JP7024842B2 - Propene homopolymer - Google Patents

Description

The present disclosure relates to a propylene homopolymer, and more particularly to a propylene homopolymer in which the relationship between the melting point and the crystallization temperature is good in a specific melting point range.

Polypropylene has high chemical stability, excellent mechanical characteristics, and is inexpensive, so it is widely used as a living industry member, an industrial member, and the like.
Further, in some polypropylenes, a polymer having a vinyl group at one end is known.

For example, the number average molecular weight (Mn) of 2 obtained by using a catalytic composition containing a chiral stereorigid transition metal compound typified by dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride has a number average molecular weight (Mn) of 2. A terminal vinyl group-containing propylene polymer having a stereoregularity of 1,000 daltons to 50,000 daltons and having a total number of vinyl groups per 1,000 carbon atoms of 7,000 ÷ Mn or more is known (Patent Document 1). Claim 10, Non-Patent Document 1).

Further, a terminal vinyl group-containing propylene polymer obtained by polymerizing in a dilute state of propylene using the catalyst composition containing this dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride can be obtained. Further, a terminal vinyl having a long-chain branched structure obtained by copolymerizing with a propylene monomer and having a polydispersity of 4.0 or less, a melting point of more than 90 ° C., and a weight average branching index (g) of less than 0.95. A group-containing propylene polymer is known (Example 25-30 of Patent Document 2 Non-Patent Document 2).

Furthermore, a 5-membered ring is formed at the 2-position of the inden ring represented by rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium. Polymerization at a relatively low temperature where bulk polymerization is possible under high propylene concentration conditions such as bulk polymerization using a catalyst containing a metallocene compound having a crosslinked inden ring having a constituent heterocycle and an aryl group at the 4-position. The weight average molecular weight (Mn) is more than 50,000 and less than 130,000, the ratio (Q value) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.0 or more and 4.0 or less, and the terminal. Known are terminal vinyl group-containing propylene polymers having a vinyl ratio of 0.7 or more, a terminal vinylidene ratio of less than 0.1, an orthodichlorobenzene-eluting component at 40 ° C. of 3% by weight or less, and a mm content of 95% or more. (Claim 1 of Patent Document 3)

The terminal vinyl group-containing propylene polymers of Patent Document 1 and Non-Patent Document 1 require slurry polymerization at a relatively high temperature and low pressure as a polymerization condition in order to obtain a terminal vinyl structure with high selectivity. The amount of heterogeneous bonds derived from the growth reaction due to irregular insertion of monomers is large.
Similarly, the terminal vinyl group-containing propylene polymer of Patent Document 2 is also obtained by performing slurry polymerization at a low pressure, and the produced propylene polymer is irregular as shown in Examples 26, 28 and 30. The amount of heterogeneous binding derived from insertion is large.
The terminal vinyl group-containing propylene polymer of Patent Document 3 is a polymer having a relatively small amount of heterogeneous bonds derived from a growth reaction due to irregular insertion of a propylene monomer, but has a number average molecular weight of more than 50,000. There is a problem that defects are likely to occur in the molding processing characteristics and the appearance of the molded product due to the fact that the crystallinity is too high with respect to the melting point and the crystallization is fast.
Therefore, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride is also used, and bulk polymerization is performed at a relatively low temperature using clay as a co-catalyst, and hydrogen is used as a molecular weight adjuster to obtain a practical molecular weight. When used, the formation of terminal vinyl groups is insufficient, and a propylene polymer having a sufficient amount of long-chain branches cannot be obtained.
Therefore, in Patent Document 4, similarly, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride is used to carry out polymerization exceeding the critical temperature of propylene to efficiently introduce long-chain branching. However, there is a problem that the melting point becomes too high.

Japanese Patent Publication No. 2001-525461 Special Table 2002-523575 Publication No. Japanese Unexamined Patent Publication No. 2009-299045 European Patent No. 2231726

Macromol. Rapid Commun. 2000, 21, 1103-1107 Macromolecules. 2002, 35 3838

In view of the above circumstances, the present disclosure provides a novel propylene homopolymer in which the relationship between the melting point and the crystallization temperature is good in a specific melting point range.

The propylene homopolymer of the present disclosure is characterized by having the following properties (i) to (ii).
Characteristic (i): Melting point (Tm) is 145 ° C. or higher and 149 ° C. or lower Characteristic (ii): Melting point (Tm) and crystallization temperature (Tc) satisfy the following formula (1) Tm-Tc≤0.907 × Tm- 99.64 ... Equation (1)

The propylene homopolymer of the present disclosure may further have the following properties (iii) to (iv).
Characteristic (iii): Isotactic triad fraction (mm) is 90% or more Characteristic (iv): Heterogeneous bond amount (2,1 bond) is 0.2 mol% or less, and heterogeneous bond amount (1,3 bond) Is 0.2 mol% or less

The propylene homopolymer of the present disclosure may further have the following property (v).
Characteristic (v): Number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 50,000 or less.

The propylene homopolymer of the present disclosure may further have the following property (vi).
Characteristics (vi): ¹³ The terminal vinyl ratio measured by C-NMR is 0.7 or more.

The propylene homopolymer of the present disclosure may further have the following properties (vii).
Characteristic (vii): Number of long-chain branches is 0.1 / 1000 monomers or more

The propylene homopolymer of the present disclosure may further have the following properties (viii).
Characteristics (viii): Tm-Tc ≧ 0.907 × Tm-103.64 ... Equation (2) in which the melting point (Tm) and the crystallization temperature (Tc) satisfy the following equation (2).

According to the present disclosure, it is possible to provide a novel propylene homopolymer having a good relationship between a melting point and a crystallization temperature in a specific melting point range.

It is a figure explaining the baseline and section of the chromatogram in GPC. It is a figure which shows the relationship between the melting point and the crystallization temperature of the propylene homopolymer of an Example.

1. 1. Propylene homopolymer The propylene homopolymer of the present disclosure is characterized by having the following properties (i) to (ii).
Characteristic (i): Melting point (Tm) is 145 ° C. or higher and 149 ° C. or lower Characteristic (ii): Melting point (Tm) and crystallization temperature (Tc) satisfy the following formula (1) Tm-Tc≤0.907 × Tm- 99.64 ... Equation (1)

Characteristic (i): Melting point (Tm)
The propylene homopolymer of the present disclosure has a melting point (Tm) of 145 ° C. or higher and 149 ° C. or lower as measured by differential thermal scanning calorimetry (DSC).
The higher the melting point of the propylene polymer, the better the heat resistance and rigidity. Further, by controlling the melting point so that it does not become too high, the solubility in a solvent can be increased.
Therefore, the melting point of the propylene homopolymer of the present disclosure is preferably 149 ° C. or lower, more preferably 148 ° C. or lower, still more preferably 147.5 ° C. or lower.
The melting point of the propylene homopolymer of the present disclosure is preferably 145 ° C. or higher, more preferably 146 ° C. or higher, still more preferably 146.5 ° C. or higher.
The melting point (Tm) can be controlled by the amount of heterogeneous bonds (stereoregularity, positional regularity) and the isotactic chain length.
In order to obtain the melting point of the propylene homopolymer of the present disclosure, a complex having the optimum heterogeneous bond amount (stereoregularity, positional regularity) and isotactic chain length is selected, and the polymerization temperature and pressure are further adjusted. The melting point can be controlled by such means.

