Terminal vinyl group-containing propylene-based polymer and method for producing the same

Abstract

To provide a terminal vinyl group-containing propylene-based polymer featuring a high proportion of terminal vinyl groups, excellent regularity, a molecular weight sufficient to achieve both flowability in powder or granular form and reactivity of terminal vinyl groups, a low melting point, and the capability to prevent transparency deterioration during melt-kneading with other resins.SOLUTION: A terminal vinyl group-containing propylene-based polymer features a proportion of terminal vinyl groups of 0.7 or more, an isotactic triad fraction (mm fraction) of 90% or more, a content of hetero linkages (2,1-linkages) of 0.03 mol% or less, a content of hetero linkages (1,3-linkages) that is greater than the content of hetero linkages (2,1-linkages) by 0.06 mol% or more, a number average molecular weight (Mn) of 10,000 or more and less than 50,000, and a melting point (Tm) of less than 150°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a vinyl-terminated propylene polymer and a method for producing the same. [Background technology]

[0002] Polypropylene has high chemical stability, excellent mechanical properties, and is inexpensive, and therefore is widely used as a material for daily life and industrial use. On the other hand, attempts to improve the functionality of polypropylene, which has unsaturated bonds, are being investigated by utilizing the reactivity caused by the unsaturated bonds. For example, vinyl-terminated propylene polymers are expected to be useful as raw materials for functionalization, and attempts have been made to modify the vinyl terminal groups by melt-kneading the vinyl-terminated propylene polymers together with a modifying agent to functionalize them. Patent Document 1 discloses a technique for obtaining a modified polypropylene by reacting a polypropylene having a double bond at one end with a nitrile oxide compound during melt-kneading.

[0003] On the other hand, the polymer to be used in the melt kneading is required to be a powder having good flowability. In order to improve the flowability of the polymer powder, it is necessary to control the molecular weight of the polymer. In addition, in a mixed resin obtained by melt-kneading a vinyl-terminated propylene polymer together with a modifier with another resin, transparency may be required in some cases. In order to maintain the transparency of the mixed resin obtained after melt-kneading, it is desirable that the melting point of the raw material polymer is not too high. In addition, the vinyl-terminated propylene polymer used as the raw material for functionalization is preferably one having a high terminal vinyl ratio and high reactivity of the terminal vinyl group. In order to increase the reactivity of the terminal vinyl group, it is desirable for the vinyl-terminated propylene polymer to have a small molecular weight.

[0004] Incidentally, it is believed that in the case of vinyl-terminated propylene polymers, the polymer growth termination reaction occurs not through the usual β-hydrogen elimination during the polymerization reaction of propylene, but through β-methyl elimination (see Non-Patent Document 1). However, under the polymerization conditions (catalyst components, etc.) that cause β-methyl elimination as disclosed in Non-Patent Document 1, only atactic polypropylene with no stereoregularity can be obtained, and the inherent mechanical properties of polypropylene are sacrificed. On the other hand, Patent Documents 2 to 5 disclose terminal vinyl group-containing propylene polymers that are excellent in regularity, have a number average molecular weight (Mn) of 10,000 or more and less than 50,000, and a melting point (Tm) of less than 150°C. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 107450 [Patent Document 2] JP 2019-26740 A [Patent Document 3] JP 2018-76482 A [Patent Document 4] Patent Publication No. 2021-73355 [Patent Document 5] Patent Publication No. 2021-73356 [Non-patent literature]

[0006] [Non-Patent Document 1] Resconi, J. Am. Chem. Soc.1992, 114, 1025-1032 Summary of the Invention [Problem to be solved by the invention]

[0007] However, there is still room for improvement in the vinyl-terminated propylene polymers disclosed in Patent Documents 2 to 5. For example, there is a demand for maintaining better transparency when melt-kneaded with other resins.

[0008] Therefore, an object of the present invention is to provide a vinyl-terminated propylene polymer having a high terminal vinyl ratio, good regularity, a molecular weight that satisfies both the flowability and the reactivity of the vinyl terminal groups when made into a powder or granule, a low melting point, and capable of suppressing a decrease in transparency when melt-kneaded with other resins.Another object of the present invention is to provide a method for producing such a vinyl-terminated propylene polymer with high activity. [Means for solving the problem]

[0009] The vinyl-terminated propylene polymer provided by the present invention is characterized by having the following properties (I), (II), (III), (IV) and (V). Property (I): Terminal vinyl ratio is 0.7 or more. Property (II): The isotactic triad fraction (mm fraction) is 90% or more. Characteristic (III): The amount of hetero bonds (2,1 bonds) is 0.03 mol % or less, and the amount of hetero bonds (1,3 bonds) is 0.06 mol % or more more than the amount of hetero bonds (2,1 bonds). Characteristic (IV): The number average molecular weight (Mn) is 10,000 or more and less than 50,000. Property (V): Melting point (Tm) is less than 150°C.

[0010] The method for producing a propylene-based polymer having a terminal vinyl group provided by the present invention is characterized in that propylene alone or propylene and at least one comonomer selected from ethylene and an α-olefin is polymerized using an olefin polymerization catalyst containing the following components (A), (B), and (C): Component (A): a metallocene compound represented by the general formula (1) described below Component (B): a compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum compound Effect of the Invention

[0011] According to the present invention, it is possible to provide a vinyl-terminated propylene polymer having a high terminal vinyl ratio, good regularity, a molecular weight that satisfies both the flowability and the reactivity of the vinyl terminal groups when made into a powder or granule, a low melting point, and the ability to suppress a decrease in transparency when melt-kneaded with other resins. Also, according to the present invention, it is possible to provide a method for producing such a vinyl-terminated propylene polymer with high activity. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a diagram illustrating the baseline and intervals of a chromatogram in GPC. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. In this specification, the use of "to" indicating a range of values ​​means that the values ​​before and after the range include the lower limit and upper limit.

[0014] 1. Propylene polymers containing terminal vinyl groups The vinyl-terminated propylene polymer of the present invention is a propylene polymer having the following properties (I), (II), (III), (IV) and (V). Property (I): Terminal vinyl ratio is 0.7 or more. Property (II): The isotactic triad fraction (mm fraction) is 90% or more. Characteristic (III): The amount of hetero bonds (2,1 bonds) is 0.03 mol % or less, and the amount of hetero bonds (1,3 bonds) is 0.06 mol % or more more than the amount of hetero bonds (2,1 bonds). Characteristic (IV): The number average molecular weight (Mn) is 10,000 or more and less than 50,000. Property (V): Melting point (Tm) is less than 150°C.

[0015] The vinyl-terminal propylene polymer of the present invention has a number average molecular weight (Mn) of 10,000 or more, and can be used as a powder or granule. In addition, the number average molecular weight (Mn) is sufficiently small, that is, less than 50,000, and the vinyl terminal ratio is high, that is, 0.7 or more, and therefore the reactivity of the vinyl terminal groups is good. The vinyl-terminated propylene polymer of the present invention also has good regularity. In the present invention, the good regularity of the propylene polymer means that it has good stereoregularity and regioregularity. The vinyl-terminated propylene polymer of the present invention has a high mm fraction of 90% or more, excellent stereoregularity, and a small amount of heterogeneous bonds (2,1 bonds) of 0.03 mol% or less, excellent regioregularity. In addition, the vinyl-terminated propylene polymer of the present invention has a sufficiently small number average molecular weight (Mn) of less than 50,000 and has good regularity as described above, so that the polymer has good fluidity when made into powder or granule. When the polymer has high stereoregularity and regioregularity, adhesion between particles is suppressed, improving the fluidity. Furthermore, the vinyl-terminated propylene polymer of the present invention has excellent stereoregularity and regioregularity, and has a specific structure in which the number of heterogeneous bonds (1,3 bonds) is greater than the number of heterogeneous bonds (2,1 bonds) by a specific amount, and has a sufficiently low melting point (Tm) of less than 150°C, thereby suppressing a decrease in transparency when melt-kneaded with other resins. Here, from the viewpoint of transparency, low-crystalline or non-crystalline resins such as propylene-ethylene random copolymers, ethylene-α-olefin copolymers, or ethylene-α-olefin-conjugated dienes are preferably used as the other resins. Since the vinyl-terminated propylene polymer of the present invention has a sufficiently low melting point (Tm) of less than 150°C, for example, when the powdered vinyl-terminated propylene polymer of the present invention is melt-kneaded with other resins together with a modifier and pelletized, the resin after the modification of the vinyl terminal groups or after granulation is likely to maintain good transparency. The vinyl-terminated propylene polymer of the present invention further has the specific structure, and hence has good compatibility with other resins, and therefore is more likely to maintain good transparency when melt-kneaded with other resins. The 1,3 bond structure is similar to an ethylene chain, and therefore has properties similar to those of an ethylene chain. Therefore, it is presumed that the vinyl-terminated propylene polymer of the present invention has good compatibility with resins containing a polyethylene structure, etc., because it contains a specific amount of 1,3 bonds. In addition, the methyl side chain of the 2,1 bond is located at a position different from that of the methyl group of a normal (1,2 bond) propylene unit, and therefore inhibits compatibility with resins containing an isotactic polypropylene structure. Therefore, it is presumed that the vinyl-terminated propylene polymer of the present invention has good compatibility with resins containing an isotactic polypropylene structure, etc., because it contains a specific amount or less of 2,1 bonds. In addition, the vinyl-terminated propylene polymer of the present invention has a sufficiently low melting point (Tm) of less than 150° C., and therefore the melt-kneading temperature can be reduced. When the vinyl terminal groups of the vinyl-terminated propylene polymer of the present invention are modified during melt-kneading using, for example, a platinum or palladium catalyst, a side reaction may occur, but by lowering the melt-kneading temperature, the side reaction can be suppressed and production efficiency can be improved.

[0016] Property (I): Terminal vinyl ratio The vinyl-terminated propylene polymer of the present invention has a vinyl terminal ratio (Rv) of 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and ideally 1.0 (all polymer chains have vinyl groups at their terminals). When the vinyl terminal ratio is the above value or more, the reactivity of the vinyl-terminated propylene polymer is improved. In the present invention, the terminal vinyl ratio means the ratio of chains having vinyl groups at their terminals to all polymer chains of the vinyl-terminated propylene polymer, and is calculated by the following formula: Terminal vinyl ratio (Rv) = {[Vi] / (total number of terminals - number of LCBs)} x 2 However, [Vi] is 1 The total number of terminal vinyl groups per 1,000 monomer units is calculated by H-NMR. 13 The total number of terminals per 1000 monomer units calculated by C-NMR. The LCB number (long chain branch number) is 13 This is the number of methine carbon atoms at the root of branched chains with 7 or more carbon atoms per 1,000 monomer units calculated by C-NMR.

[0017] The relationship between the reaction mechanism of propylene homopolymerization and the terminal structure will be explained below. In the polymerization of propylene, when a chain transfer reaction called β-methyl elimination occurs as a termination reaction, a polymer having a 1-propenyl structure (vinyl structure) as the termination terminal shown in structural formula (1-a) is produced. When a chain transfer reaction called β-hydrogen elimination occurs as a termination reaction, a polymer with a vinylidene structure (propyl-vinylidene structure) as shown in structural formula (1-b) is produced. When hydrogen is used, a chain transfer reaction to hydrogen occurs after β-hydrogen elimination, and a polymer with an i-butyl structure as shown in structural formula (1-c) is produced. Propylene may also undergo irregular 2,1 insertion. If propylene undergoes irregular insertion followed by a chain transfer reaction to hydrogen, a terminal end with an n-butyl structure as shown in structural formula (1-e) is produced. If propylene undergoes irregular insertion followed by β-hydrogen elimination, a very small amount of terminal ends with a 1-butenyl structure as shown in structural formula (1-f) or a terminal vinylene structure (2-butenyl structure) as shown in structural formula (1-g) may be produced. In propylene polymerization, β-hydrogen elimination is generally likely to occur, but β-methyl elimination can be promoted by using an olefin polymerization catalyst described below.

