Solid titanium catalyst component, olefin polymerization catalyst and olefin polymerization method

Description

1 / 97 SOLID TITANIUM CATALYST COMPONENT, CATALYST FOR OLEFIN POLYMERIZATION AND METHOD FOR OLEFIN POLYMERIZATION Technical Field

[0001] The present invention relates to a solid titanium catalyst component, a catalyst for olefin polymerization containing the solid titanium catalyst component, and a method for polymerizing an olefin using the olefin polymerization catalyst. Prior Art

[0002] To date, known catalysts used to produce an olefin polymer, such as an ethylene homopolymer, an α-olefin homopolymer, or an ethylene / α-olefin copolymer, include catalysts containing a titanium compound supported on an activated magnesium halide. Hereafter, homopolymerization and copolymerization may be collectively referred to as polymerization.

[0003] For example, catalysts containing titanium tetrachloride or titanium trichloride, called Ziegler-Natta catalysts, and catalysts containing an organometallic compound and a solid titanium catalyst component composed of magnesium, titanium, halogen and an electron donor, are widely known as such catalysts for olefin polymerization.

[0004] The latest catalysts exhibit high activity in the polymerization of α-olefins, such as ethylene, propylene, and 1-butene. The resulting α-olefin polymers may exhibit high stereoregularity.

[0005] Excellent polymerization activity and stereospecificity are reported to be demonstrated when, among the above catalysts, a catalyst composed of a solid titanium catalyst component carrying an electron donor selected from carboxylic acid esters is used. Petition 870250085949, dated 09 / 23 / 2025, page 13 / 112 2 / 97 represented by phthalic acid esters, an aluminum-alkyl compound as a cocatalyst component, and a silicon compound containing at least one Si-OR (where R is a hydrocarbon group) is used in particular (e.g., Patent Literature 1). In addition to phthalic acid esters, a large number of electron donors, such as polyether compounds, are being researched.

[0006] In connection with research involving an ester compound as an electron donor, a catalyst containing a carboxylic acid ester with two or more ester groups is also disclosed (e.g., Patent Literature 2). The present Applicant has also reported that an ester compound with a specific cyclic structure provides, in a highly active manner, a polyolefin with a wide molecular weight distribution (Patent Literature 3).

[0007] A catalyst with a substituted succinic acid ester as an electron donor is reported as a catalyst that provides a polyolefin with a wide molecular weight distribution. The present Applicant has also reported catalysts containing a polycarboxylic acid ester with a specific cyclic structure (Patent Literature 4 to 6). List of Citations Patent Literature

[0008] Patent Literature 1: JP 57-63310 A Patent Literature 2: JP 2005-517746 A Patent Literature 3: WO 2008 / 010459 Patent Literature 4: WO 2006 / 077945 Patent Literature 5: WO 2022 / 045232 Patent Literature 6: WO 2022 / 138634 Summary of the Invention Technical Problem

[0009] It is known that polypropylene (a polymer of Petition 870250085949, dated 09 / 23 / 2025, p. 14 / 112 Polypropylene (3 / 97), which represents a polymer of an olefin with 3 or more carbon atoms, has the potential to exhibit heat resistance and stiffness comparable to general-purpose engineering plastics, although it has a hydrocarbon structure. Polyolefin, being a hydrocarbon structure, is a material with relatively low environmental impacts, as it generates virtually no toxic gases during combustible disposal or thermal recycling (a recycling method to recover thermal energy from combustion, such as electrical energy).

[0010] It is well known that the heat resistance of propylene polymer depends on its stereoregularity, but it also appears to depend on the relationship between stereoregularity and molecular weight and its distribution. It is also known that stiffness is affected by molecular weight distribution as well as stereoregularity. Although techniques have been developed that control stereoregularity to a considerable degree, it is expected that, with the recent advancement of molding technology, polymers with higher stereoregularity may exhibit unexpected physical properties. Simultaneously having a wider molecular weight distribution may further improve the balance between physical properties. Furthermore, from the point of view of heat resistance and heat-resistant stiffness, a high melting point and a high heat of fusion of the polymers are preferable.

[0011] Consequently, an objective of the present invention is to provide a solid titanium catalyst component, a catalyst for olefin polymerization, and a method for polymerizing an olefin that allows the production of an olefin polymer with a wide molecular weight distribution, high melting point, and high heat of fusion. Solution to the Problem

[0012] As a result of diligent research, the present Petition 870250085949, dated 09 / 23 / 2025, page 15 / 112, inventors found that a solid titanium catalyst component containing a polyvalent amide compound with a specific structure allows the production of an olefin polymer with a wide molecular weight distribution, high melting point and high heat of fusion in a highly active manner, and concluded the present invention. Examples of the present invention are shown below.

[0013] {1} A solid titanium catalyst component, including magnesium, titanium, halogen and an amide compound specified by the following formula (1): [Chemical Formula. 1] In formula (1), C, C1 and C2 are carbon atoms. N is a nitrogen atom, R1 and R2 are each a hydrocarbon group. R3a and R6 are each a group containing an element selected from carbon, hydrogen, and elements from Groups 15, 16, and 17 of the periodic table. R11 and R12 are each a hydrogen atom or a hydrocarbon group, m is an integer from 0 to 10, and A is a linking group selected from an aliphatic group, an alicyclic group, and an aromatic group, and a plurality of A, when present, are either all groups with the same structure or are groups with structures that differ partially or totally from each other.

[0014] {2} The solid titanium catalyst component according to item {1}, wherein the amide compound is specified. Petition 870250085949, dated 09 / 23 / 2025, p. 16 / 112 5 / 97 by the following formula (2): [Chemical Formula 2] xAR6(CRM m ।XN R11R12 XC II R2(2) In formula (2), R1a R6, R11, R12, C, C1, C2 and N are as defined for formula (1), m is an integer from 1 to 10, a plurality of Rx are groups containing an element selected from carbon, hydrogen and elements of Groups 15, 16 and 17 of the periodic table, and Rx are optionally linked together to form a ring structure.