Characteristics (ii), Characteristics (viii): Relationship between melting point (Tm) and crystallization temperature (Tc) The propylene homopolymer of the present disclosure has a melting point (Tm) and crystals measured by differential thermal scanning calorimetry (DSC). The following formula (1) is satisfied with respect to the crystallization temperature (Tc).
Tm-Tc ≤ 0.907 x Tm-99.64 ... Equation (1)
Further, preferably, the following formula (1)'is satisfied.
Tm-Tc ≤ 0.907 x Tm-100.64 ... Equation (1)'
That is, the propylene homopolymer of the present disclosure has a difference between the melting point (Tm) and the crystallization temperature (Tc) measured by differential thermal scanning calorimetry (DSC) (supercooling degree (Tm-Tc): unit ° C.). However, it is characterized by being small in proportion to the melting point (Tm).
The fact that the crystallization temperature (Tc) is high in proportion to the melting point (Tm) means that it is easier to crystallize, the crystallization rate is faster, and the crystals become smaller and denser than the propylene polymer having the same melting point (Tm). do. When such a propylene polymer that is easily crystallized is used, it means that the transparency due to the crystal size and amount, the heat resistance due to the crystal amount, and the rigidity are increased in proportion to the melting point (Tm).
Therefore, the propylene homopolymer of the present disclosure needs to satisfy the above formula (1). If the degree of supercooling (Tm-Tc) is too large, the above-mentioned transparency, heat resistance, and rigidity will deteriorate in terms of melting point (Tm).

On the contrary, if the degree of supercooling (Tm-Tc) is too small, the crystallization corresponding to the melting point (Tm) is too fast, the size and amount of crystal formation cannot be controlled, and the desired physical properties may not be obtained. ..
Therefore, it is desirable that the propylene homopolymer of the present disclosure satisfies the following formula (2).
Tm-Tc ≧ 0.907 × Tm-103.64 ... Equation (2)

[Control of supercooling degree (Tm-Tc)]
The melting point (Tm) is controlled by the amount of heterogeneous bonds (stereoregularity, positional regularity) and the isotactic chain length. Further, in a normal propylene homopolymer, there is a primary correlation between Tc and Tm.
On the other hand, the fact that the crystallization temperature (Tc) corresponding to the melting point (Tm) becomes high is contributed by the primary structure other than the heterogeneous bond amount (stereoregularity, positional regularity) and the isotactic chain length. Especially when it has a branched structure, it is considered that the branched point promotes crystallization, and the more branches there are, the smaller the degree of supercooling.
Therefore, in order to obtain the polymer of the present disclosure, a complex that optimizes the heterogeneous bond amount (stereoregularity, positional regularity), isotactic chain length, and branching amount is selected, and further, the polymerization temperature and pressure are adjusted. The degree of supercooling can be controlled by making adjustments and the like.

[Measuring method of melting point (Tm) and crystallization temperature (Tc)]
In the present disclosure, the melting point (Tm) is DSC6200 manufactured by Seiko Instruments Co., Ltd., a sheet-shaped sample piece is packed in a 5 mg aluminum pan, and the temperature is once raised from room temperature to 200 ° C. at a heating rate of 100 ° C./min. After holding for 1 minute, the temperature was lowered to 20 ° C. at 10 ° C./min to determine the crystallization temperature (Tc) as the maximum crystal peak temperature (° C.) when crystallized, and then 200 ° C. at 10 ° C./min. It can be obtained as the maximum melting peak temperature (° C.) when the temperature is raised to the maximum.

Characteristics (iii): Isotactic triad fraction (mm) of 90% or more The propylene homopolymer of the present disclosure preferably has high stereoregularity.
In the present disclosure, the stereoregularity of the propylene homopolymer is not limited, but the mm fraction (isotactic triad fraction) of the propylene unit 3 chain calculated by ¹³ C-NMR is preferably 90% or more. Is 93% or more, more preferably 95% or more.
The higher the mm fraction of the propylene homopolymer, the higher the control.
Further, if the mm fraction is smaller than the above value, the mechanical properties such as the elastic modulus of the product are lowered.

The mm fraction of the propylene unit 3 chain is obtained by substituting the integrated intensity of the ¹³ C signal measured by the ¹³ C-NMR measurement into the following equation (3).
mm (%) = Imm × 100 / (Imm + 3 × Imrmrm) ・ ・ ・ Equation (3)
Here, Imm represents the integrated intensity of the ¹³ C signal in which the propylene unit 3 chain is attributed to the bonding mode of mm, and the integrated intensity of the ¹³ C signal having a chemical shift in the range of 23.6 to 21.1 ppm (hereinafter referred to as “I”). It is calculated as _{23.6 to 21.1} ”).
Imrrm represents the integral intensity of the ¹³ C signal in which the propylene unit 5 chain is attributed to the bond mode of mrrm, and is the value shown by I _{19.8 to 19.7} .
The ¹³ C-NMR measurement for obtaining the mm fraction of 3 chains of propylene units can be carried out by a method using an AV400 type NMR apparatus of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe described later.
Attribution of spectra can be made with reference to Polymer Journal, Vol. 16, p. 717 (1984), Asakura Shoten, Macromolecules, 8 卷, p. 687 (1975), and Polymer, Vol. 30, p. 1350 (1989). can.

Characteristic (iv): Heterogeneous bond amount (2,1 bond) is 0.2 mol% or less, and heterogeneous bond amount (1,3 bond) is 0.2 mol% or less There is no limitation on the positional regularity of the propylene homopolymer. However, it is preferable that the 2,1 bond calculated by ¹³ C-NMR is 0.2 mol% or less and the 1,3 bond is 0.2 mol% or less.
The 2,1 bond is more preferably 0.15 mol% or less, still more preferably 0.12 mol% or less, and particularly preferably 0.10 mol% or less.
The 1,3 bond is more preferably 0.18 mol% or less, still more preferably 0.16 mol% or less, and particularly preferably 0.15 mol% or less.
By reducing the amount of heterogeneous bonds, when mixed or applied to other propylene polymers or substrates, the mixing efficiency is increased, the coating efficiency is improved, and the coating agent is less likely to be peeled off.
Further, by controlling the regularity (stereotype / position) of propylene so as not to be too high, the solubility in a solvent can be enhanced and the reactivity of the terminal vinyl can be enhanced.

The amount of heterologous bonds (molar concentration) is calculated from the following formula using the signal intensity of ¹³ C-NMR spectrum.
Propene 2,1 bond (mol%)
= I2,1-P × 100 / (I1,2-P + I2,1-P + I1,3-P)
Propene 1,3 bond (mol%)
= I1,3-P × 100 / (I1,2-P + I2,1-P + I1,3-P)
Here, I1,2-P, I2,1-P, and I1,3-P are obtained as follows.
I1,2-P = I _48.80-44.50
I2,1-P = (I _{35.72 to 35.63} + I _{35.83 to 35.77} ) / 2
I1,3-P = I _37.41-37.21 / 2

Characteristic (v): The number average molecular weight (Mn) measured by GPC is 50,000 or less. The propylene homopolymer of the present disclosure preferably has a number average molecular weight (Mn) of 50,000 or less, more preferably 4. It is 50,000 or less, more preferably 40,000 or less.
Within the above range, the reaction efficiency of the functionalization that modifies the terminal vinyl group is good.
In addition, since the amount of terminal vinyl groups per unit mass increases, a sufficient amount of functional groups can be introduced by modification.
In addition, the solubility in the solvent is increased.
On the other hand, the number average molecular weight (Mn) is preferably 10,000 or more, more preferably 15,000 or more, and further preferably 20,000 or more.
Within the above range, a secondary structure derived from the regularity (stereo / position) characteristics of the homopolymer can be easily taken, and crystallinity (melting point and crystallization temperature) can be exhibited.
The number average molecular weight (Mn) of this propylene homopolymer can be controlled by selecting a complex having a special structure having a high β-methyl desorption reaction rate, which is a termination reaction, as a catalyst component for polymerization. Examples of such a complex structure include a bisinden complex having a bulky heterocyclic group at the 2-position described later and having an aryl group or the like which may be substituted at the 4-position.
The desorption reaction rate can also be controlled by changing the polymerization temperature, the concentration of propylene, and the pressure. For example, in the complex shown in the examples, the higher the polymerization temperature, the smaller the number average molecular weight (Mn) can be.

