Applications of propylene polymer The propylene polymer produced in the present invention has excellent spreadability while maintaining the melt tension necessary for molding, and can be used for sheet molding, blow molding, thermoforming, foam molding, etc. In particular, it can be suitably used for sheet molding or extrusion molding.
The propylene polymer produced by the present invention has a high melt tension (MT230°C) at 230°C, which is close to the temperature inside the molding machine, within a predetermined range, so the molten resin is extruded from the die and bubbles grow. During the cooling process, it is easy to suppress bubble coalescence and maintain the independence of the bubbles. On the other hand, since the MT190°C/MT230°C ratio is small within an appropriate range, the melt tension increases rapidly during the cooling process. Since it is easy to suppress deterioration of the appearance of the molded product caused by this and has excellent spreadability, it can be particularly preferably used for extruded foam sheet molding. When the propylene-based polymer produced according to the present invention is applied to extruded foam sheet molding, it becomes possible to produce an extruded foam sheet with improved balance between cell independence and sheet surface appearance.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples.
The introduction flow rate ratio of hydrogen and propylene and the variation coefficient of hydrogen concentration were evaluated as follows.
[Variation coefficient of hydrogen and propylene introduction flow rate ratio]
For the hydrogen introduction flow rate and propylene introduction flow rate, read the instantaneous readings of the flowmeter to three significant figures every 60 seconds, and use these to calculate the hydrogen and propylene introduction flow rates by dividing the hydrogen introduction flow rate at each instant by the propylene introduction flow rate. The propylene introduction flow rate ratio (H2/C3) was used. The average value and standard deviation of the introduced flow rate ratio (H2/C3) at each moment read at equal intervals were calculated, and the coefficient of variation was calculated as a value obtained by dividing the standard deviation by the average value.

[Variation coefficient of hydrogen concentration]
A small amount of gas in the gas phase in the polymerization reactor was continuously taken out every 60 seconds, and the hydrogen concentration was determined by performing gas chromatography measurement on the collected gas.
The average value and standard deviation of the hydrogen concentrations measured at equal intervals were calculated, and the coefficient of variation was calculated as the value obtained by dividing the standard deviation by the average value.
Note that physical property measurements, analyzes, etc. in other Examples were conducted in accordance with the methods described above in this specification.

(Synthesis Example 1: Preparation of component [A-1] (complex 1))
(1) Synthesis of complex 1 As component [A-1] (complex 1), rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i -propylphenyl)indenyl}]hafnium was synthesized according to the method described in Example 13 (1) of JP-A No. 2009-299046.

(2) Evaluation of terminal vinyl ratio (Rv) (2-1) Preparation of catalyst (2-a) Chemical treatment of ion-exchanged layered silicate 645.1 g of water and 82.6 g of 98% sulfuric acid were added, and the temperature was raised to 95°C.
There, commercially available montmorillonite (Benclay KK manufactured by Mizusawa Chemical Industry Co., Ltd., Al = 9.78% by mass, Si = 31.79% by mass, Mg = 3.18% by mass, Al/Si (molar ratio) = 0.320, (average particle size: 14 μm) was added thereto, and the mixture was reacted at 95° C. for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction, and the mixture was filtered to obtain 255 g of a cake-like solid.
1 g of this cake contained 0.31 g of chemically treated montmorillonite (intermediate). The chemical composition of the chemically treated montmorillonite (intermediate) was Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, and Al/Si (molar ratio) = 0.222.
1545 g of distilled water was added to the above cake to form a slurry, and the temperature was raised to 40°C. 5.734 g of lithium hydroxide hydrate was added as a solid, and the mixture was reacted at 40° C. for 1 hour. After 1 hour, the reaction slurry was filtered and washed three times with 1 L of distilled water to again obtain a cake-like solid.
When the recovered cake was dried, 80 g of chemically treated montmorillonite was obtained. The chemical composition of this chemically treated montmorillonite is Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, Al/Si (molar ratio) = 0.222, Li = 0.53. It was mass%.