[0018] All initiating ends are saturated, so that one polymer chain cannot have two unsaturated ends at the same time. In the initiation reaction with propylene, when the first propylene is inserted into the central metal of the metallocene compound after chain transfer to hydrogen or after β-hydrogen elimination, an n-propyl structure as shown in structural formula (1-h) is generated, and when the first propylene is inserted into the elimination site after β-methyl elimination, an initiation end with an i-butyl structure as shown in structural formula (1-c) is generated. In addition, when the first propylene randomly inserts into the central metal of the metallocene compound after chain transfer to hydrogen or after β-hydrogen elimination, a 2,3-dimethylbutyl structure shown in structural formula (1-i) is generated, and when the first propylene randomly inserts into the elimination site after β-methyl elimination, an initiation end of a 3,4-dimethylpentyl structure shown in structural formula (1-j) is generated.

[0019] Isomerization can also produce a polymer having an i-butenyl structure at the end, as shown in structural formula (1-d). The internal vinylidene structure shown in structural formula (1-k) is an olefin structure formed inside a polymer chain by inserting propylene into an intermediate formed by the elimination of hydrogen from an unsaturated terminal.

[0020] Of the above, the main saturated ends resulting from the main reaction are represented by structural formula (1-c) and structural formula (1-h), and the main unsaturated ends are represented by structural formula (1-a) and structural formula (1-b). The number of other terminal structures is minute compared to the number of the main terminal structures described above. On the other hand, the 1-propenyl structure shown in structural formula (1-a) is a terminal generated as a result of β-methyl elimination after regular insertion of propylene, whereas the 1-butenyl structure shown in structural formula (1-f) is a structure generated as a side reaction in which propylene is rarely randomly inserted followed by β-hydrogen elimination, and the amount of the structure generated can be estimated to be extremely small compared to the 1-propenyl structure. The ratio of the 1-butenyl structure generated to the 1-propenyl structure is considered to be equal to or lower than the probability of heterogeneous bond generation. In other words, it can be estimated that most of the number of terminal vinyl groups [Vi] mentioned above are the 1-propenyl structure shown in structural formula (1-a).

[0021] [ka]

[0022] [ka]

[0023] [Method for evaluating terminal vinyl ratio (Rv) and terminal vinylidene ratio (Rvd)] The terminal vinyl ratio (Rv) and the terminal vinylidene ratio (Rvd) are indicators showing the ratio of the number of terminal vinyl groups and the number of terminal vinylidene groups, respectively, to the total number of polymer chains. The calculation method is as follows: 1 H-NMR and 13 The number of unsaturated terminals and the number of saturated terminals are calculated per 1000 monomers using C-NMR, and the sum of these is the total number of terminals. 13 The number of LCBs is calculated per 1000 monomers using C-NMR. The total number of polymers is calculated by subtracting the number of LCBs from the total number of terminals (half). The terminal vinyl ratio (Rv) is calculated by dividing the number of terminal vinyl groups [Vi] by the total number of polymers, and the terminal vinylidene ratio (Rvd) is calculated by dividing the number of terminal vinylidene groups [Vd] by the total number of polymers.

[0024] 1 H-NMR measurements and 13 C-NMR measurement can be carried out by the following method. [Sample preparation and measurement conditions] 200 mg of sample was mixed with o-dichlorobenzene / deuterated bromobenzene (C 6 D 5 The mixture was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of a 100% alcohol (Br) solution (volume ratio) of 1:3 and hexamethyldisiloxane (a chemical shift standard substance), and dissolved uniformly in a block heater at 150°C. NMR measurements are performed using a Bruker Biospin AV400 NMR instrument equipped with a 10 mm diameter cryoprobe.

[0025] For the quantification of unsaturated ends, 1 H-NMR is used. 1 The H-NMR measurement conditions are as follows: ( 1 H-NMR measurement conditions) Equipment: Bruker Biospin AV400 NMR system Probe: 10mmφ cryo-probe Sample temperature: 120℃ Pulse angle: 4.5° Pulse Interval: 2 seconds Number of times of accumulation: 1024 times Chemical shift: The chemical shift is set to 0.09 ppm for the proton signal of hexamethyldisiloxane, and the chemical shifts of the signals due to other protons are based on this.

[0026] To quantify the saturated ends, 13 Using C-NMR. 13 The measurement conditions for C-NMR are as follows: (13 C-NMR measurement conditions) Equipment: Bruker Biospin AV400 NMR system Probe: 10mmφ cryo-probe Sample temperature: 120℃ Pulse angle: 45° Pulse Interval: 18.0 seconds Number of times: 3072 Decoupling conditions: Broadband decoupling method Chemical shift: Chemical shifts of hexamethyldisiloxane 13 The C signal was set at 1.98 ppm, and the other 13 The chemical shifts of the C signals are based on this. In the present invention, 13 The signals in the C-NMR spectrum are called " 13 It is sometimes called the "C signal" 1 The signals in the H-NMR spectrum are called 1 This is sometimes called the "H signal."

[0027] <How to calculate the number of saturated ends> The number of saturated ends is given below per 1000 monomers: 13 It is calculated using the integrated intensity of the C signal according to the following formula. Structural formula (1-c): [i-butyl] = I i-butyl ×1000 / I total-C Structural formula (1-e): [n-butyl] = I nbu ×1000 / I total-C Structural formula (1-h): [n-propyl] = I npr ×1000 / I total-C Structural formula (1-i): [2,3-dimethylbutyl] = I 2,3-dime ×1000 / I total-C Structural formula (1-j): [3,4-dimethylpentyl] = I 3,4-dime ×1000 / I total-C When other saturated ends known in the literature are detected in addition to these saturated ends, the number per 1000 monomers is calculated in the same manner using the known literature values. Here, I i-butyl , I nbu , I npr , I 2,3-dime , I 3,4-dime respectively represent characteristic values ​​of signals based on structural formula (1-c), structural formula (1-e), structural formula (1-h), structural formula (1-i), and structural formula (1-j), and are amounts represented by the following formulas. In the following, the chemical shifts in the range of 23.80 to 23.65 ppm are 13 The integrated intensity of the C signal is I 23.80~23.65 It should be written as follows. I i-butyl =I 23.80~23.65 I nbu =I 36.99~36.88 I npr =I 39.71~39.61 I 2,3-dime =I 16.30~16.20 I 3,4-dime =I 12.0~11.60 Also, I total-C is the quantity shown in the following formula: I total-C =I i-butyl +I nbu +I npr +I 2,3-dime +I 3,4-dime +I 1,2-P +I 2,1-P +I 1,3-P +IE+IB When there are other saturated structures known in the literature in addition to these saturated structures, the number of all detected structures is added to the above formula. I 1,2-P is the characteristic value of the signal based on the 1,2-inserted propylene bond, I 2,1-P is the characteristic value of the signal based on the 2,1 inserted propylene bond, I 1,3-P represents a characteristic value of a signal based on a 1,3-inserted propylene bond, IE is a characteristic value of a signal based on an ethylene bond, and IB is a characteristic value of a signal based on a butene bond. I 1,2-P I., 2,1-P I., 1,3-P I., IE, and IB will be described later in terms of the method of obtaining them.

[0028] <Calculation Method for the Number of Unsaturated Ends> The number of unsaturated ends, as the number per 1000 monomers, 1 is determined as follows using the integrated intensity of the H signal. 1 In H-NMR, the proton signals of the unsaturated bonds of the 1-propenyl structure shown in Structural Formula (1-a) and the 1-butenyl structure shown in Structural Formula (1-f) 1 are detected overlapping with the signals at 5.08 - 4.85 ppm and 5.86 - 5.69 ppm in the H-NMR spectrum. Therefore, the number of terminal vinyl groups [Vi] is the combined number of the 1-propenyl structure and the 1-butenyl structure. The number of terminal vinylidene groups [Vd] is the number of the vinylidene structure shown in Structural Formula (1-b). Structural Formula (1-a) + Structural Formula (1-f): [Vi] = I vi ×1000 / I total Structural Formula (1-b): [Vd] = I vd ×1000 / I total Similarly, the number of i-butenyl groups [i-butenyl], the number of vinylene ends [terminal vinylene], and the number of internal vinylidene [internal vinylidene] are determined from the following formulas. Structural Formula (1-d): [i-butenyl] = I ibu ×1000 / I total Structural Formula (1-g): [terminal vinylene] = I vnl ×1000 / I total Structural Formula (1-k): [internal vinylidene] = I ivd ×1000 / I total When other unsaturated ends known from the literature are detected in addition to these unsaturated ends, they are calculated in the same way as the number per 1000 monomers using the known literature values. Here, I vi I., vd I.,ibu , I vnl , I ivd represents the characteristic values of signals based on Structural Formula (1-a) + Structural Formula (1-f), Structural Formula (1-b), Structural Formula (1-d), Structural Formula (1-g), and Structural Formula (1-k), respectively, and is the quantity represented by the following formula. I vi = I 5.86~5.69 I vd = (I 4.78~4.65 ) / 2 I ibu = I 5.08~4.85 - I vi ×2 I vnl = (I 5.58~5.26 ) / 2 I ivd = (I 4.85~4.78 ) / 2 Also, I total is the quantity represented by the following formula. I total = I main / 6 + I vi + I vd + I ibu + I vnl + I ivd Also, when there are other unsaturated structures known in the literature in addition to these unsaturated structures, the total number of all detected ends is added to the above formula. I main means 1 It is the sum of the integrated intensities of proton signals bonded to saturated carbons of the polymer chain including the ends, detected in the 4.00 - 0.00 ppm range of the 1H-NMR spectrum.

[0029] <Calculation method of total end number> The total end number is 13 the sum of the number of saturated ends per 1000 monomer units calculated by 13C-NMR, and 1 the sum of the number of unsaturated ends per 1000 monomer units calculated by 1H-NMR.

[0030] <Calculation method of LCB number> The long-chain branch number (LCB number) is 13The number per 1000 propylene monomer units is calculated using the following formula using the integrated signal intensities of the branch point carbon (methine carbon) at 31.72 to 31.66 ppm and three methylene carbons bonded to the branch point carbons (methine carbon) at 44.09 to 44.03 ppm, 44.78 to 44.72 ppm, and 44.90 to 44.84 ppm when the intensity of the methylene carbons in the propylene main chain at 49.00 to 44.33 ppm is normalized to 1000 by C-NMR. Number of LCBs = [(I 44.09~44.03 +I 44.78~44.72 +I 44.90~44.84 +I 31.72~31.66 ) / 4] / I 49.00~44.33 The LCB number is not particularly limited, but is preferably 0.5 or less and 0.1 or more.

[0031] Property (II): Isotactic triad fraction (mm fraction) The vinyl-terminated propylene polymer of the present invention is 13 The isotactic triad fraction calculated from the integrated intensity of the C signal (in the present invention, this may be simply referred to as the "mm fraction") is 90% or more, preferably 95% or more, and more preferably 96% or more. A higher mm fraction means that the stereoregularity is more highly controlled. Furthermore, when the mm fraction is equal to or greater than the above value, the compatibility with other materials is improved. On the other hand, the mm fraction is preferably 99% or less, more preferably 98% or less. By controlling the mm fraction so that it does not become too high, the solubility in a solvent can be increased. In addition, by controlling the mm fraction so that it does not become too high, it is believed that the compatibility with polypropylene with low stereoregularity or polypropylene having a low stereoregularity moiety is improved.