Here, the value of the number average molecular weight (Mn) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and the measuring instrument are as follows.
Equipment: Waters GPC (ALC / GPC, 150C)
Detector: FOXBORO MIRAN, 1A, IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 mL / min Injection volume: 0.2 mL
To prepare the sample, prepare a 1 mg / mL solution using the sample and ODCB (containing 0.5 mg / mL dibutylhydroxytoluene (BHT)), and dissolve at 140 ° C. for about 1 hour. Let me do it.
The baseline and section of the obtained chromatogram are as shown in FIG.
Further, the conversion from the holding capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve using standard polystyrene prepared in advance. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brands: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method.
Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ^-4 , α = 0.7
PP: K = 1.03 × 10 ^-4 , α = 0.78

The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC of the propylene homopolymer of the present disclosure is preferably in the range of 2.0 or more and 4.0 or less.
When Mw / Mn is 4.0 or less, the amount of unnecessary low molecular weight components can be reduced, and satisfactory physical properties can be obtained.
Further, when Mw / Mn is 2.0 or more, a desired amount of high molecular weight component can be obtained, and the balance between the physical properties derived from the crystal structure and the functionality derived from the reactivity is improved.
Further, Mw / Mn is more preferably 2.3 or more and 3.9 or less, and further preferably 2.6 or more and 3.8 or less.

Characteristics (vi): ¹³ The terminal vinyl ratio measured by C-NMR is 0.7 or more. The propylene homopolymer of the present disclosure preferably has a terminal vinyl ratio of 0.7 or more.
In the present disclosure, the terminal vinyl ratio means the ratio of chains having a vinyl group at the end to the total polymer chains of the propylene homopolymer, and is calculated by the following formula.
(Terminal vinyl ratio) = {[Vi] / ((total number of terminals) -LCB number)} x 2
(However, [Vi] is the number of terminal vinyl groups per 1000 monomer units calculated by ¹ H-NMR. The total number of terminals is the total number of terminals per 1000 monomer units calculated by ¹³ C-NMR. The number of LCBs is the number of methine carbons at the root of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.)
The propylene homopolymer of the present disclosure preferably has a terminal vinyl ratio of 0.7 or more, more preferably 0.75 or more. More preferably, it is 0.8 or more, ideally 1.0 (all polymer chains have a vinyl group at the end).

[Relationship between reaction mechanism and terminal structure]
In the present disclosure, the relationship between the reaction mechanism and the obtained terminal structure in obtaining a propylene homopolymer having a terminal vinyl ratio of 0.7 or more is as follows.
In the polymerization of propylene, β-hydrogen desorption generally occurs, and the terminal of the vinylidene structure (propyl-vinylidene structure) represented by the following structural formula (1-b) is generated.
When hydrogen is used, chain transfer usually occurs preferentially to hydrogen, and the end of the i-butyl structure represented by the following structural formula (1-c) is generated.
However, when a complex having a special structure is used as a polymerization catalyst, a special chain transfer reaction generally called β-methyl elimination occurs, and the vinyl structure (1-propenyl structure) represented by the following structural formula (1-a) occurs. (Reference: Polymer. Rapid Commun. 2000, 21, 1103-1107).
Further, in the polymerization of propylene, the following terminal structure is generated due to the reaction mechanism. After propylene is inserted and β-hydrogen desorption occurs, the terminal of the i-butenyl structure represented by the following structural formula (1-d) is formed via a π-allyl intermediate formed by further extracting hydrogen from the γ-position.
In addition, propylene may cause irregular 2,1 insertion, but after such an irregular bond, it is chain-migrated to hydrogen, β-hydrogen desorption, or via a π-allyl intermediate. When hydrogen is desorbed, the n-butyl structure represented by the following structural formula (1-e), the 1-butenyl structure represented by the following structural formula (1-f), and the terminal vinylene structure represented by the following structural formula (1-g) ( 2-Butenyl structure) ends are formed. Here, the 1-butenyl structure (structural formula (1-f)) is included in the terminal vinyl group of the present disclosure.

The starting end is always a saturated hydrocarbon end, and unsaturated bonds do not appear at both ends.
This means that when the propylene homopolymer of the present disclosure is modified, only one end is modified. On the other hand, for example, a polymer having a terminal unsaturated bond obtained by thermally decomposing a propylene polymer may have a vinylidene (Vd) group at both ends, and the unsaturated bond may be modified from this. Both ends may be modified, resulting in a different morphology from the propylene homopolymers of the present disclosure.

Therefore, in order to increase the terminal vinyl ratio, the reactions that give rise to the structural formulas (1-b) to (1-e), (1-g) and (1-h) are suppressed, and the structural formula (1-a) is used. , (1-f) are preferred, such that the polymerization conditions are such that the reaction is promoted.
Among the polymerization conditions, regarding the catalyst, a 5-membered heterocycle having a structure of a bisindenylhafnium complex and having a specific substituent at the 2-position of the indene ring which is a ligand, and the indene ring, which will be described later, and the indene ring. By using a catalyst for olefin polymerization containing a metallocene compound substituted with an aryl group having a specific substituent at the 4-position of the above, the chain transfer reaction resulting in the structural formula (1-a) can be promoted.
Further, when a catalyst for olefin polymerization containing such a metallocene compound is used, surprisingly, even when hydrogen is used, the β-methyl elimination reaction occurs preferentially although the activity increases, and vinyl Structure (1-propenyl structure): Structural formula (1-a) is mainly produced. This selectivity can also be controlled by changing the polymerization temperature. For example, in the catalyst for olefin polymerization containing the metallocene compound shown in the examples, the higher the polymerization temperature, the higher the terminal vinyl ratio can be.

Further, in the present disclosure, in the polymerization of propylene, in addition to the regular monomer unit inside the polymer chain due to the reaction mechanism, the following internal olefins may be generated to form a monomer unit constituting the polymer.
After inserting propylene and causing β-hydrogen desorption, the internal vinylidene structure shown in the structural formula (1-m) is formed by further inserting propylene via a π-allyl intermediate formed by further extracting hydrogen from the γ position. Can be generated.
After propylene causes irregular 2,1 insertion and β-hydrogen desorption, further propylene is inserted via the π-allyl intermediate to form the internal trisubstituted olefin structure shown in structural formula (1-n). sell.
After inserting propylene and causing β-methyl desorption, the internal vinylene structure shown in the structural formula (1-o) is formed by further inserting propylene via a π-allyl intermediate formed by further extracting hydrogen from the γ position. Can be generated.

[How to specify the terminal vinyl ratio]
¹ H-NMR and ¹³ C-NMR can be carried out by the methods described below to specify the terminal vinyl ratio.
[Sample preparation and measurement conditions]
An NMR sample having an inner diameter of 10 mmφ, in which 200 mg of a sample is mixed with o-dichlorobenzene / deuterated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane which is a reference substance for chemical shift. Place in a tube and dissolve evenly with a block heater at 150 ° C.
The NMR measurement is performed using an AV400 type NMR device of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹ H-NMR is used to quantify the unsaturated end. ¹ The measurement conditions of 1 H-NMR are that the temperature of the sample is 120 ° C., the pulse angle is 4.5 °, the pulse interval is 2 seconds, and the number of integrations is 512 times.
The chemical shift sets the proton signal of hexamethyldisiloxane to 0.09 ppm, and the chemical shift of signals by other protons is based on this.
¹³ C-NMR is used to quantify the saturated terminal. ¹³ The measurement conditions of C-NMR are the sample temperature of 120 ° C., the pulse angle of 90 °, the pulse interval of 15 seconds, the number of integrations of 1024 times, and the measurement is carried out by the broadband decoupling method.
The chemical shift sets the ¹³ C signal of hexamethyldisiloxane to 1.98 ppm, and the chemical shift of the other ¹³ C signals is based on this.