[0015] {3} The solid titanium catalyst component according to item {1} or {2}, where Rll and R12 are hydrogen atoms.

[0016] {4} The solid titanium catalyst component according to any one of items {1} to {3}, wherein R3, R4, R5 and R6 are hydrogen atoms.

[0017] {5} A catalyst for the polymerization of olefins, including the solid titanium catalyst component (I) according to any one of items {1} to {4} and an organometallic compound catalyst component (II) containing a metallic element selected from Groups 1, 2 and 13 of the periodic table.

[0018] {6} The catalyst for olefin polymerization according to item {5}, including an electron donor (III).

[0019] {7} A method for polymerizing olefins, including the polymerization of an olefin in the presence of the catalyst for olefin polymerization according to item {5} or {6}. Advantageous Effects of the Invention Petition 870250085949, dated 09 / 23 / 2025, page 17 / 112 6 / 97

[0020] According to the solid titanium catalyst component, the catalyst for olefin polymerization and the olefin polymerization method of the present invention, an olefin polymer with a wide molecular weight distribution, a high melting point and a high heat of fusion can be produced.

[0021] Therefore, it can be expected that the use of the solid titanium catalyst component, catalyst for olefin polymerization, and polymerization method of an olefin of the present invention will allow the production of an olefin polymer that possesses, for example, not only moldability and rigidity, but also high heat resistance. Description of Embodiments

[0022] Next, the solid titanium catalyst component (I), catalyst for olefin polymerization, method for producing an olefin polymer and propylene polymer according to the present invention will be described in detail. [Solid titanium catalyst component (I)]

[0023] The solid titanium catalyst component (I) according to the present invention contains titanium, magnesium, halogen and an amide compound with a specific structure (hereinafter sometimes simply referred to as the amide compound). <Composto de amida>

[0024] The amide compound is represented by the following formula (1). [Chemical Formula. 3] R4R5 (1) Petition 870250085949, dated 09 / 23 / 2025, page 18 / 112 7 / 97

[0025] In formula (1) above, C, C1 and C2 are carbon atoms and N is a nitrogen atom. In addition, lines like - represent covalent bonds.

[0026] R1 and R2 are hydrocarbon groups. More specifically, R1 and R2 are each a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms, preferably a substituted or unsubstituted hydrocarbon with an aryl group and 6 to 20 carbon atoms, and may be a heteroatom-containing structure, which will be described later. Examples of heteroatom-containing aryl groups include those with a basic skeleton with a structure in which the aryl structure itself contains a heteroatom, such as a pyrrole ring or a pyran ring, and those in which a substituent, such as a heteroatom-containing hydrocarbon group, for example, an alkoxy group, is attached to a benzene ring.

[0027] A representative example of a heteroatom-containing structure is a structure with a heteroatom-containing substituent. A preferred example of such a substituent is a heteroatom-containing aryl group, and a particularly preferred example is an oxygen-containing aryl group.

[0028] Note that R1 and R2 of the present invention preferably have a structure in which a carbon atom is covalently bonded to the adjacent carbonyl carbon.

[0029] R1, R2, R3, R4, R5, R6, R11, R12 and A described above can be linked together to form a ring structure. Their preferred aspects will be described later.

[0030] R1 and R2 can be connected to each other to form a ring structure. Furthermore, selected substituents of R1, R11, described later, R3 and R4 can be connected to each other to form a ring structure. Furthermore, selected substituents of R2, R12, described later, R5 and R6 can be connected to each other to form a ring structure. Petition 870250085949, dated 09 / 23 / 2025, p. 19 / 112 8 / 97

[0031] A substituent selected from substituents R3 and R4 and a substituent selected from substituents R5 and R6 can also be connected to each other to form a ring structure. In this case, m, described later, is preferably 1 or more.

[0032] The ring structure formed by these substituents and the linking group A, described later, is preferably an alicyclic structure of 5 or more members, and more preferably a ring of 6 or more members, considering the mobility around carbon C1 and carbon C2 in formula (1), as described later. On the other hand, the upper limit of the number of members in the ring structure is arbitrary, but is preferably a 10-membered ring, and more preferably an 8-membered ring. Note that it may be preferable that at least one of the structures containing carbon C1 and carbon C2 be different from a cyclic structure.

[0033] R3a R6 are groups containing an element selected from carbon, hydrogen, and elements from Groups 15, 16, and 17 of the periodic table. More specifically, R3a R6 are each a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms, and a halogen atom.

[0034] A hydrogen atom, a carbon atom, or both in R3a R6 can be partially replaced by an atom selected from the group consisting of elements from Groups 15 to 17 of the periodic table, such as a nitrogen atom, an oxygen atom, a phosphorus atom, and a halogen atom. That is, aspects of R3a R6 include hydrocarbon groups containing an atom selected from the group consisting of elements from Groups 15 to 17 of the periodic table, such as nitrogen, oxygen, phosphorus, and halogen. The atom described above can be replaced in one or more positions.

[0035] In the present invention, the term atom, as in, by Petition 870250085949, dated 09 / 23 / 2025, p. 20 / 112 9 / 97 For example, a halogen atom or a hydrogen atom in the description of a substituent can, of course, refer to aspects with a bond such as H- or Cl- when expressed in a structural formula.

[0036] Furthermore, when R3 and R4 or R5 and R6 form a ring structure, this includes aspects in which a carbon-carbon double bond is formed (in this case, the carbon-carbon double bond is considered a 2-membered ring). On the other hand, R3 and R6 may be linked to the linking group A described later to form a ring structure, but in this case, aspects of double bond formation are excluded from the scope of the present invention. The reason why such a structure is suitable for the present invention will be described later.