[0032] The isotactic triad fraction (mm fraction) is 13 Measured by C-NMR 13 The integrated intensity of the C signal can be calculated by substituting it into the following formula (1). mm fraction (%)=Imm ×100 / (I mm +I mr+rm +I rr ) Formula (1) Here I mm is assigned to the mm bonding mode of three propylene units. 13 The integrated intensity of the C signal is shown in Fig. 1. The integrated intensity of the signal with a chemical shift in the range of 23.6 to 21.1 ppm (hereinafter referred to as "I 23.6~21.1 " is used as the calculation. Spectral assignments can be made with reference to Polymer Jounral, vol. 16, p. 717 (1984), Asakura Publishing, Macromolecules, vol. 8, p. 687 (1975), and Polymer, vol. 30, p. 1350 (1989). A specific method for determining the isotactic triad fraction (mm fraction) will be described below. The signals derived from the methyl group of the central propylene unit of the head-to-tail (1,2 bond) triplet chain centered on a propylene unit occur in three regions depending on their configuration. I mm =I 23.6~21.1 I mr+rm =I 21.1~20.5 I rr =I 20.5~19.8 Although the chemical shift range of each region shifts slightly depending on the molecular weight and monomer composition of the copolymer, the above three regions are easily distinguishable. Here, mm, mr+rm and rr are represented by the following structural formulas (2-a) to (2-c), respectively.

[0033] [ka]

[0034] Furthermore, when the vinyl-terminated propylene polymer of the present invention contains ethylene as a comonomer, it may have a partial structure represented by the following structural formulas (3-a) to (3-b).

[0035] [ka]

[0036] The methyl group of the central propylene unit of the partial structure PPE+EPP (PPE+EPP-methyl group) resonates in the mr+rm region, and the methyl group of the central propylene unit of the partial structure EPE (EPE-methyl group) resonates in the rr region. Therefore, when such partial structures are present, it is necessary to subtract the signal areas based on the PPE+EPP-methyl group and the EPE-methyl group from the signal areas in the mr+rm and rr regions. The signal area based on the PPE+EPP-methyl groups is determined from the signal area of ​​the corresponding methine group (resonating at about 30.8 ppm), and the signal area based on the EPE-methyl group is determined from the signal area of ​​the corresponding methine group (resonating at about 33.2 ppm).

[0037] The vinyl-terminated polypropylene of the present invention may have, in addition to a structure based on regular 1,2 insertion of propylene within the polymer, 2,1 bonds and 1,3 bonds based on irregular insertion of propylene. The following structural formulae (4-a), (4-b) and (4-c) are structures based on a 2,1 bond, and the following structural formula (4-d) is a structure based on a 1,3 bond.

[0038] [ka]

[0039] Of these, signals based on carbons A, A', A'', and T appear in the mr+rm region, and signals based on carbons B and B' appear in the rr region. It should be noted that signals due to carbons C and C' appear in the vicinity of 17.5 to 17.1 ppm, but since they are not related at all to the mm, mr+rm, and rr regions of interest, they need not be taken into consideration. Therefore, when calculating the mm fraction according to the above formula (1), it is necessary to subtract the signal areas based on carbons A, A', A", B, B', and T that are not based on head-to-tail bonded triplet sequences from the signal areas in the mr+rm region and the rr region, respectively.

[0040] The signal area based on carbon A is calculated from the signal areas of carbon C (resonating at about 17.1 ppm), carbon C' (resonating at about 17.5 ppm), carbon E (resonating at about 35.7 ppm), carbon G (resonating at about 35.8 ppm), and carbon D (resonating at about 42.1 ppm) in structural formula (4-a), which is a positional irregular partial structure, according to the following formula (2). I A =(I C +I C’ +I E +I G +I D ) / 5 Formula (2)

[0041] The signal area based on carbon A' is calculated from the signal areas of carbons H and I (resonating at around 34.7 to 34.5 ppm) of structural formula (4-b), which is a regioirregular partial structure, according to the following formula (3). I A’ =(I H +I I ) / 2 Formula (3)

[0042] The signal area based on carbon B is calculated from the signal areas of carbons H and I (resonating at around 34.7 to 34.5 ppm) of structural formula (4-b), which is a regioirregular partial structure, according to the following formula (4). I B =(I H +I I ) / 4 Formula(4)

[0043] The signal area based on carbon A″ and carbon B′ is calculated from the signal areas of carbons O and N (resonating at about 34.9 ppm) of structural formula (4-c), which is a regioirregular partial structure, according to the following formula (5). I A” =I B’ =(IO +I N ) / 2 Formula (5)

[0044] The signal area based on carbon T is calculated from the signal area of ​​carbon L (resonating at about 27.6 ppm) of structural formula (4-d), which is a regioirregular partial structure, according to the following formula (6). I T =I L Formula (6) From the above, the signal areas of mm, mr+rm, and rr can be determined, and the mm fraction of the three-unit sequence consisting of a head-to-tail bond with the propylene unit at the center can be calculated according to the above formula (1).

[0045] Characteristic (III): Amount of heterogeneous binding The vinyl-terminated propylene polymer of the present invention is 13 The amount of heterogeneous bonds (2,1 bonds) calculated from the integrated intensity of the C signal is 0.03 mol % or less, and the amount of heterogeneous bonds (1,3 bonds) is 0.06 mol % or more higher than the amount of heterogeneous bonds (2,1 bonds), that is, the following formula is satisfied. [1,3]-[2,1]≧0.06mol% In addition, [1,3] represents the amount (mol %) of heterogeneous bonds (1,3 bonds), and [2,1] represents the amount (mol %) of heterogeneous bonds (2,1 bonds).

[0046] The vinyl-terminated propylene polymer of the present invention has excellent regioregularity due to the amount of hetero bonds (2,1 bonds) being 0.03 mol % or less. The amount of hetero bonds (2,1 bonds) is preferably 0.02 mol % or less, more preferably 0.01 mol % or less, from the viewpoint of improving regioregularity. The vinyl-terminated propylene polymer of the present invention is likely to maintain good transparency when melt-kneaded with other resins because the difference ([1,3]-[2,1]) between the amount of heterogeneous bonds (1,3 bonds) and the amount of heterogeneous bonds (2,1 bonds) is 0.06 mol% or more. The difference ([1,3]-[2,1]) between the amount of heterogeneous bonds (1,3 bonds) and the amount of heterogeneous bonds (2,1 bonds) may be 0.06 mol% or more, but is preferably 0.20 mol% or less, more preferably 0.10 mol% or less. The amount of heterogeneous bonds (1,3 bonds) is not particularly limited, but from the viewpoint of improving regioregularity, it is preferably 0.20 mol % or less, more preferably 0.10 mol % or less. It is believed that heterogeneous bonds (1,3 bonds) are formed by isomerization of propylene after random insertion (2,1 insertion) before the next propylene is inserted. (Reference: Macromol. Chem. Phys. Vol. 204, p. 1323 (2003)) Therefore, the amount of heterogeneous bonds (1,3 bonds) is described as the relative amount to the amount of heterogeneous bonds (2,1 bonds). In many cases, after random insertion of propylene (2,1 insertion), the next propylene is inserted before isomerization occurs, resulting in the formation of a heterogeneous bond (2,1 bond), so that the number of 1,3 bonds is relatively small compared to the number of 2,1 bonds. In contrast, the vinyl-terminated propylene polymer of the present invention is characterized in that the number of 1.3 bonds is greater than the number of 2,1 bonds, and the difference ([1.3]-[2,1]) is 0.06 mol% or more. Incidentally, the insertion of two ethylene units after the 2,1 bond is detected as the same structure as the 1,3 bond. However, when the amount of 2,1 bonds is small and the ethylene content is small compared to the propylene content, as in the case of the vinyl-terminal propylene polymer of the present invention, the probability of two ethylene units being inserted after the 2,1 bond is very small and can be ignored.

[0047] The amount of each heterogeneous bond (molar concentration) is: 13 It is calculated using the integrated intensity of the C signal according to the following formula. Propylene 2,1 bond (mol%) =I 2,1-P×100 / (I 1,2-P +I 2,1-P +I 1,3-P +IE+IB) Propylene 1,3 bond (mol%) =I 1,3-P ×100 / (I 1,2-P +I 2,1-P +I 1,3-P +IE+IB) Here, I 1,2-P is the characteristic value of the signal based on the 1,2-inserted propylene bond, I 2,1-P is the characteristic value of the signal based on the 2,1 inserted propylene bond, I 1,3-P represents a characteristic value of a signal based on a 1,3-inserted propylene bond, IE represents a characteristic value of a signal based on an ethylene bond, and IB represents a characteristic value of a signal based on a 1-butene bond, and are quantities represented by the following mathematical formulas (7) to (11). I 1,2-P =I 49.0~44.4 Formula (7) I 2,1-P =I A +I B +I A’’ Formula (8) I 1,3-P =I T / 2 Formula(9) IE=(I 25.0~24.0 +I 30.0~29.8 +I O +I N ) / 2+(I 38.2~37.2 -I T +3×I 27.3~27.1 +I 30.5.~30.2 -I A -I npr +I H +I I ) / 4 Formula (10) IB=I 41.00~39.00 +I 43.90~42.30 / 2 Formula(11)

[0048] Characteristic (IV): Number average molecular weight The vinyl-terminated propylene polymer of the present invention has a number average molecular weight (Mn) of 10,000 or more and less than 50,000, so that it can achieve both good fluidity and good reactivity of the vinyl terminal groups when made into powder. The vinyl-terminated propylene polymer of the present invention can be used as a powder material and melt-kneaded with other materials because it has a number average molecular weight (Mn) of 10,000 or more. On the other hand, the vinyl-terminated propylene polymer of the present invention has a number average molecular weight (Mn) of less than 50,000, so that it has good fluidity when made into powder. Furthermore, because the number average molecular weight (Mn) is less than 50,000, the amount of the vinyl terminal groups per unit mass increases, so that the vinyl terminal ratio increases and the reactivity of the vinyl terminal groups becomes good. Therefore, a sufficient amount of functional groups can be introduced into the vinyl-terminated propylene polymer of the present invention by modifying the vinyl terminal groups. The number average molecular weight (Mn) of the vinyl-terminal propylene polymer of the present invention is preferably 15,000 or more, more preferably 20,000 or more, from the viewpoint of improving particle properties when made into a powder or granule, and is preferably 40,000 or less, more preferably 30,000 or less, from the viewpoint of increasing the terminal vinyl ratio, improving the reactivity of the terminal vinyl groups, and improving the flowability.