(2-b) Prepolymerization Put 20 g of the obtained chemically treated montmorillonite into a 1 L three-necked flask, add 131 mL of heptane to make a slurry, and add 50 mmol of triisobutylaluminum (a heptane solution with a concentration of 143.4 mg/mL) to this slurry. 69 mL) was added and stirred for 1 hour. After 1 hour, the solution was washed with heptane to a volume of 1/100 to make the total volume 100 mL.
The slurry solution containing the chemically treated montmorillonite was maintained at 50°C, and 4.2 mmol of tri-n-octyl aluminum (10.6 mL of a heptane solution with a concentration of 145.0 mg/mL) was added thereto and stirred for 20 minutes.
Then, add 0.3 mmol of rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}]hafnium (slurry with 50 mL of toluene). ) and stirred for 20 minutes while maintaining the temperature at 50°C.
Thereafter, 350 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40°C, propylene was introduced at a rate of 10 g/hour, and prepolymerization was carried out while maintaining the temperature at 40°C for 4 hours. Thereafter, the introduction of propylene was stopped, and residual polymerization was carried out at 40° C. for 1 hour.
After removing the supernatant of the obtained catalyst slurry by decantation, heptane was added again and decantation was performed to wash the prepolymerized catalyst. To the portion remaining after the above decantation, 12 mmol of triisobutylaluminum (16.6 mL of a heptane solution with a concentration of 143.4 mg/mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure at 40° C. for 2 hours to obtain 54.0 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.70.

(2-2) Polymerization After thoroughly drying the 3L autoclave under heating by passing nitrogen through it, the inside of the tank was replaced with propylene and cooled to room temperature. After introducing 2.86 mL of a heptane solution of triisobutylaluminum (143.4 mg/mL), 240 ml of hydrogen, and 750 g of liquefied propylene, the temperature was raised to 70°C. Thereafter, 100 mg of the catalyst, excluding the prepolymerized polymer, was pumped into a polymerization tank using high-pressure argon to initiate polymerization. After holding at 70° C. for 1 hour, unreacted propylene was quickly purged to stop polymerization. As a result, about 128 g of propylene homopolymer having an MFR of 38 was obtained.

(2-3) Terminal vinyl ratio Regarding the obtained propylene homopolymer, the terminal vinyl ratio (Rv) was evaluated by the method described in this specification.
According to structural formula (1-a) and structural formula (1-e), [Vi] = 0.61, Mn = 63467, and the terminal vinyl ratio (Rv) = 0.92.
According to the structural formula (1-b), [Vd] was 0.10, and the terminal vinylidene ratio (Rvd) was 0.15.

(Synthesis Example 2: Preparation of component [A-2] (complex 2))
(1) Synthesis of complex 2 As component [A-2] (complex 2), rac-dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium was synthesized according to the method described in Example 7 of JP-A-11-240909.

(2) Evaluation of terminal vinyl ratio (Rv) (2-1) Preparation of catalyst (2-a) Chemical treatment of ion-exchange layered silicate Evaluation of terminal vinyl ratio of the component [A-1] (complex 1) The chemical treatment of ion-exchanged layered silicates was carried out in the same manner as in .
(2-b) Put 20 g of the chemically treated montmorillonite obtained into a 1 L three-necked flask, add 131 mL of heptane to make a slurry, and add 50 mmol of triisobutylaluminum (69 mL of heptane solution with a concentration of 143.4 mg/mL). was added and stirred for 1 hour. After 1 hour, the solution was washed with heptane to a volume of 1/100 to make the total volume 100 mL.
The slurry solution containing the chemically treated montmorillonite was maintained at 50°C, and 4.2 mmol of tri-n-octyl aluminum (10.6 mL of a heptane solution with a concentration of 145.0 mg/mL) was added thereto and stirred for 20 minutes.
To this, add 0.3 mmol of rac-dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium (slurried with 50 mL of toluene), The mixture was stirred for 20 minutes while maintaining the temperature at 50°C.
Thereafter, 350 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40°C, propylene was introduced at a rate of 10 g/hour, and prepolymerization was carried out while maintaining the temperature at 40°C for 4 hours. Thereafter, the introduction of propylene was stopped, and residual polymerization was carried out at 40° C. for 1 hour.
After removing the supernatant of the obtained catalyst slurry by decantation, heptane was added again and decantation was performed to wash the prepolymerized catalyst. To the portion remaining after the above decantation, 12 mmol of triisobutylaluminum (16.6 mL of a heptane solution with a concentration of 143.4 mg/mL) was added and stirred for 10 minutes. By drying this solid under reduced pressure at 40° C. for 2 hours, 62.2 g of a dry prepolymerized catalyst was obtained. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.11.

(2-2) Polymerization After thoroughly drying a 3L autoclave under heating by passing nitrogen through it, the inside of the tank was replaced with propylene and cooled to room temperature. After introducing 2.86 mL of a heptane solution of triisobutylaluminum (143.4 mg/mL), 240 ml of hydrogen, and 750 g of liquefied propylene, the temperature was raised to 70°C. Thereafter, 30 mg of the catalyst, excluding the prepolymerized polymer, was pumped into a polymerization tank using high-pressure argon to initiate polymerization. After holding at 70° C. for 1 hour, unreacted propylene was quickly purged to stop polymerization. As a result, about 157 g of propylene homopolymer having an MFR of 1.0 was obtained.