[0037] R3a R6 are preferably relatively low-volume substituents, and particularly preferably hydrogen atoms. In solid titanium catalyst components containing organic compounds (sometimes commonly referred to as internal donors), there tend to be many instances where bulky compounds are suitable. Although the reason why such low-volume substituents tend to be suitable in the present invention is not known to date, it is believed to be probably because, as described later, the amide compound of the present invention tends to stably assume a relatively suitable conformation as a catalyst component for the polymerization of olefins, for example, and therefore, when the substituents R3a R6 on the opposite side of the amide groups have less bulky structures, the coordination of the olefin with the titanium of the solid titanium catalyst component is less likely to be disordered.

[0038] R11 and R12 are hydrogen atoms or hydrocarbon groups. These hydrocarbon groups are the same as the aspects described for R1 and R2. Petition 870250085949, dated 09 / 23 / 2025, page 21 / 112 10 / 97

[0039] R11 and R12 are sometimes, preferably, hydrogen atoms. The structure in which R11 and R12 are hydrogen, namely the structure represented by -NH, is generally considered to have active hydrogen and can generally function as a catalytic poison as an internal donor component included in solid titanium catalyst components. Although the reason why even such a -NH structure demonstrates a suitable effect in the present invention is not known at present, the present inventors speculate as follows.

[0040] The two -NH structures, as described above, are located relatively close to each other and are therefore expected to have a relatively strong interaction, such as a hydrogen bond. The -NH structure is also expected to have a relatively strong interaction with the carbonyl group of the other amide group for the same reason. Therefore, it is believed that the action as a catalytic poison may be reduced. It is also believed that the interaction described above has the effect of suppressing the rotation of the amide groups and facilitating the obtaining of a relatively stable conformation with relatively little alteration, such as, for example, a pseudo-ring structure, a conformation in which relatively large torsional movements occur and therefore a moderate interaction with titanium can be formed in the solid titanium catalyst component and active sites with high stereoregularity can be easily formed.

[0041] Based on the same idea described above, it is also expected that a structure in which R11 and R12 are linked together to form a ring structure is a preferred aspect of the present invention. Obviously, hydrocarbon groups may be preferred for R11 and R12, including an aspect in which they form a ring structure, as described above.

[0042] From this point of view, nitrogen atoms of at least Petition 870250085949, dated 09 / 23 / 2025, p. 22 / 112 11 / 97 less two amide groups possessed by the amide compound of the present invention are preferably linked by means of 2 to 10 atoms, including carbon (corresponding to a portion of -C1-AmC2-). More preferably, they are linked by means of 2 to 8 atoms, and even more preferably, by 3 to 6 atoms. Thus, it may be preferable that the two amide groups be in a positional relationship that is neither too close nor too far apart.

[0043] A in the amide compound of the present invention is a linking group selected from an aliphatic group, an alicyclic group and an aromatic group, and when there is a plurality of A, the plurality of A may be composed of all groups with the same structure, or may be groups with structures that differ partially or totally from each other. The linking group described above may also be read as a divalent substituent.

[0044] The linking group, as described above, is preferably a substituent with an aliphatic structure, an alicyclic structure, or an aromatic structure. Furthermore, among the above, a substituent selected from an alicyclic structure and an aromatic structure is preferred, and even more preferably a substituent with an alicyclic structure. Such a substituent is preferably, for example, a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms. Examples of the hydrocarbon group with a substituent described above may include substituents with the heteroatom-containing substituent described above.

[0045] As the amide compound of the present invention, compounds with a structure specified by formula (2), as described below, are more defined. [Chemical Formula 4] Petition 870250085949, dated 09 / 23 / 2025, page 23 / 112 12 / 97 R4r34k (CRx2)ni ΐ R.AR6 RliR12 R2(2)

[0046] In the above, R1a R6, R11, R12, C, C1, C2, N em are common to formula (1).

[0047] Examples of Rx above may include the same substituents as R3a R6.

[0048] When m is an integer from 1 to 10, it is sometimes preferable that a plurality of Rx be linked together to form a ring structure, such as an alicyclic structure or an aromatic structure. Such a ring structure is even more preferably an alicyclic structure.

[0049] Furthermore, insofar as the purpose of the present invention is not impaired, the chain structure (CRX2) described above may have a structure in which a heteroatom, such as a group containing oxygen or nitrogen, is included between the carbon atoms.

[0050] One of the features of the amide compound of the present invention is that it has a structure in which the linking group A and the nitrogen of the amide group are linked via a carbon atom (C1 and C2). As such a structure is considered to have relatively low stiffness, it is speculated that the relatively buoyant (e.g., twisted) conformation, as described above, is easily obtained with titanium in the solid titanium catalyst component, thus demonstrating suitable effects as described above.

[0051] m in the amide compound of the present invention is an integer from 0 to 10. The lower limiting value is preferably 1, and even more preferably 2, depending on the structure of A. On the other hand, the upper limiting value is in a way Petition 870250085949, dated 09 / 23 / 2025, page 24 / 112 13 / 97 preferred 8, in a more preferred manner 7, and in a still more preferred manner 6. Within this range, the distance between at least the two amide groups is expected to be within an appropriate range, demonstrating adequate olefin polymerization performance of the present invention. When m is 0, C1 and C2 are linked by a single bond.

[0052] The hydrocarbon group that is a specific example of R1a R12 is a monovalent hydrocarbon group with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 3 to 8 carbon atoms, even more preferably 4 to 8 carbon atoms, and particularly preferably 4 to 6 carbon atoms.Examples of such hydrocarbon groups include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a cyclohexyl group, a substituted or unsubstituted aryl group, such as a phenyl group, and a substituted or unsubstituted cycloalkenyl group. Alicyclic hydrocarbon groups and aromatic hydrocarbon groups may contain a substituent. Among such substituents, an n-butyl group, an isobutyl group, a hexyl group, an octyl group, and a phenyl group are preferred, and most preferred are an n-butyl group, an isobutyl group, and a phenyl group.