[0049] The number average molecular weight (Mn) is measured by gel permeation chromatography (GPC), and the details of the measurement method and the measurement device are as follows. Apparatus: Waters GPC (ALC / GPC, 150C) Detector: FOXBORO MIRAN, 1A, IR detector (measurement wavelength: 3.42 μm) Column: Showa Denko AD806M / S (3 columns) Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0mL / min Injection volume: 0.2mL

[0050] The sample is prepared by preparing a 1 mg / mL solution using the polymer to be measured and ODCB (containing 0.5 mg / mL dibutylhydroxytoluene (BHT)) and dissolving the polymer at 140° C. for about 1 hour. The baseline and intervals of the obtained chromatogram are as shown in Figure 1. The retention volume obtained by GPC measurement is converted to molecular weight using a calibration curve prepared in advance using standard polystyrenes. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. Brand Name: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000 A calibration curve was created by injecting 0.2 mL of a solution of each of the ODCB (containing 0.5 mg / mL BHT) at 0.5 mg / mL. The calibration curve was created using a cubic equation obtained by approximating the curve using the least squares method. Viscosity formula used for conversion to molecular weight: [η] = K × M α The following numerical values ​​are used: PS (polystyrene): K = 1.38 x 10 -4 , α=0.7 PP (polypropylene): K = 1.03 x 10 -4 , α=0.78

[0051] As shown in the manufacturing method described later, when a metallocene compound having a bisindenyl hafnium complex structure and a 5-membered heterocycle having a specific substituent at the 2-position of the indene ring as a ligand and an aryl group having a specific substituent at the 4-position of the indene ring is used as a polymerization catalyst component, the β-methyl elimination reaction rate, which is a termination reaction, is fast, so that a propylene-based polymer containing a terminal vinyl group having a low molecular weight is easily obtained at a relatively low temperature. In addition, this elimination reaction rate can also be controlled by changing the polymerization temperature, the propylene concentration, or the pressure. For example, when a metallocene compound shown in the examples is used, the number average molecular weight (Mn) of the obtained propylene-based polymer tends to decrease as the polymerization temperature is increased.

[0052] Characteristics (V): Melting point (Tm) (℃) The vinyl-terminated propylene polymer of the present invention has a melting point (Tm) of less than 150° C. This makes it easy to maintain good transparency when the vinyl-terminated propylene polymer of the present invention is melted and kneaded with other resins. In addition, since the vinyl-terminated propylene polymer of the present invention has a melting point (Tm) of less than 150° C., it can be melted at a relatively low temperature, and therefore the temperature when melt-kneading with other materials can be lowered, thereby suppressing side reactions during melt-kneading. The melting point (Tm) of the vinyl-terminated propylene polymer of the present invention is preferably 148° C. or lower, more preferably 146° C. or lower, and even more preferably 144° C. or lower, from the viewpoint of suppressing a decrease in transparency when melt-kneaded with other resins and suppressing side reactions during melt-kneading. On the other hand, the melting point (Tm) of the vinyl-terminated propylene polymer of the present invention is preferably 125° C. or higher, more preferably 135° C. or higher, and even more preferably 139° C. or higher, from the viewpoint of improving particle properties when made into a powder or granule.

[0053] The melting point (Tm) is measured by a differential scanning calorimeter (DSC). Specifically, a DSC6200 manufactured by Seiko Instruments Inc. is used, and 5 mg of a sheet-shaped sample piece is packed in an aluminum pan, and the temperature is raised from room temperature to 200°C at a heating rate of 100°C / min, and then the temperature is lowered to 20°C at a rate of 10°C / min to crystallize the sample. The crystallization temperature (Tc) is calculated as the maximum crystallization peak temperature (°C), and the melting point (Tm) is calculated as the maximum melting peak temperature (°C) when the temperature is then raised to 200°C at a rate of 10°C / min. The sheet-like sample can be obtained by sandwiching the powder of the vinyl-terminated propylene polymer between press plates, preheating it at 190°C for 2 minutes, pressing it at 5 MPa for 2 minutes, and then cooling it at 0°C and 10 MPa for 2 minutes.

[0054] Among the vinyl-terminated propylene polymers of the present invention having the above properties (I), (II), (III), (IV) and (V), those further having the following properties (IV-i) and (Vi) are referred to as vinyl-terminated propylene polymers (X1). Characteristic (IV-i): The number average molecular weight (Mn) is 25,000 or more and 45,000 or less. Characteristics (Vi): Melting point (Tm) is 140°C or higher and lower than 150°C. The vinyl-terminated propylene polymer (X1) tends to suppress deterioration in the mechanical properties of a mixed resin obtained by melt-kneading it with another resin.

[0055] On the other hand, among the vinyl-terminated propylene polymers of the present invention having the above properties (I), (II), (III), (IV) and (V), those further having the following properties (IV-ii) and (V-ii) are referred to as vinyl-terminated propylene polymers (X2). Characteristic (IV-ii): The number average molecular weight (Mn) is 10,000 or more and less than 25,000. Property (V-ii): Melting point (Tm) is less than 140°C. The above vinyl-terminated propylene polymer (X2) tends to have excellent reactivity when melt-kneaded and reacted with other resins.

[0056] Characteristics (VI): Soluble content below 90℃ The vinyl-terminated propylene polymer of the present invention preferably further has the following property (VI). Property (VI): In an elution curve obtained by temperature rising elution fractionation (TREF) measurement using o-dichlorobenzene (ODCB), the amount of components eluted at a temperature of 90° C. or less is 20% by mass or more and 100% by mass or less. The amount of components eluted at temperatures of 90° C. or less tends to increase as the melting point (Tm) of the vinyl-terminated propylene polymer decreases. In the vinyl-terminated propylene polymer of the present invention, when the amount of components eluted at temperatures of 90° C. or less (sometimes referred to as the "soluble content at 90° C. or less" in the present invention) is 20% by mass or more, a decrease in transparency can be suppressed when melt-kneaded with other resins, and side reactions during melt-kneading can be suppressed by lowering the melt-kneading temperature. Therefore, in the vinyl-terminated propylene polymer of the present invention, the soluble content at 90° C. or less is more preferably 22% by mass or more, and further preferably 24% by mass or more. In the vinyl-terminated propylene polymer of the present invention, the amount of soluble matter at 90°C or less in temperature rising elution fractionation (TREF) using o-dichlorobenzene (ODCB) can be made to be equal to or more than the above lower limit by, for example, using a metallocene compound as a polymerization catalyst component and ethylene as a comonomer.

[0057] Property (VII): Soluble content below 40℃ The vinyl-terminated propylene polymer of the present invention preferably further has the following property (VII). Property (VII): In an elution curve obtained by temperature rising elution fractionation (TREF) measurement using o-dichlorobenzene (ODCB), the amount of components eluted at a temperature of 40° C. or less is less than 5 mass %. The components that are eluted at a temperature of 40° C. or lower include so-called low crystallinity components such as low molecular weight components such as oligomers, components with low stereoregularity, components with extremely high comonomer content, etc. Therefore, in the vinyl-terminated propylene polymer of the present invention, when the amount of components that are eluted at a temperature of 40° C. or lower (sometimes referred to as the “soluble content at 40° C. or lower” in the present invention) is less than 5 mass%, the heat resistance and rigidity of the product can be prevented from decreasing. In the vinyl-terminated propylene polymer of the present invention, the amount of soluble matter at 40° C. or less is more preferably 3% by mass or less, and further preferably 2.5% by mass or less. In the vinyl-terminated propylene polymer of the present invention, the amount of soluble matter at 40°C or less in temperature rising elution fractionation (TREF) using o-dichlorobenzene (ODCB) can be reduced by decreasing the amount of comonomer such as ethylene during polymerization.

[0058] The details of the method for measuring the amount of soluble matter below 90°C and the amount of soluble matter below 40°C in the elution curve obtained by temperature rising elution fractionation (TREF) measurement using o-dichlorobenzene (ODCB) are as follows. Dissolve the sample in ODCB at 140 °C to form a solution. After introducing this into a TREF column at 140 °C, cool it to 100 °C at a cooling rate of 8 °C / min, then continue to cool it to 40 °C at a cooling rate of 4 °C / min, and hold for 10 minutes. Subsequently, while linearly heating the column from 40 °C to 140 °C at a heating rate of 100 °C / 60 min for 60 minutes, flow the solvent ODCB through the column at a flow rate of 1 mL / min to elute the sample and obtain an elution curve. Regarding the total amount of elution, the ratio of the component eluting at 40 °C, that is, the amount of the component dissolved at 40 °C, is defined as the soluble component amount (mass%) below 40 °C, and regarding the total amount of elution, the ratio of the amount of the component eluting up to 90 °C is defined as the soluble component amount (mass%) below 90 °C. <TREF measurement conditions> Column size: 4.3 mm φ × 150 mm Column packing agent: 100 μm surface-inactivated glass beads Solvent: o-dichlorobenzene (ODCB) Sample concentration: 5 mg / mL Sample injection volume: 0.1 mL Solvent flow rate: 1 mL / min Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)

[0059] <Content of comonomer units other than propylene> The terminal vinyl group-containing propylene-based polymer of the present invention may be a homopolymer of propylene or a copolymer of propylene and at least one comonomer selected from ethylene and α-olefins. However, in order to be a propylene-based polymer having the above-described characteristics (I), (II), (III), (IV), and (V), it is preferably a copolymer of propylene and a comonomer containing at least ethylene. Comonomers enter the propylene chain and change the primary structure of the propylene polymer. One of the results is that they have the effect of lowering the melting point of the propylene polymer. Therefore, by increasing the content of comonomers, the crystallinity does not become too high and the reactivity of the terminal vinyl groups can be increased. In addition, the melting point of the propylene polymer is lowered, so that the decrease in transparency when melt-kneaded with other resins is suppressed and the melt-kneading temperature can be lowered. The vinyl-terminated propylene polymer of the present invention has a content of structural units derived from ethylene of preferably 0.5 mol% or more, more preferably 1.0 mol% or more, as a lower limit. This allows the melting point to be appropriately lowered, the crystallinity not to be too high, and the transparency to be suppressed from decreasing when melt-kneaded with other resins, and the reactivity of the vinyl terminal groups to be increased. The upper limit is preferably 5.0 mol% or less, more preferably 4.0 mol% or less. This allows the propylene chains to be prevented from becoming too short, the crystallinity to be well balanced, and the transparency to be suppressed from decreasing when melt-kneaded with other resins. In addition, when the content of structural units derived from ethylene is 0.5 mol % or more and less than 2.0 mol %, the above-mentioned terminal vinyl group-containing propylene-based polymer (X1) is easily obtained, and when the content of structural units derived from ethylene is 2.0 mol % or more and 5.0 mol % or less, the above-mentioned terminal vinyl group-containing propylene-based polymer (X2) is easily obtained.

[0060] When the vinyl-terminated propylene polymer of the present invention contains structural units derived from comonomers other than ethylene, the propylene polymer is likely to have the above-mentioned properties (I), (II), (III), (IV) and (V), so that the content of structural units derived from all comonomers including ethylene is preferably 0.5 mol% or more as a lower limit, more preferably 1.0 mol% or more as an upper limit, and is preferably 10.0 mol% or less, more preferably 7.0 mol% or less, and even more preferably 5.0 mol% or less as an upper limit.

[0061] The content (molar concentration) of comonomer units is 13It is calculated from the signal intensity of the C-NMR spectrum using the following formula. Ethylene content [C2] (mol%) =IE×100 / (I 1,2-P +I 2,1-P +I 1,3-P +IE+IB) Propylene content [C3] (mol%) =(I 1,2-P +I 2,1-P +I 1,3-P )×100 / (I 1,2-P +I 2,1-P +I 1,3-P +IE+IB) 1-Butene content [C4] (mol%) =IB×100 / (I 1,2-P +I 2,1-P +I 1,3-P +IE+IB) Here, I 1,2-P , I 2,1-P , I 1,3-P , IE, and IB are as defined above.