(2-3) Terminal vinyl ratio Regarding the obtained propylene homopolymer, the terminal vinyl ratio (Rv) was evaluated by the method described in this specification.
According to the structural formula (1-a) and the structural formula (1-e), [Vi]=0, Mn=148356, and the terminal vinyl ratio (Rv)=0.
According to the structural formula (1-b), [Vd] = 0.17 and the terminal vinylidene ratio (Rvd) = 0.6.

(Preparation Example 1: Preparation of catalyst for propylene polymerization)
(1) Chemical treatment of ion-exchanged layered silicate Chemical treatment of ion-exchanged layered silicate was carried out in the same manner as in the evaluation of the terminal vinyl content of component [A-1] (complex 1) to obtain 80 g of chemically treated montmorillonite. Ta. The chemical composition of this chemically treated montmorillonite is Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, Al/Si (molar ratio) = 0.222, Li = 0.53. It was mass%.

(2) Prepolymerization Put 20 g of the chemically treated montmorillonite obtained above into a three-necked flask (volume 1 L), add heptane (131 mL) to make a slurry, and add 50 mmol of triisobutylaluminum (concentration 143.4 mg/ 69 mL of heptane solution) was added and stirred for 1 hour. After 1 hour, the slurry solution containing the chemically treated montmorillonite was washed to 1/100 with heptane, and the total volume of the slurry solution containing the chemically treated montmorillonite was adjusted to 100 mL, and the temperature was maintained at 50°C.
432 μmol of triisobutylaluminum (0.6 mL of a heptane solution with a concentration of 143.4 mg/mL) was added to the slurry solution and stirred for 5 minutes. In another flask (volume 200 mL), rac-dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)- Solution 1 was prepared by dissolving hafnium (108 μmol) in toluene (33 mL). The solution 1 was added to the slurry solution in a 1 L flask, and the mixture was stirred for 60 minutes while maintaining the temperature at 50°C.
Furthermore, 3528 μmol of tri-normal octylaluminium (8.9 mL of a heptane solution with a concentration of 145.0 mg/mL) was added to the slurry solution and stirred for 10 minutes. In another flask (volume 200 mL), rac-dichloro[1,1'-dimethylsilylene bis{2-(5-methyl-2-furyl)- Solution 2 was prepared by dissolving 4-(4-i-propylphenyl)indenyl}]hafnium (252 μmol) in toluene (36 mL). The solution 2 was added to the slurry solution in a 1 L flask, and the mixture was stirred for 20 minutes while maintaining the temperature at 50°C.
Thereafter, 321 mL of heptane was added to the slurry solution, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40°C, propylene was introduced at a flow rate of 10 g/hr, and prepolymerization was carried out while maintaining the temperature at 40°C for 4 hours. Thereafter, the introduction of propylene was stopped, and residual polymerization was carried out at 40° C. for 1 hour.
After removing the supernatant of the obtained catalyst slurry by decantation, heptane was added again and decantation was performed to wash the prepolymerized catalyst. To the portion remaining after the above decantation, 12 mmol of triisobutylaluminum (16.6 mL of a heptane solution with a concentration of 143.4 mg/mL) was added and stirred for 10 minutes. By drying this solid under reduced pressure at 40° C. for 2 hours, 62.0 g of a dry prepolymerized catalyst (prepolymerized catalyst 1) was obtained. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.10.