[0053] Furthermore, in the case of hydrocarbon groups containing elements from Groups 15 to 17 of the periodic table, such as nitrogen, oxygen, phosphorus and halogen, specifically, preferable examples may include a group containing a structure Petition 870250085949, dated 09 / 23 / 2025, p. 25 / 112 14 / 97 carbonyl, as a carboxylic acid ester group, an aldehyde group, an acetyl group or an oxycarbonylalkyl group, an alkoxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group and a siloxy group. The heteroatom is preferably nitrogen and oxygen, and more preferably oxygen.

[0054] The heteroatom-containing substituent is preferably an aryl group containing an oxygen-containing substituent, and a preferred example is specifically a structure in which an oxygen-containing substituent, such as an alkoxy group, an aryloxy group, an alkoxyalkyl group, an aryloxyalkyl group, and a substituent in which the oxygen of the above substituent is replaced by a carbonyl or carboxyl group, is attached to an aromatic skeleton. Among such substituents, a substituent in which an alkoxy group or an aryloxy group is attached to an aromatic skeleton is preferred, and a substituent in which an alkoxy group is attached to an aromatic skeleton is more preferred. The number of carbon atoms in the oxygen-containing substituent is preferably from 1 to 10, more preferably from 1 to 8, and even more preferably from 1 to 6.More specifically, preferable examples, in addition to the methoxyphenyl group, include an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, and a phenoxyphenyl group. An aryl group containing such an oxygen-containing substituent may be used in a particularly preferred manner for R1 and R2.

[0055] Among such substituents, examples of R3 to R6, R11 and Petition 870250085949, dated 09 / 23 / 2025, p. 26 / 112 15 / 97 R12 may include a hydrogen atom, a hydrocarbon group, such as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, and a substituted or unsubstituted aryl group; and a hydrocarbon group containing a heteroatom, such as a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group. Among these, hydrogen atoms are preferred, as mentioned above. As a hydrocarbon group, substituents with 1 to 8, even 1 to 7, and especially 1 to 6 carbon atoms, are preferred.Furthermore, among the groups mentioned above, heteroatom-free alkyl groups are preferred.

[0056] Specific examples of the linkage group A of the present invention may include divalent substituents corresponding to the structure of the monovalent substituents described above.

[0057] Among them, preferred examples may include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,3-butylene group, a 2,3-butylene group, a 2,4-pentylene group, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a 1,2-cycloheptalene group, a 1,3-cycloheptalene group, a 1,4-cycloheptalene group, a 1,2-phenylene group and a 1,3-phenylene group.