[0062] 2. Method for producing vinyl-terminated propylene polymer An example of a method for producing the above-mentioned vinyl-terminal propylene polymer of the present invention is a method for polymerizing propylene alone or propylene and at least one comonomer selected from ethylene and an α-olefin, using an olefin polymerization catalyst containing the following components (A), (B) and (C): Component (A): A metallocene compound represented by the following general formula (1):

[0063] [ka]

[0064] [In general formula (1), R 11 and R 12 independently represent a heterocyclic group constituting a 5-membered ring having at least one hydrocarbon group having 1 to 3 carbon atoms as a substituent which may have a heteroatom, provided that the heteroatom of the heterocyclic group is not directly bonded to the indene ring. R 13 and R 14 is independently an aryl group having a substituent only at the 4-position, and the substituent is a hydrocarbon group having 3 to 6 carbon atoms which may contain at least one atom selected from a heteroatom and a halogen atom. However, R 11 and R 12 The substituents of the heterocyclic group in R 13 and R 14 and the total number of carbon atoms and heteroatoms contained in the substituents of the heterocyclic group that is the largest among the substituents of the heterocyclic group is smaller than the total number of carbon atoms and heteroatoms contained in the substituents of the aryl group. X 11 and Y 11 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a halogenated hydrocarbon group having from 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having from 1 to 20 carbon atoms. Q 11 represents 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 germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms.] Component (B): a compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum compound

[0065] According to the above-mentioned method, the above-mentioned vinyl-terminated propylene polymer of the present invention can be produced with high activity. In the present invention, it is believed that the reaction rate is increased by homopolymerizing or copolymerizing propylene using a catalyst containing a specific metallocene compound represented by the above general formula (1), and a propylene-based polymer having a small molecular weight can be synthesized under conditions of relatively low temperature and low pressure. Furthermore, by using a catalyst containing the specific metallocene compound represented by the above general formula (1), the present invention can easily produce a propylene-based polymer having a high terminal vinyl ratio, good regularity, Mn of 10,000 or more and less than 50,000, and a controlled amount of hetero bonds (2,1 bonds) and hetero bonds (1,3 bonds).

[0066] 2-1. Olefin polymerization catalysts (1) Component (A) Component (A) is a metallocene compound represented by the above general formula (1). In general formula (1), R 11 and R 12 are independently heterocyclic groups constituting a 5-membered ring having at least one hydrocarbon group having 1 to 3 carbon atoms as a substituent, which may have a heteroatom, provided that the heteroatom of the heterocyclic group is not directly bonded to the indene ring. R 11 and R 12 By having a substituent of appropriate size on the heterocyclic group, the direction of the propylene inserted during the propylene polymerization reaction is regularly controlled. 11 and R 12 The substituent on the aryl group makes it easier for the methyl group at the β-position of the growing polymer chain to face the vacant coordination site on the transition metal, facilitating the β-methyl elimination reaction and allowing the production of polypropylene into which terminal vinyl groups have been introduced with high selectivity. R 11 and R 12 are preferably identical to each other. Also, R 11 and R 12 In the case of R, the carbon atom adjacent to the heteroatom of the heterocyclic group constituting the five-membered ring is preferably bonded to the indene ring in general formula (1). 11 and R 12 is more preferably a 2-thienyl group or a 2-pyrrolyl group having at least one substituent, and further preferably a 2-thienyl group having at least one substituent. R 11 and R 12The hydrocarbon group which the aryl group has as a substituent may have from 1 to 3 carbon atoms, preferably 1 or 2, and more preferably 1 carbon atom. Also, R 11 and R 12 Examples of heteroatoms that may be contained in the hydrocarbon group that is a substituent of include silicon, oxygen, sulfur, nitrogen, boron, phosphorus, etc. These may be present in the carbon chain and may be interposed between the carbon-carbon bonds. Also, R 11 and R 12 are preferably independently a heterocyclic group constituting a 5-membered ring having a substituent only at position 5. In this case, the substituent at position 5 of the heterocyclic ring is the above-mentioned hydrocarbon group having 1 to 3 carbon atoms which may have a heteroatom. R 11 and R 12 The hydrocarbon group having 1 to 3 carbon atoms which is substituted on the ring is preferably a primary or secondary alkyl group.

[0067] R 11 and R 12 A preferred example of the structure is a five-membered heterocyclic structure represented by the following general formula (2).

[0068] [ka] [In the general formula (2), T is S or NR 20 R 20 represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms; R 21 and R 22 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms which may have a heteroatom; R 21 and R 22 At least one of R 21 and R 22 The heteroatom of the hydrocarbon group in R is not directly bonded to the heterocyclic group constituting the five-membered ring. 21 and R 22 does not bond to form a ring.

[0069] In the general formula (2), T is S (sulfur atom) or NR 20 Among them, S (sulfur atom) is preferable. 20 R is preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 20 The hydrocarbon group having 1 to 6 carbon atoms in R may be a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. 20 The alkoxy group having 1 to 6 carbon atoms in R is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group or an ethoxy group. 20 is particularly preferably a methyl group or a methoxy group. In addition, in the general formula (2), R 21 is a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and R 22 is preferably a hydrogen atom, and R 21 is a methyl group, and R 22 It is more preferable that is a hydrogen atom.

[0070] In general formula (1), R 13 and R 14 is independently an aryl group having a substituent only at the 4-position, and the substituent 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. R 13 and R 14 are preferably identical to each other. The aryl group is preferably a phenyl group. R 13 and R 14 Examples of heteroatoms which may be contained in the hydrocarbon group which is substituted include silicon, oxygen, sulfur, nitrogen, boron, and phosphorus. Also, R 13 and R 14 When the hydrocarbon group which is a substituent of contains a heteroatom, the heteroatom may be present in the carbon chain and may be interposed between the carbon-carbon bonds. R 13 and R 14 Examples of the halogen atom which may be contained in the hydrocarbon group which is a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 13 and R 14 The hydrocarbon group which the aryl group has as a substituent may have 3 or more and 6 or less carbon atoms, preferably 3 or more and 5 or less, more preferably 3 or 4, and further preferably 4 carbon atoms. The hydrocarbon group having 3 to 6 carbon atoms as a substituent on the aryl group may be, for example, any of an alkyl group, a cycloalkyl group, and an aromatic hydrocarbon group, but is preferably a tertiary hydrocarbon group, and more preferably a tertiary alkyl group.

[0071] R 13 and R 14 A preferred example of the structure is a structure having a substituent at the 4-position of the phenyl group (Ph) represented by the following general formula (3). 4-R 31 -Ph- General formula (3) [In 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. 31 R in general formula (1) 11 and R 12 has a structure different from that of the substituents of

[0072] R 31 Preferred examples of the aryl group include an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a trimethylsilyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a furyl group, and a t-butyl group is particularly preferred.

[0073] The metallocene compound represented by the above general formula (1) is R 11 and R 12 The substituents of the heterocyclic group constituting the five-membered ring in 13 and R 14 and the total number of carbon atoms and heteroatoms of the substituents of the heterocyclic group that is the largest is smaller than the total number of carbon atoms and heteroatoms of the substituents of the aryl group. That is, R 11 and R 12 In the case where there are a plurality of non-identical substituents on the heterocyclic group in the above, for example, when the heterocyclic group has substituents with different structures at the 4th and 5th positions, the total number of the substituents with the largest total number of carbon atoms and heteroatoms (sometimes referred to as the "maximum substituent") is compared with the total number of carbon atoms and heteroatoms of the substituents on the aryl group. At this time, the total number of carbon atoms and heteroatoms of the maximum substituent on the heterocyclic group is smaller than the total number of carbon atoms and heteroatoms of the substituents on the aryl group. The difference between the total number of carbon atoms and heteroatoms of the maximum substituent on the heterocyclic group and the total number of carbon atoms and heteroatoms of the substituents on the aryl group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 3 or more and 6 or less.

[0074] In addition, when there is only one substituent on the heterocyclic group, the substituent is the maximum substituent. In addition, the substituent of the heterocyclic group and the substituent of the aryl group may not have a heteroatom. When the substituent does not have a heteroatom, the number of heteroatoms is 0. Preferred examples include R 11 and R 12 The heterocyclic group is substituted with a methyl group (1 carbon atom and 0 heteroatoms, total number 1), and R 13 and R 14The substituent at the 4-position of the phenyl group in is a t-butyl group (4 carbon atoms and 0 heteroatoms, for a total of 4) or a trimethylsilyl group (3 carbon atoms and 1 heteroatom, for a total of 4).

[0075] According to the production method of the present invention, the above-mentioned vinyl-terminated propylene-based polymer of the present invention can be produced with high activity. The reason for this is not necessarily clear, but it is believed that the metallocene compound represented by the general formula (1) has an aryl group R 13 and R 14 It is believed that the presence of a substituent with three or more carbon atoms changes the electron density of the transition metal (Hf) in the metallocene compound, which increases the reaction rate of insertion of propylene monomers into propylene chains during the propylene polymerization reaction, thereby increasing the polymer growth rate.

[0076] Further, the following is also considered as another function that enables the production of the vinyl-terminated propylene polymer of the present invention with high activity. The metallocene compound represented by the general formula (1) is R 13 and R 14 The substituent on the aryl group in is bulky. Therefore, the bulky substituent directs the direction of the growing polymer chain during the polymerization reaction to avoid the six-membered ring portion of the indene ring ligand on the transition metal (Hf) in general formula (1). As a result, the direction of the propylene that is next inserted into the growing polymer chain is the same as that of the growing polymer chain that is oriented to avoid the six-membered ring portion and the heterocyclic group R 11 and R 12 The propylene insertion is controlled by both the heterocyclic group R 11 and R 12 R has the effect of allowing propylene insertion to occur regioregularly and stereoregularly, while at the same time controlling the orientation of the methyl group at the β-position of the growing polymer chain. 11 and R 12As a result, the methyl group elimination reaction at the β-position is increased, so that terminal vinyl groups can be efficiently produced, and the molecular weight of the polypropylene produced can be reduced by efficiently inducing a terminal vinylization reaction. In this way, in the production method of the present invention, propylene insertion is carried out regioregularly and stereoregularly due to the effect of the combination of a heterocyclic group having a specific substituent and an aryl group having a specific substituent that the metallocene compound has, and further, both the propagation reaction rate and the β-methyl elimination reaction rate are controlled, so that it is considered that a propylene-based polymer having a specific length of polymer chain, i.e., a specific molecular weight (number average molecular weight of 10,000 or more and less than 50,000), a high terminal vinyl ratio, and excellent regioregularity and stereoregularity can be produced with high activity. In addition, in the production method of the present invention, when propylene is irregularly (2,1) inserted, the direction of the methyl group of the inserted propylene controls the direction of the methyl of the next propylene due to the effect of the combination of a heterocyclic group having a specific substituent and an aryl group having a specific substituent that the metallocene compound has. Specifically, the methyl group of the irregularly (2,1) inserted propylene delays the insertion of the next propylene, and during that time, an isomerization reaction is likely to occur, so that a hetero-bond can be left in the molecular chain as a 1,3 bond that has progressed from a 2,1 bond. Therefore, it is considered that the production method of the present invention can obtain a propylene-based polymer containing terminal vinyl groups in which the amount of hetero-bonds (1,3 bonds) is 0.06 mol % or more greater than the amount of hetero-bonds (2,1 bonds). Therefore, in the present invention, in the metallocene compound represented by the above general formula (1) used in the olefin polymerization catalyst, R 11 and R 12 The above substituents and the aryl group R 13 and R 14 It is believed that by using a specific combination of the above substituents, a balance between the propagation reaction and the termination reaction due to β-methyl elimination can be achieved, and as a result, the above-mentioned vinyl-terminated propylene polymer of the present invention can be obtained with high activity.

[0077] Above X 11 and Y11 are each independently a ligand that forms a σ bond with Hf. The metallocene compound represented by the general formula (1) is 11 and Y 11 When the X is eliminated and cationized, the metallocene becomes an active metallocene having olefin polymerization ability. The components (B) and (C) described later act on the metallocene compound represented by the general formula (1) above, and the X contained in the metallocene compound is converted into an active metallocene having olefin polymerization ability. 11 and Y 11 is dropped off and becomes cationized. X 11 and Y 11 are independently 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, 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. 11 and Y 11 is not particularly limited as long as it is a ligand that can be detached by the action with component (B) and component (C) described below. From the viewpoint of stability of metallocene compounds, X 11 and Y 11 is preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group.