(Example 1: Production of propylene polymer)
After sufficiently replacing the interior of the stirred high-pressure reaction vessel (L/D=1.2) with an internal volume of 100 ^m3 with propylene, sufficiently purified liquefied propylene was supplied at a flow rate of 20 T/hr and triisobutylaluminum at a flow rate of 80 kg/hr. The temperature was maintained at 70±0.1° C., and the liquid in the tank was continuously drawn out so that the amount of liquid in the tank was maintained at 29.1T.
Next, after hydrogen was gradually added at a rate of 0.080 kg/hr to stabilize the hydrogen concentration in the tank, prepolymerized catalyst 1 was gradually added, and the amount of hydrogen was further finely adjusted until the hydrogen was finally reduced to 0. .110 kg/hr, and prepolymerized catalyst 1 was continuously introduced at a flow rate of 1.40 g/hr (weight excluding prepolymerized polymer), and the polymer density in the polymerization reactor was 40 wt. %, and the propylene polymer (powder) began to be continuously discharged at 8.0 T/hr. Thereafter, when the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes, Collection of propylene polymer (powder) has begun.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 5.50 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.009.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the following granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(granulation)
Tetrakis [methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate], which is a phenolic antioxidant, is added to 100 parts by weight of propylene polymer powder. Methane (product name: IRGANOX1010, manufactured by BASF Japan Co., Ltd.) 0.125 parts by weight, phosphite-based antioxidant tris(2,4-di-t-butylphenyl)phosphite (product name: IRGAFOS 168, BASF) Japan Co., Ltd.) was mixed for 3 minutes at room temperature using a high-speed stirring mixer (product name: Henschel mixer), and then melt-kneaded using a twin-screw extruder to produce propylene. Pellets of the polymer were obtained. The twin-screw extruder used was KZW-25 manufactured by Technovel, the screw rotation speed was 400 RPM, and the kneading temperature was set at 80, 160, 210, and 230 °C from the bottom of the hopper (the same temperature from the bottom to the die exit). did.

(Example 2: Production of propylene polymer)
In the polymerization of the propylene polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.112 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 5.60 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.009.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above-mentioned granulation conditions to obtain propylene polymer pellets. Using the granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 3: Production of propylene polymer)
In the polymerization of propylene-based polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.114 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 5.70 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.008.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above-mentioned granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 4: Production of propylene polymer)
In the polymerization of the propylene polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.116 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 5.80 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.008.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above-mentioned granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 5: Production of propylene polymer)
In the polymerization of propylene-based polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.068 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the introduction flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 3.40 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.014.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 6: Production of propylene polymer)
In the polymerization of the propylene polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.083 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 4.41 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.011.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 7: Production of propylene polymer)
In the polymerization of the propylene polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.093 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 4.94 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.010.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 8: Production of propylene polymer)
In the polymerization of propylene-based polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.100 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 5.00 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.010.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Example 9: Production of propylene polymer)
In the polymerization of the propylene polymer in Example 1, the final hydrogen introduction flow rate was changed from 0.110 kg/hr to 0.118 kg/hr, and while adjusting the catalyst amount, the polymer density in the polymerization reactor was adjusted to 40 wt. % and the amount of propylene polymer (powder) drawn out was maintained at 8.0 T/hr. After that, the coefficient of variation of the flow rate ratio of continuously introduced hydrogen to continuously introduced propylene became 0.020 or less, and the MFR of the propylene polymer stabilized within the range of ±0.5 g/10 minutes. After 6 hours had passed, we started collecting powder.
During recovery, the average flow rate ratio of continuously introduced hydrogen to continuously introduced propylene was 5.90 wtppm, standard deviation was 0.048 wtppm, and coefficient of variation was 0.008.
After thoroughly drying the obtained propylene polymer (powder), it was granulated under the above granulation conditions to obtain propylene polymer pellets. Using the granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 1 shows the polymerization conditions and evaluation results.

(Comparative Example 1: Production of propylene polymer)
After the interior of the stirring autoclave with an internal volume of 200 liters was sufficiently replaced with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. After adding 1.13 g of hydrogen and 0.12 mol of triisobutylaluminum (0.47 L of a heptane solution with a concentration of 50 g/L), the internal temperature was raised to 70°C. Next, 0.86 g (weight excluding the prepolymerized polymer) of Prepolymerized Catalyst 1 was injected with argon to initiate polymerization. Internal temperature was maintained at 70°C. After 120 minutes, 100 ml of ethanol was injected under pressure to purge unreacted monomers, and the inside of the autoclave was purged with nitrogen to stop the polymerization.
The obtained powder was thoroughly dried to obtain 19.7 kg of propylene polymer. The propylene polymer was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 2 shows the polymerization conditions and evaluation results.

(Comparative Example 2: Production of propylene polymer)
Polymerization was carried out in the same manner as in Comparative Example 1 except that the amount of hydrogen added was changed to 1.14 g. As a result, 20.9 kg of propylene polymer was obtained. The propylene polymer was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 2 shows the polymerization conditions and evaluation results.

(Comparative Example 3: Production of propylene polymer)
Polymerization was carried out in the same manner as in Comparative Example 1 except that the amount of hydrogen added was changed to 1.15 g. As a result, 21.3 kg of propylene polymer was obtained. The propylene polymer was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 2 shows the polymerization conditions and evaluation results.