[0058] Examples of such amide compounds may include the following structures. Some structural formulas of the exemplary compounds below have stereoisomers and, although Petition 870250085949, of 23 / 09 / 2025, p. 27 / 112 16 / 97 some isomeric structures are represented, there may be other isomeric structures that are not exemplified. [Chemical Formula 5] Ph. NH HN„ Ph Ph. UH HN . .Ph Ph. UH HN. .Ph Ph. NH HN, .Ph Ph. UH HN. .Ph YYYYYYYYY 0 0 OOO 0 0 o O 0 A-1 A-2 A-3 A-4 A-5 Me Me Μθ, E. ί. npr\^^ / 'Pr 'Pru^\^'Pr Bu^ / x^Bu Ph. UH HN. .Ph Ph. .NH HN . .Ph Ph. .NH HN. .Ph Ph. .NH HN. .Ph Ph. UH HN. .Ph YYYYYYYYYY 0 0 OOOO 0 o O 0 A-6 A-7 A-8 A-9 A-10 Me Et CyYxr / Gy Ph^ / \^Ph Me.|-,^,Me Et\|A^.Et UH HN .NH HN I. .Ph UH HY . 0 0 OOO 0 OOOO A-11 A-12 A-13 A-14 A-15 A-27 Petition 870250085949, dated 09 / 23 / 2025, page 28 / 112 17 / 97 [Chemical Formula 6] A-28 A-29 Me A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A-43 A-47 Me OO A-48 A-54 [Chemical Formula 7] B-11 B-12 B-13 B-14 Petition 870250085949, dated 09 / 23 / 2025, p. 29 / 112 18 / 97 B-15 B-16 B-17 B-18 B-19 B-20 B-21 B-22 Petition 870250085949, dated 09 / 23 / 2025, p. 30 / 112 19 / 97 [Chemical Formula 8] B-24 B-35 B-36 B-37 B-38 Petition 870250085949, dated 09 / 23 / 2025, p. 31 / 112 20 / 97 [Chemical Formula 9] 'Bu And OO B-41 OO B-42 B-55 Petition 870250085949, dated 09 / 23 / 2025, p. 32 / 112 21 / 97 [Chemical Formula 10] C-10 C-19 C-20 C-21 C-22 Petition 870250085949, dated 09 / 23 / 2025, p. 33 / 112 22 / 97 [Chemical Formula 11] C-24 C-35 C-36 C-37 C-38 Petition 870250085949, dated 09 / 23 / 2025, p. 34 / 112 23 / 97 [Chemical Formula 12] C-39 C-41 C-42 C-43 C-47 C-55 Petition 870250085949, dated 09 / 23 / 2025, p. 35 / 112 24 / 97 [Chemical Formula 13] D-5 D-6 D-7 D-8 D-9 D-10 D-11 D-12 D-16 D-19 D-20 D-21 Petition 870250085949, dated 09 / 23 / 2025, p. 36 / 112 25 / 97 [Chemical Formula 14] D-26 D-27 D-28 D-29 D-31 D-45 D-46 Petition 870250085949, dated 09 / 23 / 2025, p. 37 / 112 26 / 97 [Chemical Formula 15] D-50 D-57 D-58 D-59 Petition 870250085949, dated 09 / 23 / 2025, p. 38 / 112 27 / 97 [Chemical Formula. 16] Petition 870250085949, dated 09 / 23 / 2025, page 39 / 112 28 / 97 Petition 870250085949, dated 09 / 23 / 2025, page 40 / 112 29 / 97 [Chemical Formula. 18] pH NH HN THE THE pH E-2 E-3 E-4 E-1 'Pr OO 'PrnBu O OnBu E-5 E-6 E-7 E-8 OMe OO OMe E-11 CF3O O CF3 Me2N OO NMe20 0 0 0 OO E-13 E-14 E-15 E-16 00 OO 00 E-17 E-18 E-19 E-20 Cy CF3 Petition 870250085949, dated 09 / 23 / 2025, page 41 / 112 30 / 97 [Chemical Formula. 19] the E-25 oo E-26 E-34 MeO OMe CF3 E-35 E-36 E-39 E-40 Me E-43 E-44 E-27 E-28 E-32 Petition 870250085949, dated 09 / 23 / 2025, page 42 / 112 31 / 97 [Chemical Formula. 20] E-49 E-60 E-62 E-63 E-64 Petition 870250085949, dated 09 / 23 / 2025, page 43 / 112 32 / 97 [Chemical Formula. 21] E-66 E-70 E-75 E-76 E-82 E-83 Petition 870250085949, dated 09 / 23 / 2025, page 44 / 112 33 / 97 [Chemical Formula. 22] Me2N OO NMe20 0 0 0 0 0 F-13 F-14 F-15 F-16 00 00 00 F-17 F-18 F-19 F-20 Petition 870250085949, dated 09 / 23 / 2025, page 45 / 112 34 / 97 [Chemical Formula. 23] Bye pH F-43 F-44 Petition 870250085949, dated 09 / 23 / 2025, page 46 / 112 35 / 97 [Chemical Formula. 24] F-60 F-61 F-62 F-65 F-66 F-67 F-68 F-64 F-69 Petition 870250085949, dated 09 / 23 / 2025, page 47 / 112 36 / 97 [Chemical Formula. 25] Ph.,NH HN 'Pr Ph.. ,NH HN Bu ¥ ¥ ¥ ¥ 0 0 0 0 F-71 F-71 Me Ya Τχ XX Ph, AH HN, .Ph Ph. NH HN, _Ph YYYY 0 0 0 0 F-75 F-76 Ph. ,NH HN. .Ph Ph. AH HN. .Ph lí YYY 0 0 0 0 F-80 F-81 F3C^íA Me2N^^ TI τχ Ph..NH HN..Ph Ph. AH HN^. YYYY 0 0 0 0 F-85 F-86 McO. / .-\.OMo F3C^^.CF3 TT XX Ph^-NH HN Ph Ph.,NH HN.. YYYYOO 0 0 F-90 F-91 HH Ph,.NH HN, 'Bu NPhy HNH '¥Bu ¥ ¥ ¥ ¥ ¥ O 0 0 0 0 0 F-72 F-73 F-74 Me Me Μβ,^^^Μβ Me,_5, AAA Ph^.NH HN..Ph Ph^.NH HN..Ph Ph^0.NH HN^_8 Ph0 YYY0YY F-79 XX XJ XI FIRST FIRST Ph. AH HN. .Ph Ph. AH HN. .Ph Ph. AH HN^^Ph y ir yyyy 0 0 O 0 0 0 F-82 F-83 F-84 OMe CF3 NMe2 X Ph Ph. .NH HN, .Ph Ph..NH HN^.Ph Ph,AH HN^.Ph YYYYYY 0 0 0 0 0 0 F-87 F-88 F-89 Me2N_^_NMe2 XX Ph Ph.AH HN^.Ph YY 0 0 F-92 Petition 870250085949, dated 09 / 23 / 2025, p. 48 / 112 37 / 97 [Chemical Formula. 26] But But Ο Ο G-16 G-17 Ο 'Bu Bu Cv Cy ο Et G-2 G-22 G-23 Pr YOU ARE G-12 'Bu Cy YOU ARE G-3 Ο G-8 G-13 G-18 CY Cy OO G-26 Ph.D G-27 Me YOU ARE G-28 [Chemical Formula 27] G-31 Bu you are G-32 'Bu YOU ARE G-33 Ph.D Me YOU ARE G-36 Me OO G-37 Et Et OO G-38 'Pr 'Pr O O G-14 'Bu Et G-29 Pr OO G-39 Bu O G-5 G-10 'Bu 'Bu G-15 G-20 G-19 G-24 G-34 'Bu 'Bu G-25 G-30 Pr Cy O G-35 'Pr O G-40 Bu O G-41 'Bu 'Bu OO G-42 'Bu 'Bu OO G-43 cy. Cy OO G-44 Ph O G-45 G-46 Et O G-47 G-49 G-50 THE G-48 Petition 870250085949, dated 09 / 23 / 2025, p. 49 / 112 38 / 97 G-51 G-52 G-53 G-54 [Chemical Formula. 28] G-65 G-63 G-64 G-67 G-68 G-69 [Chemical Formula. 29] Petition 870250085949, dated 09 / 23 / 2025, p. 50 / 112 39 / 97 G-101 [Chemical Formula 30] Petition 870250085949, dated 09 / 23 / 2025, p. 51 / 112 40 / 97 [Chemical Formula 31] Petition 870250085949, dated 09 / 23 / 2025, p. 52 / 112 41 / 97 Petition 870250085949, dated 09 / 23 / 2025, page 53 / 112 42 / 97 [Chemical Formula 33] o / —\ / ° yN n—\ Me 1 Me 1-1 I-2 O. / ---\ o AnnX 'PrX—Z'Pr O / ---\ z° AnnX BuX--- / Bu I-5 I-6 I-7 I-8 I-4 / ° An PhN-- / Me I-9 1-10 Petition 870250085949, dated 09 / 23 / 2025, page 54 / 112 43 / 97 [Chemical Formula 34] Me Ph. .NH Me HN. .Ph Ph. NH HN. .Ph Ph. .NH HN. .Ph YYYYYY 0 0 0 0 0 J-6 J-7 J-8 Me i..N.XN. .Ph Y Me Me A 0 J-13 Ph. .N.XN. .Ph Ph. .N. ^N^^Ph A Me Me γ γ Me Me γ 0 0 0 J-14 J-15 Me Me Ph. .N. .N. .Ph Y Me Me γ 0 0 Ph J-18 Ph. .N. / N. .Ph Y Me Me γ O 0 Ph. .N. / Ph Y Me Me γ J-19 J-20 Me J-21 J-17 J-22 Me Me Me^ / YY\^Me Ph. .N. .N. / Ph Me Me γ^ 0 J-23 ., Me Me .. Me γΑΑγ Me Ph. / N. A. / Ph γ-^ Me Me γ^ 0 0 J-24 J-27 ι. N. ^N. / Ph Ph. .N. / N. / Ph Ph. .Ν. / N. . Y Me Me γ γ^ Me Me γ γ Me Me γ Ph.D. / N. / N^ .Ph And Me Me 0 0 0 0 0 J-32 J-33 J-34 0 J-35 Ph-x / A,MN^.Ph Ph^.NM M>r Me Me >r γ Me Me j< Phx / N^M.. / N^Ph Y Me Me γ 0 0 0 J-36 J-37 0 J-38 J-41 Ph.D. .Ν N. .Ph πnBunBuzY 0 0 Ph^.NN^.Ph And Bn BnzY 0 J-43 J-48 PhX<-N'M M -NxxPhY Me Me γ 0 0 J-49Ph^XN'M M -NX / PhY Me Me γ 0 0 J-50 Petition 870250085949, dated 09 / 23 / 2025, p. 55 / 112 44 / 97 [Chemical Formula 35] K-17 K-18 K-19 K-20 Petition 870250085949, dated 09 / 23 / 2025, p. 56 / 112 45 / 97 Κ-21 [Chemical Formula 37] L-4 L-5 L-10 L-12 Petition 870250085949, dated 09 / 23 / 2025, p. 57 / 112 46 / 97 L-33 L-34 L-35 L-36 L-40 Petition 870250085949, dated 09 / 23 / 2025, p. 58 / 112 47 / 97 L-65 L-66 L-67 Petition 870250085949, dated 09 / 23 / 2025, p. 59 / 112 48 / 97