[0078] Above Q 11 is 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 germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. 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. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include alkylene groups such as methylene, methylmethylene, dimethylmethylene, and 1,2-ethylene groups; arylalkylene groups such as diphenylmethylene groups; and the like. Examples of silylene groups which may have a hydrocarbon group having 1 to 20 carbon atoms include silylene groups; alkylsilylene groups such as methylsilylene groups, dimethylsilylene groups, diethylsilylene groups, di(n-propyl)silylene groups, di(i-propyl)silylene groups, and di(cyclohexyl)silylene groups; (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene groups; arylsilylene groups such as diphenylsilylene groups; and alkyloligosilylene groups such as tetramethyldisilylene groups. Examples of germylene groups which may have a hydrocarbon group having 1 to 20 carbon atoms include germylene groups; alkylgermylene groups in which the silicon of the above-mentioned alkylsilylene groups is substituted with germanium; (alkyl)(aryl)germylene groups in which the silicon of the above-mentioned (alkyl)(aryl)silylene groups is substituted with germanium; and arylgermylene groups in which the silicon of the above-mentioned arylsilylene groups is substituted with germanium. Among these, a silylene group having a hydrocarbon group with 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group with 1 to 20 carbon atoms is preferred, with an alkylsilylene group or an alkylgermylene group being particularly preferred.

[0079] Of the compounds represented by the above general formula (1), the following compounds are preferred. (1) Dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl]hafnium (2) Dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-thienyl)-4-(4-trimethylsilylphenyl)indenyl]hafnium (3) Dichloro[1,1'-dimethylsilylenebis{2-(5-ethyl-4-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl]hafnium

[0080] (2) Component (B) Component (B) is a compound or an ion-exchangeable layered silicate that reacts with component (A) to form an ion pair. The component (B) may be used alone or in combination of two or more thereof, and is preferably an ion-exchangeable layered silicate.

[0081] (2-1) Compound that forms an ion pair with component (A) Examples of the compound that reacts with component (A) to form an ion pair include aluminum oxy compounds and boron compounds. Specific examples of the aluminumoxy compound include compounds represented by the following general formulas (I) to (III).

[0082] [ka]

[0083] In the above general formulas (I) and (II), R a R represents a hydrogen atom or a hydrocarbon group. a is preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. a may be the same or different, and p represents an integer of 0 to 40, and preferably an integer of 2 to 30. The compounds represented by the above general formulas (I) and (II) are also called aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferred. In general formula (III), R b represents a hydrocarbon group having 1 to 10 carbon atoms, and preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0084] Examples of the boron compound include complexes of cations such as carbonium cation and ammonium cation with organic boron compounds such as triphenyl boron, tris(3,5-difluorophenyl) boron and tris(pentafluorophenyl) boron, and various organic boron compounds such as tris(pentafluorophenyl) boron.

[0085] (2-2) Ion-exchange layered silicate An ion-exchangeable layered silicate (hereinafter sometimes simply referred to as silicate) is a silicate compound that has a crystal structure in which layers formed by ionic bonds or the like are stacked in parallel with each other through bonding forces, has ions between the layers, and the contained interlayer ions are exchangeable. Most silicates are naturally produced as the main component of clay minerals. They are generally purified by dispersing and swelling them in water and measuring the difference in sedimentation rate, but it is not necessary to completely remove impurities, and they may contain impurities other than ion-exchangeable layered silicates (quartz, 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-exchangeable layered silicates of component (B). Moreover, the silicate used in the present invention is not limited to naturally occurring silicates, but may be synthetically produced silicates.

[0086] Specific examples of ion-exchangeable layered silicates include layered silicates having a 1:1 type structure or a 2:1 type structure, as described in "Clay Mineralogy" by Shiramizu Haruo, Asakura Publishing (1988). The 1:1 type structure refers to a structure based on stacking 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 two layers of tetrahedral sheets sandwiching one layer of octahedral sheet. Specific examples of ion-exchangeable 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, lisardite, and antigorite. Specific examples of ion-exchangeable layered silicates having a 2:1 type structure include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, etc., vermiculite group silicates such as vermiculite, mica group silicates such as mica, illite, sericite, glauconite, etc., attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group, etc. These may form mixed layers. Among these, it is preferable that the main component is an ion-exchangeable layered silicate having a 2:1 type structure, more preferably that the main component is a smectite group silicate, and even more preferably that the main component is montmorillonite. The type of interlayer cation (the positive ion contained between the layers of the ion-exchangeable layered silicate) is not particularly limited, but preferred main components are alkali metals in Group 1 of the periodic table, such as lithium and sodium, alkaline earth metals in Group 2 of the periodic table, such as calcium and magnesium, and transition metals, such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold, which are relatively easily available.

[0087] The ion-exchangeable layered silicate may be used in a dry state or in a liquid slurried state. The shape of the ion-exchangeable layered silicate is not particularly limited, and may be a naturally occurring shape or a shape at the time of artificial synthesis, or may be an ion-exchangeable layered silicate whose shape has been processed by operations such as pulverization, granulation, and classification. Among these, the use of granulated ion-exchangeable layered silicate is particularly preferred because it gives good polymer particle properties when the ion-exchangeable layered silicate is used as component (B).

[0088] The ion-exchanged layered silicate can be used as it is without any particular treatment, but is preferably subjected to a chemical treatment, which means contacting the ion-exchanged layered silicate with acids, salts, alkalis, organic substances, or the like. A common effect of chemical treatments is the exchange of interlayer cations, but in addition, various chemical treatments have the following various effects. For example, acid treatment with acids not only removes impurities from the silicate surface, but also increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystal structure. This increases the acid strength of the silicate and contributes to increasing the number of acid sites per unit weight. Alkali treatment with alkalis destroys the crystal structure of the clay mineral, causing a change in the structure of the clay mineral.

[0089] Specific treatment agents (acids, salts, etc.) and chemical treatment conditions are described in detail below. In the present invention, a combination of these acids and salts may be used as the treatment agent. (i) Acids The acid treatment can remove impurities on the surface, exchange cations present between layers, and dissolve some or all of the cations of Al, Fe, Mg, etc. incorporated in the crystal structure. Examples of acids used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Among these, inorganic acids are preferred, sulfuric acid, hydrochloric acid, and nitric acid are more preferred, and sulfuric acid is even more preferred.

[0090] (ii) Salts Examples of salts include salts composed of a cation selected from the group consisting of organic cations, inorganic cations, and metal ions, and an anion selected from the group consisting of organic anions, inorganic anions, and halide ions. For example, preferred examples include compounds composed of a cation containing at least one type of atom selected from Groups 1 to 14 of the periodic table, and at least one type of anion selected from the group consisting of an anion of a halogen, an anion of an inorganic Bronsted acid, and an anion of an organic Bronsted acid.

[0091] (iii) Other treatments In addition to the acid or salt treatment, an alkali treatment or an organic treatment may be carried out as necessary. Examples of the alkali treatment agent include LiOH, NaOH, KOH, and Mg(OH). 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 etc. Examples of the treatment agent for treating organic matter include trimethylammonium, triethylammonium, dodecylammonium, N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-dimethyloctadecylammonium. These treatment agents may be used alone or in combination of two or more. These combinations may be used in combination for treatment agents added at the start of treatment or in combination for treatment agents added during treatment. Chemical treatment may also be carried out multiple times using the same or different treatment agents.

[0092] (iv) Chemical treatment conditions The above-mentioned various treatment agents may be dissolved in a suitable solvent to be used as a treatment agent solution, or the treatment agent itself may be used as a solvent. There is no particular limitation on the solvent that can be used, but water and alcohols are common, and water is particularly preferred. For example, when performing acid treatment as a chemical treatment, it is possible to change and control the ion-exchange layered silicate compound to a predetermined composition and structure by controlling the acid treatment conditions such as the acid treatment agent concentration, the ratio of the ion-exchange layered silicate to the treatment agent, the treatment time, and the treatment temperature. For the method of treating the ion-exchanged layered silicate, reference can be made to the description in paragraphs 0042 to 0071 of JP-A-2009-299046.

[0093] The ion-exchanged layered silicate used in the present invention usually contains a clay component. The molar ratio of aluminum atoms (Al) to silicon atoms (Si) (Al / Si molar ratio) contained in the ion-exchanged layered silicate is an index of the strength of acid treatment with respect to the clay component. The Al / Si molar ratio in the ion-exchanged layered silicate is preferably 0.01 to 0.25, more preferably 0.03 to 0.24, and further preferably 0.05 to 0.23. The aluminum and silicon in the ion-exchange layered silicate are measured by creating a calibration curve according to the JIS method of chemical analysis and quantifying with fluorescent X-rays.

[0094] (3) Component (C) The 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 (4) [In the general formula (4), R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen atom, a hydrogen atom, an alkoxy group or an amino group, n represents an integer of 1 to 3, and m represents an integer of 1 to 2.]

[0095] Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-normal propylaluminum, tri-normal butylaluminum, triisobutylaluminum, tri-normal hexylaluminum, tri-normal octylaluminum, tri-normal decylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride, etc. Among these, preferred are trialkylaluminum and alkylaluminum hydrides in which n=3 and m=1. More preferred are trialkylaluminums in which R has 1 to 8 carbon atoms. The organoaluminum compounds may be used alone or in combination of two or more kinds.

[0096] (4) Preparation of catalyst The olefin polymerization catalyst preferably used in the present invention contains the above-mentioned components (A), (B) and (C), which can be obtained by contacting them in a polymerization vessel or outside the polymerization vessel. The amounts of the components (A), (B) and (C) used are arbitrary. For example, the amount of the component (A) used relative to the component (B) is preferably in the range of 0.1 μmol to 1000 μmol, more preferably 0.5 μmol to 500 μmol, per 1 g of the component (B). The amount of component (C) used relative to component (A) is preferably 0.01 to 5×10 in terms of the molar ratio of aluminum in component (C) to the transition metal in component (A). 6 , more preferably 0.1 to 1×10 4 The range is. The order of contacting the above components (A), (B) and (C) is arbitrary. Two of these components may be contacted and then the remaining component may be contacted, or all three components may be contacted simultaneously. In order to ensure sufficient contact, a solvent may be used. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and liquefied monomers. Specific examples of the aliphatic saturated hydrocarbons and aromatic hydrocarbons include hexane, heptane, and toluene. In addition, liquefied propylene may be used as the liquefied monomer.

[0097] (5) Prepolymerization The olefin polymerization catalyst is preferably subjected to prepolymerization, which comprises contacting an olefin and polymerizing a small amount of the olefin. Prepolymerization can improve catalytic activity and reduce production costs. The olefin to be used is not particularly limited, but examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc., and preferably propylene. The olefin may be fed to the prepolymerization reactor at a constant rate or at a constant pressure, or any combination thereof, or by changing the rate stepwise. The prepolymerization temperature is not particularly limited, but is preferably in the range of -20°C to 100°C. The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01-100, more preferably 0.1-50, in terms of the mass ratio of the prepolymerized polymer to the component (B). Also, component (C) can be added during the prepolymerization. During or after the contact of the above components, a polymer such as polyethylene or polypropylene or a solid inorganic oxide such as silica or titania may be allowed to coexist. The catalyst may be dried after the preliminary polymerization. The drying method is not particularly limited, and examples thereof include drying under reduced pressure, drying by heating, and drying by passing a dry gas. These methods may be used alone or in combination of two or more methods. In the drying step, the catalyst may be stirred, vibrated, fluidized, or left to stand.