(Comparative Example 4: Production of propylene polymer)
Polymerization was carried out in the same manner as in Comparative Example 1 except that the amount of hydrogen added was changed to 1.16 g. As a result, 21.3 kg of propylene polymer was obtained. The propylene polymer was granulated under the above granulation conditions to obtain propylene polymer pellets. Using granulated pellets, MFR, Mw/Ms, branching index g' (Mnabs), g' (Mwabs), g' (Mzabs), MT230°C, MT190°C, maximum winding speed at 210°C (MaxDraw210 ℃) was measured.
Table 2 shows the polymerization conditions and evaluation results.

(Summary of results)
The propylene polymers of Examples 1 to 9 produced by the method for producing propylene polymers of the present invention were polymerized and recovered while keeping the introduced flow rate ratio of hydrogen and propylene constant, and the melt tension ratio (MT190°C/MT230°C ℃) and the melt tension at 230°C were controlled within a specific range, it was revealed that it was possible to produce a propylene polymer with excellent spreadability while maintaining the melt tension necessary for molding.
On the other hand, the propylene-based polymers of Comparative Examples 1 to 4, which were produced using the conventional production method, had hydrogen added at the beginning of the polymerization and were produced using a polymerization method that could vary the ratio of hydrogen to propylene. If the ratio (MT190°C/MT230°C) is not within a specific range and the melt tension at 230°C is increased to a certain range, the spreadability will worsen, and if the spreadability is improved, the melt tension at 230°C will become smaller. It became clear that the melt tension necessary for molding could not be maintained.
FIG. 2 shows the relationship between MFR and maximum winding speed for Examples 1 to 9 and Comparative Examples 1 to 4. Comparing data at the same MFR level, the Examples exhibit higher maximum take-up speeds than the Comparative Examples. For this reason, there is a step of recovering the propylene polymer from the polymerization reactor while continuously introducing at least hydrogen and propylene into the polymerization reactor, and in the recovery step, the hydrogen and propylene are continuously introduced into the polymerization reactor. It can be seen that the spreadability commensurate with the fluidity is improved by keeping the introduction flow rate ratio constant and by keeping the melt tension ratio (MT190°C/MT230°C) within a specific range.

Claims (2)

In a method for producing a propylene polymer in which propylene is continuously polymerized in the presence of a propylene polymerization catalyst containing the following components [A-1], component [A-2], component [B] and component [C]. ,
It has a step of recovering the propylene-based polymer from the polymerization reactor while continuously introducing at least hydrogen and propylene into the polymerization reactor, and in the recovery step, the hydrogen and propylene are introduced at a flow rate at which the hydrogen and propylene are continuously introduced. keeping the ratio constant,
The ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer is 1.8 or more and 2.5 or less, and MT230°C is 3. A method for producing a propylene polymer, characterized in that the amount is 6 g or more and 15.0 g or less.
Component [A-1]: Metallocene compound represented by general formula (a1) .

[In general formula (a1), R ¹¹ and R ¹² each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 30 carbon atoms that may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these; Or represents a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, M 11 ^represents hafnium, X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]
Component [A-2]: Metallocene compound represented by general formula (a3) .

[In general formula (a3), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. represent. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group or germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms; M 21 ^represents hafnium; X ²¹ and Y ²¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: A compound or ion exchange layered silicate that reacts with component [A-1] and component [A-2] to form an ion pair.
Component [C]: Organoaluminum compound. A branched propylene homopolymer having the following properties (A) to (E).
(A) The ratio of the melt tension at 230°C (MT230°C) to the melt tension at 190°C (MT190°C) (MT190°C/MT230°C) of the propylene polymer is 1.8 or more and 2.5 or less.
(B) The MT230°C of the propylene polymer is 3.6 g or more and 15.0 g or less.
(C) The melt flow rate (MFR) measured at a temperature of 230° C. and a load of 2.16 kg is 3.0 g/10 minutes or more and 13.0 g/10 minutes or less.
(D) The ratio (Q value) of weight average molecular weight (Mw) to number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) is 3.8 or more and 4.5 or less.
(E) The maximum winding speed (MaxDraw) determined by the following measurement method and the melt flow rate (MFR) satisfy the relationship shown by the following formula (1').
(MaxDraw)≧62×log(MFR)+7...Formula (1')
<Maximum winding speed measurement method>
Using a melt tension tester, when extruding resin into a string under the following conditions and winding it up on a roller, the winding speed was increased from 4.0 m/min to an acceleration of 5.4 cm/s ² . The winding speed immediately before the string-like material is cut is defined as the maximum winding speed (MaxDraw).
Capillary: 2.1mm diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10mm/min Temperature: 210℃

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