[0059] In the structural formulas represented above, a methyl group is denoted as Me, an ethyl group is denoted as Et, a butyl group is denoted as Bu, and a phenyl group is denoted as Ph. In addition, i represents iso and et represents tertiary.

[0060] One of these compounds may be used alone, or two or more of them may be used in combination. Provided that the purpose of the present invention is not impaired, these amide compounds may be used in combination with a catalyst component (b) and a catalyst component (c), which will be described later.

[0061] In addition, the amide compound can be formed during the preparation of the solid titanium catalyst component (I).

[0062] There is a tendency for the method to produce an olefin polymer of the present invention to likely provide a polymer with a wide molecular weight distribution and a high melting point and heat of fusion in a highly active manner.Although the reason for this is currently unknown, the present inventors believe that, including the contents described above, the amide fraction in the amide compound of the present invention tends to be relatively tightly coordinated with the titanium and magnesium in the solid titanium catalyst component, while, especially from the point of view of the rigidity centered around carbons C1 and C2, which are bonded to the nitrogen of the amide groups in the structural formula (1), the amide compound of the present invention is considered to have a loose structure, thus assuming a conformation with movement in a limited range and, therefore, an olefinic polymer with high stereoregularity and wide molecular weight distribution (with a dispersion on the high molecular weight side) is easily obtained. In this case, the stereoregularity of the polymers, especially those on the high molecular weight side, is high, making them... Petition 870250085949, dated 09 / 23 / 2025, pp. 60 / 112 49 / 97 even though they are easily crystallizable, despite their molecular weight, and since the effect of the nucleating agent is also expressed, it can be assumed that a polymer with a high melting point and heat of fusion is easily obtained.

[0063] The olefinic polymer obtained by the method of the present invention is a polymer obtained using a catalyst that can assume a conformation with a certain degree of dispersion and, therefore, can be a polymer with dispersion also on the low molecular weight side. This can result in the dissolution of more components in a hydrocarbon solvent, such as decane. Generally, it is feared that such dissolved components weaken the crystalline structure of olefinic polymers, but the heat of fusion of the olefinic polymer of the present invention tends to be high. This is probably due to the fact that the effect of the nucleating agent of the high molecular weight components described above takes precedence.

[0064] In addition to the amide compound, a magnesium compound and a titanium compound are used in the preparation of the solid titanium catalyst component (I) of the present invention.<Composto de magnésio>

[0065] Specific examples of such magnesium compounds may include known magnesium compounds, such as: - Magnesium halides, such as magnesium chloride and magnesium bromide; - alkoxymagnesium halides, such as methoxymagnesium chloride, ethoxymagnesium chloride and phenoxymagnesium chloride; - alkoxymagnesium compounds, such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, and 2-ethylhexoxymagnesium; - aryloxymagnesium, such as phenoxymagnesium; and - Magnesium carboxylic acid salts, such as magnesium stearate.

[0066] One of these magnesium compounds can be used Petition 870250085949, dated 09 / 23 / 2025, pp. 61 / 112 50 / 97 can be used alone, or two or more of them can be used in combination. Furthermore, such a magnesium compound can be a complex compound with another metal, a composite compound, or a mixture with another metallic compound.