[Calculation method of the number of unsaturated ends]
In ¹ H-NMR, the proton signal of the unsaturated bond of structural formula (1-a) 1-propenyl and structural formula (1-f) 1-butenyl is 5.08 to 4.85 ppm in ¹ H-NMR spectrum. Is detected by overlapping with a signal of 5.86 to 5.69 ppm. Therefore, the number of terminal vinyl groups [Vi] is the total number of 1-propenyl and 1-butenyl, the amount of unsaturated bonds per 1000 monomers, and the signal intensity of ^{1 1} H-NMR spectrum is used as the following formula. Ask from.
Structural formula (1-a) + Structural formula (1-f): [Vi] = Ivi × 1000 / Ital

The number of terminal vinylidene groups [Vd] is calculated from the following formula using the signal intensity of ¹ H-NMR spectrum as the number of propyl-vinylidene and the amount of unsaturated bonds per 1000 monomers in total.
Structural formula (1-b): [Vd] = Ivd × 1000 / Ital
Similarly, the number of i-butenyl groups [i-butenyl], the number of vinylene terminals [terminal vinylene], and the number of internal vinylidene [internal vinylidene] can be obtained from the following equations.
Structural formula (1-d): [i-butenyl] = Iibu × 1000 / Ital
Structural formula (1-g): [Terminal vinylene] = Ivnl × 1000 / Ital
Structural formula (1-m): [Internal vinylidene] = Ivid × 1000 / Ital

Here, Ivi, Ivd, Iibu, Ivnl, and Iivd are structural formula (1-a) + structural formula (1-f), structural formula (1-b), structural formula (1-d), and structural formula, respectively. (1-g) represents a characteristic value of a signal based on the structural formula (1-m), and is an amount represented by the following formula.
Ivi = (I _5.08-4.85 + I _5.86-5.69 ) / 3,
Ivd = (I _4.79-4.65 ) / 2,
Iibu = I _5.30-5.08 ,
Ivnl = (I _5.58-5.30 ) / 2,
Iivd = (I _4.85-4.79 ) / 2

I indicates the integrated intensity, and the subscript value 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.
In addition, Total is a quantity represented by the following formula.
Itotal = IC3 + Ivi + Ivd + Iibu + Ivnl + Iivd
IC3 represents a characteristic value of a signal based on propylene, and is a quantity represented by the following formula.
IC3 = 1/6 x Imain
Imain is the sum of the polymer main chain and the proton signal at the saturated end detected in ¹ H-NMR spectrum from 4.00 to 0.00 pm.

[Calculation method of the number of saturated ends]
The number of saturated terminals below is calculated from the following formula using the signal intensity of ¹³ C-NMR spectrum as the number per 1000 monomers.
Structural formula (1-c): [i-butyl] = Ii-butyl × 1000 / Ital-C
Structural formula (1-e): [n-butyl] = Inbu × 1000 / Ital-C
Structural formula (1-h): [n-propyl] = Impr × 1000 / Ital-C
Structural formula (1-i): [2,3-dimethylbutyl] = I2,3-dime × 1000 / Ital-C
Structural formula (1-j): [3,4-dimethylpentyl] = I3,4-dime × 1000 / Ital-C

Further, the propylene homopolymer of the present disclosure includes the following 2,1 bonds, 1,3 based on the irregular insertion of propylene, in addition to the structure based on the regular 1,2 insertion of propylene inside the polymer. Can have a bond.

Here, Ii-butyl, Inbu, Impr, I2,3-dim, and I3,4-dim are structural formulas (1-c), structural formulas (1-e), structural formulas (1-h), and structures, respectively. It represents the characteristic value of the signal based on the formula (1-i) and the structural formula (1-j), and is a quantity represented by the following formula.
Ii-butyl = (I _23.80-23.70 + I _25.80-25.70 ) / 2
Inbu = I _14.06-14.02
Impr = (I _{14.44 to 14.42} + I _{30.46 to 30.45} ) / 2
I2,3-dime = (I _{16.21 to 16.17} + I _{31.86 to 31.81} ) / 2
I3,4-dime = _I12.0-11.60

Further, Ital-C is a quantity represented by the following formula.
Ital-C = Ii-butyl + Inbu + Impr + I2,3-dime + I3,4-dime + I1,2-P + I2,1-P + I1,3-P
I1,2-P is the characteristic value of the signal based on the bond of 1,2 inserted propylene, I2,1-P is the characteristic value of the signal based on the bond of 2,1 inserted propylene, and I1,3-P is the characteristic value of the signal based on the bond of 2,1 inserted propylene. , 1, 3 Represents a characteristic value of a signal based on the bond of inserted propylene, and is an amount represented by the following formula.
I1,2-P = I _48.80-44.50
I2,1-P = (I _{35.72 to 35.63} + I _{35.83 to 35.77} ) / 2
I1,3-P = I _37.41-37.21 / 2

[Calculation method of total number of ends]
The total number of terminals is the total number of terminals per 1000 monomer units calculated by ¹³ C-NMR and ¹ H-NMR, respectively, and specifically, structural formulas (1-a) to structural formulas per 1000 monomer units. It is the sum of the number of terminals up to (1-j).

Characteristic (vii): The number of long-chain branches is 0.1 / 1000 monomers or more The propylene homopolymer of the present disclosure may have a long-chain branch (LCB) structural portion represented by the following structural formula (A).

[However, in the structural formula (A), P ¹ , P ² , and P ³ are propylene polymer residues, each having one or more propylene units, and C _br is a branched chain having 7 or more carbon atoms. The methine carbon at the root is shown, and C _a , C _b , and C _c indicate the methylene carbon adjacent to the methine carbon (C _br ). ]
In the structural formula (A), there are three main chains of the propylene polymer: P1-C _br -P ² line, P ^{1 -} C _br -P ³ line, or P ² -C _br -P ³ line. Exists. Therefore, correspondingly, the C _br -P ³ line, the C _br -P ² line, or the C _br -P ¹ line can be the above-mentioned branched chain. In itself, P ¹ , P ² , and P ³ may contain a branched carbon (C _br ) different from that of the C _br described in the structural formula (A).
Here, the attribution of the LCB structure is 44.1 to 43.9 ppm, 44.7 to 44.5 ppm and 44.9 to 44.7 ppm of three methylene carbons (Ca, by ¹³ C- _NMR of the propylene polymer. C _b , C _c ) is observed, and it is observed as methine carbon (C _br ) at 31.7 to 31.5 ppm. It is characterized in that three methylene carbons close to C _br are observed in three non-equivalent parts of the diastereotopic.
The number of LCBs is the number of methine carbons (C _br ) at the root of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.
A branched chain having more than 6 carbon atoms and a branched chain having 6 or less carbon atoms can be distinguished by the difference in the peak position of the methine carbon at the root of the branch (Macromol.chem. Phys. 2003, Vol. 204, 1738). See page.).
In the present disclosure, the number of LCBs is not particularly limited, but is usually preferably 0.1 / 1000 monomers or more and 0.5 / 1000 monomers or less.

2. 2. Production of Propylene Copolymer The propylene homopolymer of the present disclosure is obtained by homopolymerizing propylene, for example, by using a catalyst for olefin polymerization containing the following components (A), (B) and (C). Can be manufactured.
Component (A): Metallocene compound represented by the following general formula (1)

[R ¹¹ and R ¹² independently form a 5-membered ring having at least one hydrocarbon group having 3 or more carbon atoms which may have a heteroatom as a substituent (however, 5-membered group). The heteroatom of the heterocyclic group constituting the ring does not directly bond to the alkazienyl group).
R ¹³ and R ¹⁴ are independently aryl groups having a substituent only at the 4-position, and the substituent contains at least one atom selected from the group consisting of a hetero atom and a halogen atom. It is also a good hydrocarbon group having 3 to 6 carbon atoms.
X ¹¹ and Y ¹¹ independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms. , An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms.
^Q11 has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a gelmilene group that may be present.
However, the substituent of the heterocyclic group constituting the 5-membered ring and the substituent of the aryl group are not the same, and among the substituents of the heterocyclic group, the substitution having the largest total number of carbon atoms and heteroatoms. The total number of groups is larger than the total number of carbon atoms and heteroatoms of the substituent of the aryl group. ]
Component (B): A compound that reacts with the component (A) to form an ion pair or an ion-exchangeable layered silicate component (C): an organoaluminum compound.