[0098] 2-2.Monomer The monomer used is propylene alone or in combination with a comonomer selected from the group consisting of ethylene and α-olefins. As the α-olefin, for example, an α-olefin having 4 to 10 carbon atoms can be used. More specifically, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane, styrene, etc. The comonomer copolymerized with propylene may be one or a combination of two or more selected from the group consisting of ethylene and α-olefins. In the present invention, since a propylene-based polymer having the above-mentioned properties (I), (II), (III), (IV) and (V) can be easily obtained, it is preferable to polymerize propylene and at least one selected from ethylene and 1-butene, and it is more preferable to polymerize at least propylene and ethylene.

[0099] 2-3. Polymerization method In the present invention, the method for polymerizing the monomer may be any method that efficiently brings the olefin polymerization catalyst into contact with the monomer. The polymerization method may be, for example, The monomer is converted into a liquid monomer under a temperature and pressure environment in which the monomer is condensed, A. A method of polymerizing liquid monomers without diluting them with a liquid inert hydrocarbon (bulk polymerization), B. A method of diluting the monomer in a liquid state with a liquid inert hydrocarbon and polymerizing the monomer in a liquid state (dilution polymerization), and converting the monomer into a non-condensable monomer under a temperature and pressure environment in which the monomer does not condense; C. Polymerization of non-condensable monomers in the gas phase (gas phase polymerization) D. A method of polymerizing non-condensable monomers in a liquid inert hydrocarbon (slurry polymerization), etc. In the above methods A and C, substantially no inert hydrocarbon is used. Here, substantially no inert hydrocarbon is used means that no inert hydrocarbon may be present in the reaction system, or a trace amount of inert hydrocarbon that does not affect the polymerization reaction may be present. As the liquid inert hydrocarbon, for example, an aliphatic hydrocarbon such as hexane, heptane, octane, or decane is preferably used. The polymerization method may be either continuous polymerization or batch polymerization. Prior to the continuous polymerization or batch polymerization, preliminary polymerization may be carried out. The number of polymerization stages may be one or more. For example, two-stage bulk polymerization, gas phase polymerization after bulk polymerization, two-stage gas phase polymerization, or more than two-stage polymerization may be used.

[0100] The above-mentioned vinyl-terminated propylene polymer of the present invention can be obtained, for example, by polymerizing the above-mentioned monomers using the above-mentioned olefin polymerization catalyst at a polymerization temperature of 60° C. or more and 90° C. or less by the above-mentioned method A. In the above-mentioned method A, a liquid inert hydrocarbon is not substantially used, but a trace amount of an inert solvent may be contained in the reaction system. For example, the ratio (M1 / M2) of the number of moles of propylene (M1) to the sum (M2) of the number of moles of propylene and the number of moles of the inert hydrocarbon may be 0.99 or more and 1.0 or less. In the polymerization for obtaining the vinyl-terminated propylene polymer of the present invention, the lower limit of the polymerization temperature is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 75° C. or higher, and the upper limit is preferably 90° C. or lower, more preferably 85° C. or lower, and even more preferably 80° C. or lower. In the polymerization for obtaining the vinyl-terminated propylene polymer of the present invention, the polymerization pressure is preferably 1 to 4.5 MPa (G), more preferably 2 to 4 MPa (G).

[0101] The present invention uses a catalyst system including a metallocene compound having a bisindenylhafnium complex structure, in which a 5-membered heterocycle having a specific heteroatom and a specific substituent at the 2-position of the indene ring as a ligand, and an aryl group having a specific substituent at the 4-position of the indene ring, to perform polymerization in a temperature range suitable for the polymerization method, and is capable of highly active production of a propylene-based polymer having a specific molecular weight (number average molecular weight of 10,000 or more and less than 50,000), a high terminal vinyl ratio, excellent regioregularity and stereoregularity, and an amount of hetero bonds (1,3 bonds) that is 0.06 mol % or more higher than the amount of hetero bonds (2,1 bonds).

[0102] Furthermore, in the production method of the present invention, it is preferable to supplementarily introduce hydrogen during polymerization in order to improve activity. It is believed that the activity is improved because dormant active sites, such as π-allyl-transition metal complexes formed as a result of side reactions and those immediately after propylene 2,1 insertion, are reactivated by hydrogen. In many transition metal complex catalysts, the chain transfer rate to hydrogen is high, and hydrogen acts as an effective chain transfer agent to generate saturated ends, so the introduction of hydrogen makes it difficult to produce terminal vinyl structures. However, in the production method of the present invention, surprisingly, even if hydrogen is added, the chain transfer rate to hydrogen is slow, but hydrogen acts as a reactivation agent, so the vinyl end ratio is still maintained high. Therefore, in the production method of the present invention, the activity is improved and the vinyl end ratio is maintained high by using hydrogen as an auxiliary in the polymerization step.

[0103] The amount of hydrogen used in the polymerization is preferably 0 to 2.0 × 10 in terms of the feed molar ratio of hydrogen to propylene (hydrogen / propylene). -3 mol / mol, more preferably greater than 0 mol / mol and up to 1.0×10 -3 mol / mol or less, more preferably 2.0×10 -5 ~5.0×10 -4 mol / mol, and even more preferably 3.0×10 -5 ~3.0×10 -4 The range is mol / mol. By using hydrogen within the above range, the vinyl-terminated propylene polymer of the present invention can be produced with high activity, and polymer particles having good particle properties can be obtained.

[0104] In the production method of the present invention, it is preferable to carry out copolymerization using, as a comonomer, an α-olefin having 2 to 20 carbon atoms other than propylene, in addition to the propylene monomer. As the comonomer, ethylene is preferably used. In order to obtain the propylene-based polymer of the present invention having a good balance between catalytic activity and melt tension, the amount of ethylene used is 70×10 in terms of the feed molar ratio of ethylene to propylene (ethylene / propylene).-3 mol / mol or less, more preferably 1.0×10 -3 ~60×10 -3 mol / mol, more preferably 10×10 -3 ~50×10 -3 By using ethylene in the above range, the crystallinity of the vinyl-terminated propylene polymer of the present invention can be reduced, and the vinyl-terminated propylene polymer of the present invention having a number average molecular weight (Mn) of 10,000 or more and less than 50,000 and a melting point (Tm) of less than 150° C. and further the above properties (I), (II), and (III) can be obtained with high activity. Furthermore, by combining hydrogen and ethylene within the above range, polymer particles having higher activity and better particle properties can be obtained. Comonomers such as 1-hexene, 1-octene, 4-methyl-1-pentene, etc. may also be used as long as they do not impair the properties of the present invention.

[0105] Characteristic (VIII): Coarse powder amount The vinyl-terminated propylene polymer of the present invention preferably further has the following property (VIII). Characteristic (VIII): The amount of coarse powder is 1 mass% or less. When the amount of coarse powder in the propylene polymer exceeds 1% by mass, usually, in bulk polymerization, problems such as contamination or fouling of a polymerization vessel occur. In response to this problem, the above-mentioned production method can reduce the amount of coarse powder in the obtained propylene polymer to 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. The amount of coarse powder is measured using a vibrating sieve particle size measuring device, and the ratio (mass %) of the polymer mass remaining on a sieve with an opening of 2000 μm or more to the total polymer mass that passed through the sieve is specified as the amount of coarse powder.

[0106] Property (IX): Bulk density The vinyl-terminated propylene polymer of the present invention preferably further has the following property (IX). Property (IX): Bulk density is 0.30 g / ml or more. The properties of the polymer particles of the propylene-based polymer can also be evaluated by the bulk density. The bulk density is an index that correlates with the average particle size of the polymer and the amount of coarse powder due to aggregation, etc., and the higher the bulk density, the better the shape of these polymer particles. According to the above-mentioned production method, the bulk density of the obtained propylene-based polymer can be made 0.30 g / ml or more, preferably 0.40 g / ml or more, more preferably 0.42 g / ml or more, and even more preferably 0.43 g / ml or more. The bulk density is measured in accordance with ASTM D1895-69.

[0107] 3. Uses of vinyl-terminated propylene polymers The vinyl-terminated propylene polymer of the present invention is a propylene polymer in which the terminal structure is highly controlled so as to contain a high proportion of vinyl terminal structures, and can be used as a powder material, and since it can suppress the decrease in transparency of the mixture obtained by melt-kneading with other materials, it can be suitably used as pellets cut into granular form after blending with various synthetic resins and heating and melt-kneading with a melt kneader. In addition, the vinyl-terminated propylene polymer of the present invention can be blended with various additives such as known antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, antiblocking agents, colorants, inorganic or organic fillers, etc., as necessary. EXAMPLES

[0108] Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. In the following examples, the measurements of physical properties and analyses were carried out according to the following methods.

[0109] (1) Catalytic activity (CE) (g / g) The catalytic activity was calculated by dividing the polymer yield (g) by the amount of catalyst (g) introduced (excluding the prepolymerized polymer).

[0110] (2) Number average molecular weight (Mn) The properties were measured by the method described above in the description of the characteristic (IV) and by gel permeation chromatography (GPC) using the method described hereinabove.

[0111] (3) Ethylene content The ethylene content is 13 The ethylene content [C2] (mol%) was calculated from the signal intensity of the C-NMR spectrum using the above-mentioned calculation formula.

[0112] (4) Isotactic triad fraction (mm fraction) The mm fraction was calculated by the method described above in the description of characteristic (II), and the unit is %.

[0113] (5) Heterogeneous binding amount Using the method described above in the description of characteristic (III), the amount of hetero bonds (2,1 bonds) ([2,1]) and the amount of hetero bonds (1,3 bonds) ([1,3]) were calculated, and [1,3]-[2,1] was calculated. The unit is mol%. Incidentally, the insertion of two ethylene units after the 2,1 bond is detected as the same structure as the 1,3 bond. However, in the following examples, the amount of 2,1 bonds is 0 and the ethylene content is minute compared to the propylene content, so that it is considered that the insertion of two ethylene units after the 2,1 bond will not be detected as a 1,3 bond.

[0114] (6) Number of LCBs The number of long chain branches (LCB) having 7 or more carbon atoms per 1000 monomer units was measured by the method described above in the description of property (I).

[0115] (7) Terminal vinyl ratio The terminal vinyl ratio was measured by the method described above in the description of property (I).

[0116] (8) Melting point (Tm): The melting point (Tm) was measured by DSC in the manner described above in the description of property (V).

[0117] (9) Soluble content below 40°C The proportion (mass %) of the amount of the component eluted at 40° C. in temperature rising elution fractionation (TREF) measurement using o-dichlorobenzene (ODCB) was measured by the method described above in the description of characteristic (VII).

[0118] (10) Soluble content below 90°C The proportion (mass %) of the amount of components eluted at a temperature of 90° C. or less in temperature rising elution fractionation (TREF) measurement using o-dichlorobenzene (ODCB) was measured by the method described above in the description of characteristic (VI).

[0119] (11) Bulk density (BD) Bulk density was measured according to ASTM D1895-69.

[0120] (12) Amount of coarse powder Using a vibrating sieve particle size measuring device, the ratio (mass %) of the polymer mass remaining on a sieve with an opening of 2000 μm or more to the total polymer mass that passed through the sieve was taken as the amount of coarse powder.