[0067] Among these magnesium compounds, a magnesium compound containing halogen is preferred, and magnesium halide, in particular magnesium chloride, is preferably used. Alkylmagnesium, such as ethoxymagnesium, is also preferably used. The magnesium compound may be a compound derived from another substance, such as a compound obtained by placing an organomagnesium compound, as a Grignard reagent, in contact with, for example, titanium halide, silicon halide or alcohol halide. <Composto de titânio>

[0068] Examples of titanium compounds may include tetravalent titanium compounds represented by the general formula: Ti (OR')gX4-g, where R' is a hydrocarbon group, X is a halogen atom, and g is 0 dgd 4. More specific examples may include: - titanium tetrahalides, such as TiCl4 and TiBr4; - alkoxytitanium trihalides, such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(On-C4H9)Cl3, Ti(OC2H5)Br3 and Ti(O-iso-C4H9)Br3; - alkoxytitanium dihalides, such as Ti(OCH3)2Cl2 and Ti(OC2H5)2Cl2; - alkoxytitanium monohalides, such as Ti(OCH3)3Cl, Ti(O-nC4H9)3Cl and Ti(OC2H5)3Br; and - tetra-alkoxytitanium, such as Ti(OCH3)4, Ti(OC2H5)4, Ti(OC4H9)4 and Ti(O-2-ethylhexyl)4.

[0069] Among these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. One of these titanium compounds may be used alone, or two or more of them may be used in Petition 870250085949, dated 09 / 23 / 2025, pp. 62-112 51 / 97 combination.

[0070] Examples of such magnesium compounds and titanium compounds may also include those described in detail, for example, in Patent Literature 1 and Patent Literature 2. <Método para preparar o componente catalítico de titânio sólido (I)>

[0071] In the preparation of the solid titanium catalytic component (I) used in the present invention, known methods may be used without limitation, except for the use of the amide compound described above. Examples of specific preferred methods may include the following methods (P-1) to (P-4).

[0072] (P-1) Method involving placing a solid adduct composed of a magnesium compound and a catalytic component (b) described later, the amide compound, and a liquid titanium compound in contact with each other in a suspended state in the presence of an inert hydrocarbon solvent.

[0073] (P-2) Method involving placing a solid adduct composed of a magnesium compound and a catalytic component (b), the amide compound and a liquid titanium compound in contact with each other in divided portions.

[0074] (P-3) Method involving bringing into contact a solid adduct composed of a magnesium compound and a catalytic component (b), the amide compound and a liquid titanium compound, in suspension and in divided portions, in the presence of an inert hydrocarbon solvent.

[0075] (P-4) Method involving contacting a liquid magnesium compound consisting of a magnesium compound and a catalytic component (b), a liquid titanium compound and the amide compound.

[0076] The reaction temperature is in the range of, in a preferred mode, -30 °C to 150 °C, in a more preferred mode, -25 °C to 130 °C and in a still more preferred mode, -25 °C to Petition 870250085949, dated 09 / 23 / 2025, p. 63 / 112 52 / 97 120 °C.

[0077] The production of the solid titanium catalyst component can also be carried out in the presence of a known medium, as required. Examples of such media include slightly polar aromatic hydrocarbons such as toluene and known aliphatic hydrocarbons, and alicyclic hydrocarbon compounds such as heptane, octane, decane and cyclohexane, with aliphatic hydrocarbons being preferable examples among these.

[0078] When the reaction is carried out within the above range, the effect of obtaining a polymer with a wide distribution of molecular weight, activity and stereoregularity of the resulting polymer can be achieved simultaneously at a higher level.<Componente catalítico (b)>

[0079] The catalytic component (b) used to form the solid adduct and the liquid magnesium compound is preferably a known compound capable of solubilizing the magnesium compound in a temperature range from approximately room temperature to 300 °C, preferably, for example, alcohols, aldehydes, amines, carboxylic acids and mixtures thereof. Examples of such compounds may include those described in detail in Patent Literature 1 and Patent Literature 2.

[0080] More specific examples of alcohols capable of dissolving the magnesium compound may include: - aliphatic alcohols, such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol and dodecanol; - alicyclic alcohols, such as cyclohexanol and methylcyclohexanol; - aromatic alcohols, such as benzyl alcohol and alcohol Petition 870250085949, dated 09 / 23 / 2025, page 64 / 112 53 / 97 methylbenzyl; and - Aliphatic alcohols with an alkoxy group, such as n-butyl cellosolve.

[0081] Examples of carboxylic acids may include organic carboxylic acids with 7 or more carbon atoms, such as caprylic acid and 2-ethylhexanoic acid. Examples of aldehydes may include aldehydes with 7 or more carbon atoms, such as capric aldehyde and 2-ethylhexyl aldehyde.

[0082] Examples of amines may include amines with 6 or more carbon atoms, such as heptylamine, octylamine, nonylamine, laurylamine, and 2-ethylhexylamine.

[0083] Preferred examples of the catalytic component (b) are the above alcohols, particularly preferred being, for example, ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol and decanol.

[0084] Although the amounts of magnesium compound and catalytic component (b) used in the preparation of the solid adduct and liquid magnesium compound also vary according to, for example, the types and conditions of contact, the magnesium compound is used in an amount of 0.1 to 20 mol / liter and, preferably, 0.5 to 5 mol / liter, based on the unit volume of catalytic component (b). In addition, a medium inert to the solid adduct may be used in combination, as needed. Preferred examples of the medium include known hydrocarbon compounds such as heptane, octane and decane.