[Catalyst for olefin polymerization]
(1) Ingredient (A)
The component (A) is a metallocene compound represented by the above general formula (1).
In the general formula (1), R ¹¹ and R ¹² are heterocyclic groups independently constituting a 5-membered ring having a hydrocarbon group having 3 or more carbon atoms which may have a hetero atom as a substituent. However, the heteroatom of the heterocyclic group constituting the 5-membered ring does not directly bond with the alkazienyl group.
In R ¹¹ and R ¹² , the orientation of the inserted propylene is regularly controlled by introducing a substituent of appropriate size on the heterocyclic group. Furthermore, this substituent facilitates the β-methyl group of the growing polymer chain to move toward the empty coordination field on the transition metal, so that the β-methyl elimination reaction facilitates and the propylene having a terminal vinyl group introduced in a highly selective manner. A polymer can be obtained.

R ¹¹ and R ¹² are preferably identical to each other.
Further, in R ¹¹ and R ¹² , it is preferable that the carbon next to the hetero atom of the heterocyclic group constituting the 5-membered ring is bonded to the alkazienyl group in the general formula (1).
The number of carbon atoms of the hydrocarbon group may be 3 or more, preferably 7 or less, more preferably 6 or less, still more preferably 5 or less, and particularly preferably 4.
Examples of the heteroatom include silicon, oxygen, sulfur, nitrogen, boron, phosphorus and the like, which may be present in the carbon chain and intervened between carbon-carbon bonds.
Further, R ¹¹ and R ¹² are heterocyclic groups independently constituting a 5-membered ring having a substituent only at the 5-position, and the substituent may have a hetero atom and has 3 carbon atoms. It is preferable that the hydrocarbon group is as described above (however, the heteroatom of the heterocyclic group constituting the 5-membered ring does not directly bond with the alkazienyl group).
The hydrocarbon group having 3 or more carbon atoms as the substituent of the heterocyclic group may be any of alkyl, cycloalkyl and aromatic hydrocarbon groups, but is preferably a tertiary hydrocarbon group.

Preferred structures of R ¹¹ and R ¹² include a complex 5-membered ring structure represented by any of the following general formulas (2-1), (2-2) or (2-3).

[R ²¹ and R ²² are independently hydrocarbon groups having 3 or more carbon atoms which may have hydrogen atoms or heteroatoms, and at least one of R ²¹ and R ²² may have heteroatoms. Represents a good hydrocarbon group with 3 or more carbon atoms. However, the heteroatom of the hydrocarbon group does not directly bond with the heterocyclic group constituting the 5-membered ring. Further, R ²¹ and R ²² do not combine to form a ring. ]

Preferred examples of R ²¹ and R ²² are i- ^propyl , n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl. It is a group, a frill group, particularly preferably t-butyl, and R ²² is preferably a hydrogen atom.

In the general formula (1), R ¹³ and R ¹⁴ are independently aryl groups having a substituent only at the 4-position, and the substituent is at least one selected from the group consisting of a hetero atom and a halogen atom. It is a hydrocarbon group having 3 to 6 carbon atoms which may contain an atom of.
It is preferable that R ¹³ and R ¹⁴ are the same as each other.
The aryl group is preferably a phenyl group.
Examples of the heteroatom include silicon, oxygen, sulfur, nitrogen, boron, phosphorus and the like.
When the hydrocarbon group contains a heteroatom, the heteroatom may exist in the carbon chain and intervene between carbon-carbon bonds.
The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The number of carbon atoms of the hydrocarbon group may be 3 or more and 6 or less, preferably 5 or less, more preferably 4 or less, and further preferably 3.
The hydrocarbon group having 3 to 6 carbon atoms as the substituent of the aryl group may be any of alkyl, cycloalkyl and aromatic hydrocarbon groups, but is preferably a secondary hydrocarbon group.

Preferred structures of R ¹³ and R ¹⁴ include a structure having a substituent at the 4-position on the phenyl group represented by the following general formula (3).
4-R ³¹ -Ph- ・ ・ ・ General formula (3)
[R ³¹ is a hydrocarbon group having 3 to 6 carbon atoms which may contain at least one atom selected from the group consisting of heteroatoms and halogen atoms. However, R ³¹ is different from R ²¹ and R ²² . ]
Preferred examples of R ³¹ are i-propyl, n-butyl, i-butyl, s-butyl, trimethylsilyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl group, frill group, and particularly. It is preferably i-propyl.

In the present disclosure, the substituent of the heterocyclic group constituting the 5-membered ring and the substituent of the aryl group are not the same, and the total number of carbon atoms and heteroatoms among the substituents of the heterocyclic group is The total number of the largest substituents is greater than the total number of carbon and heteroatoms of the aryl group substituents.
That is, when there are a plurality of non-identical substituents on the heteroatoms (R ¹¹ and R ¹² ) (for example, when the heteroatoms have different structures at the 4th and 5th positions), each of them. The total number of carbon atoms and heteroatoms of the substituent is the maximum. The total number of carbon atoms and heteroatoms of the substituent and the total number of carbon atoms and heteroatoms of the substituent on the aryl group are calculated. When compared, the total number of substituents having the largest total number of carbon atoms and heteroatoms on the heterocyclic group is the total number of carbon atoms and heteroatoms of the substituents on the aryl group. Greater than.
When only one substituent is present on the heterocyclic group, the substituent is the substituent having the maximum total number. Further, the substituent of the heterocyclic group and the substituent of the aryl group may not have a heteroatom, and when the substituent does not have a heteroatom, the number of the heteroatoms is set to 0. Further, the substituent of the aryl group may not have a carbon atom, and when it does not have a carbon atom, the number of carbon atoms is set to 0.
As a preferred embodiment, the substituents on the heterocyclic groups R ¹¹ and R ¹² are t-butyl groups (4 carbon atoms and 0 heteroatoms for a total of 4), and the aryl group is R ¹³ . And the substituent at the ⁴ -position on R14 is an i-propyl group (3 carbon atoms and 0 heteroatoms, for a total of 3).

According to the above-mentioned metallocene compound, the propylene homopolymer of the present disclosure can be produced with high activity.
The reason why high activity is obtained is not always clear, but by introducing a substituent having 3 or more carbon atoms on the aryl groups R ¹³ and R ¹⁴ , the electron density of the transition metal is changed, so that propylene is obtained. It is considered that the rate of insertion into the cell increases and the rate of growth increases.
Further, as another action of increasing the activity, the substituent on the aryl group causes the growth polymer chain to be formed by its bulkiness, and the 6-membered ring portion of one indene ring ligand on the transition metal in the general formula (1). Aim to avoid. As a result, the orientation of the next inserted propylene is controlled by both the growing polymer chain oriented to avoid this 6-membered ring portion and the heterocyclic groups R ¹¹ and R ¹² , position and conformation. Propylene insertion is performed.
At this time, the heterocyclic groups R ¹¹ and R ¹² simultaneously increase the efficiency of the β-position methyl group elimination reaction due to the effect of controlling the orientation of the β-position methyl group of the growth polymer chain, thereby making the terminal vinyl group more efficient. The steric and positional regularity control is performed by the combination of the substituents ^on the aryl groups ^R13 and ^R14 and the substituents ^on the heterocyclic groups R11 and R12. There is.
Ultimately, the combined effect of each substituent controls both the growth reaction rate and the β-methyl elimination reaction rate, resulting in a polymer chain of a specific length, that is, a polymer of a specific molecular weight. Be done.
Therefore, in the present disclosure, the substituents on the heterocyclic groups R ¹¹ and R ¹² and the substituents on the aryl groups R ¹³ and R ¹⁴ are combined with specific substituents to cause a growth reaction. By balancing the termination reaction due to β-methyl desorption, a propylene homopolymer having a specific molecular weight can be obtained with high regularity and high activity.

The X ¹¹ and Y ¹¹ are ligands that independently form a sigma bond with Hf, and together with the component (B) and the component (C), generate an active metallocene having an olefin polymerization ability.
Therefore, as long as this purpose is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand.
X ¹¹ and Y ¹¹ independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms. , An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and from the viewpoint of stability of the metallocene compound, a halogen atom and 1 to 20 carbon atoms. Hydrocarbon group is preferable, and chlorine, bromine, methyl group, ethyl group, isopropyl group, and phenyl group are particularly preferable.