[0121] [Example 1] (1) Synthesis of component (A) Synthesis of rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl}]hafnium: (1-a) Synthesis of dimethylbis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl}silane: 2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indene (8.4g, 24.4mmol) and THF (150ml) were added to a 1000ml glass reaction vessel and cooled to -70℃. n-Butyllithium-hexane solution (15.5ml, 24.3mmol, 1.57mol / L) was added dropwise thereto. After the addition, the mixture was stirred for 2 hours while gradually returning to room temperature. The mixture was cooled again to -70℃, 1-methylimidazole (0.02ml) was added, and dimethyldichlorosilane (1.47ml, 12.1mmol) was added dropwise thereto. After the addition, the mixture was stirred for 1 hour while gradually returning to room temperature. Distilled water was added to the reaction solution, which was then transferred to a separatory funnel and washed with saline until it became neutral. Sodium sulfate was added to the funnel to dry the reaction solution. The sodium sulfate was filtered off, and the solvent was removed under reduced pressure to obtain a pale yellow solid of dimethylbis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl}silane (9 g).

[0122] (1-b) Synthesis of rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl}]hafnium: In a 500 ml glass reaction vessel, 9 g (12.2 mmol) of dimethylbis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl}silane, 30 ml of diethyl ether, and 90 ml of toluene were added, and n-butyllithium-hexane solution (15.5 ml, 24.3 mmol, 1.57 mol / L) was added dropwise in an ice bath. After the addition, the mixture was returned to room temperature and stirred for 1 hour. Then, 110 ml of toluene was added, and the mixture was cooled to -70°C in a dry ice-methanol bath. 3.9 g (12.2 mmol) of hafnium tetrachloride was added thereto. After that, the mixture was gradually returned to room temperature and stirred overnight. The solvent was removed under reduced pressure, the extract was extracted with toluene, and then washed with a toluene-hexane mixture to obtain 1 g (yield 8%) of racemic dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)indenyl}]hafnium (purity 99% or more) as yellow-orange crystals. The racemic mixture was analyzed by proton nuclear magnetic resonance (1 The identified values ​​by H-NMR are shown below. 1 H-NMR (CDCl 3 ) Identification results Racemic: δ1.07(s,6H), δ1.31(s,18H), δ2.48(s,6H), δ6.62(s,2H), δ6.7-7.1(m,4H), δ7.2-7.6(m,10H), δ7.41(d,2H), δ7.55(d,2H)

[0123] (2) Synthesis of component (B) (chemical treatment of ion-exchangeable layered silicate) Into a 1 L three-neck flask equipped with a stirring blade and a reflux device, 645.1 g of distilled water and 82.6 g of 98% sulfuric acid were added and heated to 95°C. 100 g of 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 for 320 minutes at 95° C. After 320 minutes, 0.5 L of distilled water was added to stop the reaction, and 255 g of a cake-like solid was obtained by filtration. This cake (1 g) contained 0.31 g of the chemically treated montmorillonite (intermediate). The chemical composition of the chemically treated montmorillonite (intermediate) was Al = 7.68 mass%, Si = 36.05 mass%, Mg = 2.13 mass%, and the Al / Si (molar ratio) = 0.222. 1545g of distilled water was added to the cake to make a slurry, and the temperature was raised to 40℃. 5.734g of lithium hydroxide hydrate was added as a solid, and the reaction was carried out at 40℃ for 1 hour. After 1 hour, the reaction slurry was filtered and washed with 1L of distilled water three times, and a cake-like solid was obtained again. The collected cake was dried to obtain 80 g of chemically treated montmorillonite, which had a chemical composition of Al=7.68% by mass, Si=36.05% by mass, Mg=2.13% by mass, Al / Si (molar ratio)=0.222, and Li=0.53% by mass.

[0124] (3) Preparation of olefin polymerization catalyst In a three-neck flask (volume 1 L), 10 g of the chemically treated montmorillonite obtained in (2) above was placed, and heptane (65 mL) was added to make a slurry. Triisobutylaluminum (25 mmol: 35 mL of a heptane solution with a concentration of 143 mg / mL) was added to this and stirred for 1 hour, and then the mixture was washed with heptane until the residual liquid ratio became 1 / 100, and the total volume was made up to 50 mL. In addition, in a separate flask (volume 200 mL), rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-thienyl)-4-(4-t-butylphenyl)-indenyl}]hafnium (component (A)) (0.15 mmol) obtained in (1) above was dissolved in toluene (30 mL) to prepare solution 1. To the 1 L flask containing the above-mentioned chemically treated montmorillonite, tri-n-octylaluminum (2.1 mmol: 5.3 mL of a heptane solution with a concentration of 144 mg / mL) was added, and then the above-mentioned solution 1 was added and stirred at room temperature for 1 hour. Then, 215 mL of heptane was added, and the resulting 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 carried out while maintaining 40°C for 2 hours. Then, the propylene feed was stopped, and residual polymerization was carried out for 1.5 hours. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (10 mmol: 8.3 mL of a heptane solution with a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes. The solid was dried under reduced pressure for 40 minutes to obtain 13.6 g of a dried prepolymerized catalyst. The prepolymerization ratio (amount of prepolymerized polymer divided by amount of solid catalyst) was 0.33. This prepolymerized catalyst was designated as Catalyst 1.

[0125] (4) Polymerization The inside of a 20 L autoclave was replaced with propylene and cooled to room temperature. 18.7 mL of a heptane solution of triisobutylaluminum (140 mg / mL), 0.26 N (normal) L of hydrogen, and 54 g of ethylene were introduced into the polymerization tank of this autoclave. Next, 5 kg of liquid propylene was introduced into the tank, and the temperature was raised to 63°C. The amounts of hydrogen and ethylene introduced were 0.0002 mol / mol and 0.016 mol / mol, respectively, in terms of the feed molar ratio to propylene. Thereafter, 100 mg of the catalyst 1 (excluding the prepolymerized polymer) was pumped into the polymerization tank with high-pressure argon to initiate polymerization, and the temperature was quickly raised to 70° C. The temperature was maintained at 70° C., and after 3 hours from the start of polymerization, the unreacted propylene was quickly purged to terminate the polymerization. As a result, 892 g of a propylene-ethylene copolymer was obtained.

[0126] [Example 2] Polymerization was carried out in the same manner as in Example 1, except that the amount of ethylene introduced was changed to 107 g, and 1,230 g of a propylene-ethylene copolymer was obtained.

[0127] [Example 3] Polymerization was carried out in the same manner as in Example 1, except that the amount of ethylene introduced was changed to 160 g. As a result, 1,415 g of a propylene-ethylene copolymer was obtained.

[0128] [Table 1]

[0129] [Discussion of the Examples] The propylene-based polymers obtained in each Example had a number average molecular weight (Mn) of 23030 to 27100, and were usable as powders and granules, but had a sufficiently small number average molecular weight (Mn) from the viewpoint of reactivity, and had a high terminal vinyl ratio of 0.94 or more, and excellent reactivity of the terminal vinyl group. In addition, the propylene-based polymers obtained in each Example had a high mm fraction of 96.0% or more, excellent stereoregularity, an amount of heterogeneous bonds (2,1 bonds) of less than 0.01 mol% and an amount of heterogeneous bonds (1,3 bonds) of 0.07 to 0.10 mol%, and thus had a small amount of heterogeneous bonds and excellent regioregularity. The propylene-based polymers obtained in each Example thus had good regularity and a sufficiently small number average molecular weight (Mn), and therefore had good fluidity when made into powders and granules. Furthermore, the propylene-based polymers obtained in each Example had a heterogeneous bond (1,3 bond) amount that was 0.07 to 0.10 mol % more than the heterogeneous bond (2,1 bond) amount, and a melting point (Tm) of 135 to 144° C., so that the decrease in transparency when melt-kneaded with other resins could be suppressed. Furthermore, the propylene-based polymers obtained in each Example had a low melting point (Tm), so that the melt-kneading temperature could be lowered, and therefore side reactions could be suppressed and production efficiency could be improved. In Examples 1 to 3, the polymerization was carried out by using an olefin polymerization catalyst containing the above-mentioned components (A), (B) and (C), using ethylene as a comonomer, and introducing hydrogen during polymerization, thereby obtaining a propylene-based polymer having the above-mentioned characteristics, a small amount of coarse powder, a high bulk density and good particle properties.

Claims

1. A vinyl-terminated propylene polymer having the following properties (I), (II), (III), (IV) and (V): Property (I): The terminal vinyl ratio is 0.7 or more. Property (II): The isotactic triad fraction (mm fraction) is 90% or more. Characteristic (III): The amount of hetero bonds (2,1 bonds) is 0.03 mol % or less, and the amount of hetero bonds (1,3 bonds) is 0.06 mol % or more more than the amount of hetero bonds (2,1 bonds). Property (IV): The number average molecular weight (Mn) is 10,000 or more and less than 50,000. Property (V): Melting point (Tm) is less than 150°C.

2. The vinyl-terminated propylene polymer according to claim 1, further having the following property (VI): Property (VI): In an elution curve obtained by temperature rising elution fractionation (TREF) measurement using o-dichlorobenzene (ODCB), the amount of components eluted at a temperature of 90° C. or less is 20% by mass or more and 100% by mass or less.

3. A method for producing the vinyl-terminated propylene polymer according to claim 1, comprising the steps of: A method for producing a propylene-based polymer having a terminal vinyl group, comprising polymerizing propylene alone or propylene together with at least one comonomer selected from ethylene and an α-olefin using an olefin polymerization catalyst comprising the following components (A), (B), and (C): Component (A): a metallocene compound represented by the following general formula (1): 【Chemistry 1】 [In general formula (1), R １１ and R １２ each independently represents a heterocyclic group constituting a 5-membered ring having at least one hydrocarbon group having from 1 to 3 carbon atoms as a substituent which may have a heteroatom, provided that the heteroatom of the heterocyclic group is not directly bonded to the indene ring. R １３ and R １４ is independently an aryl group having a substituent only at the 4-position, and the substituent is a hydrocarbon group having 3 to 6 carbon atoms which may contain at least one atom selected from a hetero atom and a halogen atom. However, R １１ and R １２ and the substituent of the heterocyclic group in R １３ and R １４ and the total number of carbon atoms and heteroatoms contained in the substituents of the heterocyclic group that is the largest among the substituents of the heterocyclic group is smaller than the total number of carbon atoms and heteroatoms contained in the substituents of the aryl group. X １１ and Y １１ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a halogenated hydrocarbon group having from 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having from 1 to 20 carbon atoms. Q １１ represents 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 germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Component (B): a compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum Compound

4. In the metallocene compound represented by the general formula (1), R １１ and R １２ The method for producing a vinyl-terminated propylene polymer according to claim 3 , wherein each of the above independently has a structure represented by the following general formula (2): 【Chemistry 2】 [In the general formula (2), T is S or NR ２０ represents R ２０ represents a hydrogen atom, a hydrocarbon group having from 1 to 6 carbon atoms, a hydroxyl group, or an alkoxy group having from 1 to 6 carbon atoms; R ２１ and R ２２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms which may have a heteroatom; R ２１ and R ２２ At least one of R ２１ and R ２２ The heteroatom of the hydrocarbon group in R is not directly bonded to the heterocyclic group constituting the five-membered ring. ２１ and R ２２ does not bond to form a ring.

5. In the metallocene compound represented by the general formula (1), R １１ and R １２ The method for producing a propylene-based polymer having a terminal vinyl group according to claim 3 or 4, wherein each of the heterocyclic groups is independently a heterocyclic group constituting a 5-membered ring having a substituent only at the 5-position.

6. 5. The method for producing a vinyl-terminated propylene polymer according to claim 3, wherein at least propylene and ethylene are polymerized in the polymerization.

7. 5. The method for producing a vinyl-terminated propylene polymer according to claim 3, wherein in the polymerization, at least propylene and ethylene are polymerized, and hydrogen is introduced during the polymerization.

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