The above Q11 has a divalent hydrocarbon group having ¹ to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms which may contain a divalent halogen that bonds two five-membered rings. Represents a silylene group or a gelmilene group which may be present.
When two hydrocarbon groups are present on the above-mentioned silylene group or gelmilene group, they may be bonded to each other to form a ring structure.
Specific examples of the above ^Q11 include alkylene groups such as methylene, methylmethylene, dimethylmethylene, and 1,2-ethylene;
Arylalkylene groups such as diphenylmethylene;
Silylen group;
Alkylylylene groups such as methylcilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene;
(Alkyl) (aryl) silylene groups such as methyl (phenyl) silylene;
Arylcyrylene groups such as diphenylcilylene;
Alkyloligosilylene groups such as tetramethyldisyrylene;
Germilen group;
The above-mentioned alkylgermylene group in which silicon of a silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium;
(Alkyl) (aryl) gelmilene group;
Arylgelmillene groups and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylcilylene group and an alkylgelmilene group are particularly preferable.

Among the compounds represented by the general formula (1), the following compounds can be exemplified as preferable compounds.
(1) Dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium (2) dichloro [1,1 '-Dimethylsilylenebis {2- (5-phenyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium (3) dichloro [1,1'-dimethylsilylenebis {2- (5) -T-butyl-4-methyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium

(2) Ingredient (B)
The component (B) is a compound or an ion-exchangeable layered silicate that reacts with the component (A) to form an ion pair.
The component (B) may be used alone or in combination of two or more. It is preferably an ion-exchangeable layered silicate.

(2-1) A compound that forms an ion pair with the component (A) Examples of the compound that reacts with the component (A) to form an ion pair include an aluminum oxy compound and a boron compound, and examples of the aluminum oxy compound include aluminum oxy compounds and boron compounds. Specific examples thereof include compounds represented by the following general formulas (I) to (III).

In the above general formulas (I) and (II), Ra represents ^a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. .. Further, the plurality of ^Ras may be the same or different from each other. Further, p represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (I) and (II) are compounds also referred to as aluminoxane, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above-mentioned aluminoxane can be used in combination in a plurality of types within each group and between each group. The above aluminoxane can be prepared under various known conditions.
In the general formula (III), R ^b 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 10: 1 to 10: 1 to one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the general formula ^RBB (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction.
The boron compound is a complex of a cation such as a carbonium cation or an ammonium cation with an organoboron compound such as triphenylboron, tris (3,5-difluorophenyl) boron or tris (pentafluorophenyl) boron, or a complex. Various organoboron compounds such as tris (pentafluorophenyl) boron can be mentioned.

(2-2) Ion-exchangeable layered silicate Ion-exchangeable layered silicate (hereinafter, may be simply abbreviated as silicate) means that layers composed of ionic bonds or the like are stacked in parallel with each other due to their binding force. A silicate compound having a crystal structure, having interlayer ions between layers, and having exchangeable interlayer ions contained therein.
Most silicates are naturally produced primarily as the main component of clay minerals. It is generally dispersed / swollen in water and purified by the difference in sedimentation rate, but it is not necessary that the contaminants are completely removed, and contaminants other than ion-exchangeable layered silicate (quartz). , Cristobalite, etc.) may be included. Depending on the type, amount, particle size, crystallinity, and dispersed state of these impurities, it may be preferable to pure silicate or more, and such a complex is also included in the ion-exchangeable layered silicate of the component (B). ..
Further, the silicate used in the present disclosure is not limited to a naturally produced silicate, and may be an artificial synthetic product.

Specific examples of ion-exchangeable layered silicates include layered silicates having a 1: 1 type structure or a 2: 1 type structure described in "Clay Minerals" by Haruo Shiramizu, Asakura Shoten (1988). Can be mentioned.
The 1: 1 type structure refers to a structure based on a stack in which a one-layer tetrahedral sheet and a one-layer octahedral sheet are combined as described in the above-mentioned "Clay Minerals" and the like.
The 2: 1 type structure shows a structure based on a stack in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.
Specific examples of the ion-exchangeable layered silicate having a 1: 1 type structure include kaolin-type silicates such as dikite, naclinite, kaolinite, metahaloysite, and halloysite, and serpentine-type silicates such as chrysotile, lysaldite, and antigolite. Examples include salt.
Specific examples of the ion-exchangeable layered silicate having a 2: 1 type structure include smectite silicates such as montmorillonite, byderite, nontronite, saponite, hectrite and stephensite, vermiculite silicates such as vermiculite, and mica. , Elite, sericite, mica silicates such as vermiculite, attapargite, sepiolite, parigolskite, bentonite, pyrophyllite, talc, chlorite group and the like. These may form a mixed layer.
Among these, those in which the main component is an ion-exchangeable layered silicate having a 2: 1 type structure are preferable. More preferably, the main component is 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-exchangeable layered silicate) is not particularly limited, but the main components are alkali metals of Group 1 of the periodic table such as lithium and sodium, calcium, magnesium and the like. Alkaline earth metals of Group 2 of the Periodic Table of the Period, 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.

(2-3) Treatment of Ion-Exchangeable Layered Silicate The ion-exchangeable layered silicate may be used in a dry state or in a liquid slurry state.
The shape of the ion-exchangeable layered silicate is not particularly limited, and may be a naturally produced shape or a shape at the time of artificial synthesis, or the shape may be changed by operations such as crushing, granulation, and classification. A processed ion-exchange layered silicate may be used.
Of these, the granulated ion-exchangeable layered silicate is particularly preferable because it gives good polymer particle properties when the ion-exchangeable layered silicate is used as a catalyst component.
For the method for treating the ion-exchangeable layered silicate, the description in paragraphs 0042 to 0071 of JP-A-2009-299046 can be referred to.

The component (B) preferably used in the present disclosure is a chemically treated ion-exchangeable layered silicate, and has an atomic ratio of Al / Si of 0.01 to 0.25, preferably 0.03 to 0.24. , And more preferably in the range of 0.05 to 0.23. The Al / Si atomic ratio is considered to be an index of the acid treatment strength of the clay portion.
Aluminum and silicon in the ion-exchangeable layered silicate are measured by a method of preparing a calibration curve by a method of chemical analysis by the JIS method and quantifying by fluorescent X-rays.

(3) Ingredient (C)
The component (C) used in the present disclosure is an organoaluminum compound, and an organoaluminum compound represented by the following general formula (4) is preferably used.
(AlR _n X _3-n ) _m ... General formula (4)
[In the above general formula (4), 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. Represents each of the integers of. ]
The organoaluminum compound can be used alone or in combination of two or more.
Specific examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormalaloctylaluminum, trinormalaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferred. More preferably, it is trialkylaluminum in which R has 1 to 8 carbon atoms.

(4) Preparation of catalyst The catalyst for olefin polymerization preferably used in the present disclosure includes the above-mentioned component (A), component (B) and component (C). These can be obtained by contacting them inside or outside the polymerization tank. The catalyst for olefin polymerization may be prepolymerized in the presence of olefin.
The amount of the component (A), the component (B) and the component (C) to be used is arbitrary.
For example, the amount of the component (A) used with respect to the component (B) is preferably in the range of 0.1 μmol to 1000 μmol, more preferably 0.5 μmol to 500 μmol with respect to 1 g of the component (B).
The amount of the component (C) used with respect to the component (A) is preferably 0.01 to 5 × ¹⁰⁶ , more preferably 0, in terms of the molar ratio of the aluminum of the component (C) to the transition metal of the component (A). It is in the range of 1 to 1 × 10 ⁴ .
The order in which the component (A), the component (B), and the component (C) are brought into contact is arbitrary, and two of these components may be brought into contact with each other and then the remaining one component may be brought into contact with the three components. The 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.

(5) Prepolymerization The catalyst for olefin polymerization is preferably subjected to prepolymerization consisting of contacting olefins and polymerizing in a small amount. The catalytic activity can be improved by prepolymerization, and the manufacturing cost can be suppressed.
The olefin used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It can be exemplified, preferably propylene.
As the olefin feeding method, any method can be used, such as a feeding method for maintaining the olefin in the prepolymerization tank at a constant speed or a constant pressure state, a combination thereof, and a stepwise change.
The prepolymerization temperature and the prepolymerization time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C., 5 minutes to 24 hours, respectively.
The mass ratio of the prepolymerized polymer to the component (B) is preferably 0.01 to 100, and more preferably 0.1 to 50.
Further, the component (C) can be added at the time of prepolymerization.
A method such as coexistence of a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania is also possible at the time of or after the contact of each of the above components.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. You may use it. In the drying step, the catalyst may be agitated, vibrated, flowed, or allowed to stand.

[Polymerization method]
In the present disclosure, any mode can be adopted as long as the catalyst for olefin polymerization and the monomer are in efficient contact with each other. Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using the inert solvent, or a gas phase polymerization method in which each monomer is kept in a gaseous state substantially without using a liquid solvent. Etc. can be adopted.
Further, as the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
Further, the number of polymerization stages may be one, and a mode such as two stages of bulk polymerization, vapor phase polymerization after bulk polymerization, and two stages of vapor phase polymerization is also possible, and further, it is possible to produce with a larger number of polymerization stages. ..
Above all, it is preferable to carry out one-stage bulk polymerization using propylene as a solvent.

The polymerization temperature is preferably 0 to 90 ° C, more preferably 60 to 85 ° C, and even more preferably 70 to 80 ° C.
The polymerization pressure is preferably 0 to 5 MPaG, more preferably 0 to 4 MPaG.

In the case of the production method disclosed in JP-A-2009-299046, a terminal vinyl group-containing propylene polymer having a low molecular weight is obtained by relatively increasing the β-methyl desorption reaction rate by performing bulk polymerization at a higher temperature. However, on the other hand, local heat generation cannot be removed, growth particles collapse, and fine powder is generated. In addition, the growth particles fuse with each other to form agglomerates and lumps, which exceeds the critical temperature of propylene as a solvent. As a result, there is a problem that the shape and properties of the polymer particles are deteriorated.
In response to such problems, the present disclosure relates to a 5-membered polymer ring having a structure of a bisindenylhafnium complex and having a specific substituent at the 2-position of the inden ring which is a ligand, and the inden ring. By polymerizing in a temperature range suitable for bulk polymerization using a catalytic system containing a metallocene compound substituted with an aryl group having a specific substituent at the 4-position, the shape and properties of the polymer are good at a specific molecular weight or less. A propylene homopolymer can be obtained.
Further, in order to improve the activity, hydrogen can be supplementarily used during the polymerization step.
The reason why the activity is improved is considered to be a dormant active site, for example, a π-allyl-transition metal complex as a side reaction or a reaction immediately after the insertion of 2,1 of propylene. It is thought to be activated.
In many transition metal complex catalysts, the rate of chain transfer to hydrogen is fast and functions as an effective chain transfer agent to produce saturated ends, making it difficult to form terminal vinyl structures.
However, in the present disclosure, surprisingly, even when hydrogen is added, the action as a chain transfer agent is poor, and the action of reactivation still keeps the vinyl terminal ratio high.
Therefore, in the present disclosure, by using hydrogen as an auxiliary during the polymerization step, the activity is improved and the vinyl terminal ratio is kept high.

The amount of hydrogen used for polymerization is 0 to 2.0 × 10 ^-4 , preferably more than 0 and 2.0 × 10 ^-4 or less, more preferably 2.0 ×, with hydrogen as the feed mass ratio of propylene. The range is ^10-5 to 1.5 × 10 ^-4 , more preferably 3.0 × 10 ^-5 to 1.0 × 10 ^-4 .
When bulk polymerization is carried out, the concentration of the gas phase portion is carried out in the range of 0 to 10000 ppm, preferably 100 to 8000 ppm, more preferably 200 to 1000 ppm on average to improve the activity and obtain the target polymer. Obtainable.

Next, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to the following examples.
The physical property measurement, analysis, etc. in the following examples follow the following methods.

(1) Melt flow rate (MFR):
The measurement was carried out according to the melt flow rate (test conditions: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758. The unit is g / 10 minutes.
(2) Molecular weight and molecular weight distribution (Mw, Mn, Mw / Mn):
It was measured by gel permeation chromatography (GPC) by the method described herein above.
(3) Melting point (Tm), crystallization temperature (Tc):
Using DSC6200 manufactured by Seiko Instruments, a sheet-shaped sample piece was packed in a 5 mg aluminum pan, the temperature was once raised from room temperature to 200 ° C. at a heating rate of 100 ° C./min, and after holding for 5 minutes, 10 ° C./min. The crystallization temperature (Tc) was obtained as the maximum crystal peak temperature (° C) when the temperature was lowered to 20 ° C. and then crystallized, and then the maximum melting point when the temperature was raised to 200 ° C. at 10 ° C./min. The melting point (Tm) was determined as the peak temperature (° C.).
(4) mm fraction of 3 chains of propylene unit:
The measurement was carried out by the method described in the above specification using an AV400 type NMR apparatus of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe. The unit is%.
(5) Catalytic activity (CE) (g / ghr)
The catalytic activity is a value per unit time obtained by dividing the yield (g) of the polymer by the introduced catalytic amount (g) (value excluding the prepolymerized polymer).
(6) Composition analysis:
The composition of the ion-exchangeable layered silicate was measured by fluorescent X-rays after preparing a calibration curve by chemical analysis by the JIS method.

[Example 1]
(1) Synthesis of complex (complex 1) rac-dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] Hafnium was synthesized according to the method of Example 13 of JP-A-2009-299046 and Example 1 of JP-A-2009-91512.

(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchangeable layered silicate Add 645.1 g of distilled water and 82.6 g of 98% sulfuric acid to a 1 L three-necked flask equipped with a stirring blade and a reflux device. , The temperature was raised to 95 ° C.
Commercially available montmorillonite (Benclay KK manufactured by Mizusawa Industrial Chemicals, Al = 9.78% by mass, Si = 31.79% by mass, Mg = 3.18% by mass, Al / Si (molar ratio) = 0.320, An average particle size of 14 μm) was added, 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 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 reacted at 40 ° C. for 1 hour. After 1 hour, the reaction slurry was filtered and washed 3 times with 1 L of distilled water to obtain a cake-like solid again.
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% by mass.

(2-b) Prepolymerization 20 g of the obtained chemically treated montmorillonite was placed in a 1 L 3-necked flask, and 131 mL of heptane was added to form a slurry, to which 50 mmol of triisobutylaluminum (concentration 143.4 mg / mL heptane solution) was added. 69 mL) was added and the mixture was stirred for 1 hour. After 1 hour, it was washed with heptane to 1/100 to make the total volume 100 mL.
The slurry solution containing this chemically treated montmorillonite was kept at 50 ° C., 4.2 mmol of trinormal octyl aluminum (10.7 mL of a heptane solution having a concentration of 143.4 mg / mL) was added thereto, and the mixture was stirred for 20 minutes.
There, rac-dichloro [1,1'-dimethylsylylenebis {2- (5-t-butyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium 0.3 mmol (toluene 50 mL) (Slurry made in 1) was added, and the mixture was stirred for 20 minutes while maintaining the temperature at 50 ° C.
Then 350 mL of heptane was added and the slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining 40 ° C. for 4 hours. Then, the propylene feed 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 by the decantation, 12 mmol of triisobutylaluminum (16.6 mL of a heptane solution having a concentration of 143.4 mg / mL) was added, and the mixture was stirred for 10 minutes. The solid was dried under reduced pressure at 40 ° C. for 2 hours to obtain 29.8 g of a dry prepolymerization catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymer by the amount of solid catalyst) was 0.49. This prepolymerization catalyst was designated as catalyst 1.

(3) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 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 (140 mg / mL) and 160 N ₍ normal) ml of H2, 750 g of liquid propylene was introduced, and then the temperature was raised to 75 ° C. Then, 80 mg of the catalyst 1 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization. After holding at 75 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 188 g of a propylene homopolymer was obtained.
The evaluation results of the obtained polymer are shown in Table 1.

[Examples 2, 3, 4, 5]
In Example 1, 240, 480, 640, 960 N (normal) ml of H ₂ was introduced into the tank, 750 g of liquid propylene was introduced, and the catalyst 1 was 80, 50, 40 by mass excluding the prepolymerized polymer. The same polymerization was carried out except that 40 mg was used.
The evaluation results of the obtained polymer are shown in Table 1.

[Example 6]
The 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 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 (140 mg / mL) and 750 g of liquid propylene, the temperature was raised to 80 ° C. Then, 200 mg of the catalyst 1 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization. After holding at 80 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 296 g of a propylene homopolymer was obtained.
The evaluation results of the obtained polymer are shown in Table 1.

[Examples 7 and 8]
In Example 6, 160, 240 N (normal) ml of H ₂ was introduced into the tank, 750 g of liquid propylene was introduced, and 80, 80 mg of the catalyst 1 was used in the mass excluding the prepolymerized polymer. Polymerization was performed.
The evaluation results of the obtained polymer are shown in Table 1.

[Example 9]
The 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 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 (140 mg / mL) and 750 g of liquid propylene, the temperature was raised to 85 ° C. Then, 160 mg of the catalyst 1 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization. After holding at 85 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 357 g of a propylene homopolymer was obtained.
The evaluation results of the obtained polymer are shown in Table 1.

[Comparative Example 1]
(1) Synthesis of complex (complex 2) rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] of hafnium Synthesis:
rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] Hafnium is synthesized in JP2012-149160. Was carried out in the same manner as in the method described in Synthesis Example 1.
(2) Preparation of catalyst In the (2-b) prepolymerization of Example 1, rac-dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (4) -Isopropyl-phenyl) -Indenyl}] Instead of hafnium, rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl }] The same operation was performed except that hafnium was used.
As a result, 54.0 g of a dry prepolymerization catalyst was obtained. The prepolymerization ratio (value obtained by dividing the amount of prepolymer by the amount of solid catalyst) was 1.70. This prepolymerization catalyst was designated as catalyst 2.
(3) Polymerization A 3 L autoclave was heated and dried well in advance by circulating nitrogen, and then 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 (140 mg / mL) and 750 g of liquid propylene, the temperature was raised to 75 ° C. Then, 200 mg of the catalyst 2 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization. After holding at 75 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 350 g of a propylene homopolymer was obtained.
The evaluation results of the obtained polymer are shown in Table 1.

[Comparative Example 2]
This comparative example is described in Macromol. Rapid Commun. It was done according to 2000 and 21.
(1) Synthesis of complex (complex 3) Synthesis of rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride):
Rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was synthesized according to the method described in Example 2 of JP-A-8-208733.
(3) Polymerization 500 ml of toluene and 3.4 ml of organoaluminum oxy compound (hexane solution manufactured by Toso Finechem Co., Ltd., MMAO-3A 1.47 mmol Al / ml) were introduced into a 1 L autoclave sufficiently substituted with nitrogen, and the mixture was heated to 105 ° C.
Further, (complex 3) rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride 1 mg was dissolved in toluene and introduced. Then propylene was quickly introduced until it reached 0.35 MPa and this pressure was maintained at 105 ° C. for 30 minutes. Finally, the polymerization was stopped by press-fitting ethanol.
The obtained polymer solution was added to ethanol, filtered, and dried under reduced pressure to obtain 33 g of the polymer.
The evaluation results of the obtained polymer are shown in Table 1.

[Comparative Example 3]
(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchangeable layered silicate Add 96% sulfuric acid (1500 g) to 2260 g of distilled water in a separable flask, and then use montmorillonite (Benclay manufactured by Mizusawa Chemical Co., Ltd.) as the layered silicate. SL: average particle size 19 μm) 600 g was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./min and reacted at 90 ° C. for 480 minutes. The reaction slurry was cooled to room temperature in 1 hour and washed with distilled water to pH 3. The obtained solid was pre-dried at 130 ° C. under a nitrogen stream for 2 days, and then coarse particles of 53 μm or more were removed. Got
The composition of this chemically treated smectite is Al: 2.72% by mass, Si: 43.48% by mass, Mg: 0.36% by mass, Fe: 0.61% by mass, and Al / Si = 0.065 [mol]. / Mol].

(2-b) Prepolymerization Put 20 g of the chemically treated smectite obtained above in a three-necked flask (volume 1 L) and add heptane (114 mL) to make a slurry, to which triethylaluminum (50 mmol: concentration 71 mg / mL) 81 mL of heptane solution) was added, and the mixture was stirred for 1 hour, washed with heptane to 1/1000, and heptane was added so that the total volume became 200 mL.
In another flask (volume 200 mL), heptane (85 mL) was charged with (complex 3) rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride (0.3 mmol) synthesized in Comparative Example 2. After adding the slurry, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution having a concentration of 140 mg / mL) was added, and the mixture was stirred and reacted at room temperature for 60 minutes. This solution was added to a 3 L flask containing the chemically treated smectite and stirred at room temperature for 60 minutes. Then 214 mL of heptane was added and the slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 20 g / hour and prepolymerization was performed while maintaining 40 ° C. for 2 hours. Then, the propylene feed was stopped and residual polymerization was carried out for 1 hour. The supernatant of the obtained catalyst slurry was removed by decantation, triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added to the remaining portion, and the mixture was stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 47.6 g of a dry prepolymerization catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymer by the amount of solid catalyst) was 1.38. This prepolymerization catalyst was designated as catalyst 3.

(3) Polymerization After drying well in advance by passing nitrogen under heating through a 3L autoclave, the inside of the tank was replaced with propylene and cooled to room temperature. 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, and then the temperature was raised to 70 ° C. Then, 100 mg of the prepolymerized catalyst by weight excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon, and polymerized at 70 ° C. for 1 hour. Unreacted propylene was quickly purged to terminate polymerization. As a result, about 78 g of a propylene homopolymer was obtained.
The evaluation results of the obtained polymer are shown in Table 1.

[Comparative Example 4]
In the polymerization of (3) of Comparative Example 3, the same polymerization was carried out except that 750 g of liquid propylene was introduced after introducing 300 N ₍ normal) ml of H2, then the temperature was raised to 70 ° C., and the polymerization was carried out at 70 ° C. for 1 hour. I did it.

[Discussion of Examples]
FIG. 2 is a diagram showing the relationship between the melting point and the crystallization temperature of the propylene homopolymers of Examples and Comparative Examples.
As shown in FIG. 2, Examples 1 to 9 satisfy the condition that the characteristic (i): melting point (Tm) is 145 ° C. or higher and 149 ° C. or lower, and the relationship between the melting point (Tm) and the crystallization temperature (Tc). In, it can be seen that the characteristic (iii) and the characteristic (viii) are satisfied at the same time.
On the other hand, in Comparative Examples 1 to 4, it can be seen that the ones satisfying the characteristics (i) and the characteristics (ii) at the same time could not be obtained.
Further, as shown in Examples 1 to 2, 4 to 5, and 7 to 8 in Table 1, when the polymerization temperature and the amount of catalyst are the same, the catalytic activity may be improved by increasing the amount of hydrogen introduced. It became clear.

Claims (3)

A propylene homopolymer having the following properties (i) to (ii), (v) and properties (viii) .
Characteristic (i): Melting point (Tm) is 145 ° C. or higher and 149 ° C. or lower Characteristic (ii): Melting point (Tm) and crystallization temperature (Tc) (° C.) satisfy the following formula (1) Tm-Tc ≦ 0.907 × Tm-99.64 ... Equation (1)
Characteristic (v): Number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 50,000 or less.
Characteristics (viii): Melting point (Tm) and crystallization temperature (Tc) (° C) satisfy the following formula (2).
Tm-Tc ≧ 0.907 × Tm-103.64 ... Equation (2) The propylene homopolymer according to claim 1, further having the following property (vi).
Characteristics (vi): ¹³ The terminal vinyl ratio measured by C-NMR is 0.7 or more. The propylene homopolymer according to claim 1 or 2, further having the following property (vii).
Characteristic (vii): Number of long-chain branches is 0.1 / 1000 monomers or more

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