[0085] Although the compositional ratio of magnesium to the catalytic component (b) in the resulting solid adduct and in the liquid magnesium compound cannot be specified in general, as the ratio varies according to the type of compound used, the catalytic component (b) per mole of magnesium in the magnesium compound is in a range of, preferably, 2.0 mol or more, more preferably 2.2 mol or more, even more preferably 2.6 mol or more, and Petition 870250085949, dated 09 / 23 / 2025, p. 65 / 112 54 / 97 particularly preferred 2.7 mol or more, and more preferably 5 mol or less. <Aromatic carboxylic acid ester and / or compound with two or more ether linkages through multiple carbon atoms>

[0086] The solid titanium catalyst component (I) of the present invention may also contain an aromatic carboxylic acid ester and / or a compound with two or more ether linkages through multiple carbon atoms (hereinafter also referred to as catalyst component (c)). The catalyst component (c), when contained in the solid titanium catalyst component (I) of the present invention, may increase the activity and stereoregularity, as well as further expand the molecular weight distribution.

[0087] Aromatic carboxylic acid esters and known polyether compounds, preferably used in conventional catalysts for olefin polymerization, such as the compounds described in Patent Literature 2 and JP 2001354714 A, can be used without limitation as the catalyst component (c).

[0088] Specific examples of aromatic carboxylic acid esters include aromatic carboxylic acid monoesters, such as benzoic acid esters and toluic acid esters, and aromatic polycarboxylic acid esters, such as phthalic acid esters. Among these, aromatic polycarboxylic acid esters are preferred, with phthalic acid esters being more preferred. Phthalic acid esters are preferably alkyl phthalates, such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate, with di-isobutyl phthalate being particularly preferred.

[0089] More specific examples of the polyether compound include compounds represented by the following formula (3): [Chemical Formula. 40] Petition 870250085949, dated 09 / 23 / 2025, p. 66 / 112 55 / 97 R32 R^-G-O+CF R33 I mi 1 RH R35 (3) wherein m is an integer from 1 < m < 10 and, more preferably, an integer from 3 í m < 10; and R11, R12 and R31 to R36 are each independently a hydrogen atom or a substituent with at least one element selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.

[0090] When m is 2 or more, a plurality of R11 and R12 may be equal or different. Any R11, R12, R31 to R36, and preferably R11 and R12, may together form a ring other than a benzene ring.

[0091] Specific examples of such compounds may include: - Monosubstituted dialkoxypropanes, such as 2-isopropyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane and 2-cumyl-1,3-dimethoxypropane; - disubstituted dialkoxypropanes, such as 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-1,2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 2-cyclohexyl-2cyclohexylmethyl-1,3-dimethoxypropane; dialkoxyalkanes such as 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, Petition 870250085949, dated 09 / 23 / 2025, page 67 / 112 56 / 97 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane and 2,4-diisoamyl-1,5-dimethoxypentane; - trialkoxyalkanes, such as 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane and 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane; and - dialkoxycycloalkanes, such as 2,2-diisobutyl-1,3-dimethoxy-4-cyclohexenyl, 2-isopropyl-2-isoamyl-1,3-dimethoxy-4cyclohexenyl, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxy-4cyclohexenyl, 2-isopropyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexenyl, 2-isobutyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexenyl, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexenyl, 2isopropyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexenyl and 2isobutyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexenyl.

[0092] Entre estes, os 1,3-diéteres são preferéveis, sendo particularly preferéveis 2-isopropyl-2-isobutil-1,3dimethoxypropano, 2,2-di-isobutil-1,3-dimethoxypropano, 2isopropyl-2-isopentyl-1,3-dimethoxypropano, 2,2-dicyclohexyl-1,3-dimethoxypropano e 2,2-bis(ciclo-hexylmethyl)-1,3dimethoxypropano.

[0093] One of these compounds may be used alone, or two or more may be used in combination.

[0094] The amide compound, the catalyst component (b) and the catalyst component (c), as above, can generally be considered as belonging to components that are termed electron donors by those skilled in the art. Electron donor components are known to exhibit, for example, the effect of increasing the stereoregularity of the resulting polymer, the effect of controlling the compositional distribution of the resulting copolymer, the effect of an aggregating agent of controlling the shape and size of the catalyst particles, while maintaining high catalytic activity.

[0095] The amide compound of the present Petition 870250085949, dated 09 / 23 / 2025, pp. 68 / 112 The 57 / 97 invention also features the ability to further control the molecular weight distribution by the electron donor.

[0096] In the solid titanium catalyst component (I) used in the present invention, the halogen / titanium atomic ratio (i.e., the number of moles of halogen atoms / the number of moles of titanium atoms) is desirably from 2 to 100 and, preferably, from 4 to 90; the amide / titanium compound (a molar ratio) (i.e., the number of moles of amide compound / the number of moles of titanium atoms) is desirably from 0.01 to 100 and, preferably, from 0.2 to 10; and with respect to catalyst component (b) and catalyst component (c), the catalyst component (b) / titanium atoms (a molar ratio) is desirably from 0 to 100 and preferably from 0 to 10, and the catalyst component (c) / titanium atoms (a molar ratio) is desirably from 0 to 100 and preferably from 0 to 10.

[0097] Magnesium / titanium (an atomic ratio) (i.e., the number of moles of magnesium atoms / the number of moles of titanium atoms) is desirably from 2 to 100 and, preferably, from 4 to 50.

[0098] The content of components that may be present in addition to the amide compound described above, such as catalyst component (b) and catalyst component (c), is preferably 20% by weight or less and, more preferably, 10% by weight or less based on 100% by weight of the amide compound.

[0099] As for the more detailed conditions for the preparation of the solid titanium catalyst component (I), the conditions described, for example, in EP 585869 A1 (the descriptive report of the Publication of European Patent Application No. 0585869) and in the Patent Literature 2 may preferably be used, except for the use of the amide compound. [Catalyst for olefin polymerization] Petition 870250085949, dated 09 / 23 / 2025, p. 69 / 112 58 / 97

[00100] The catalyst for olefin polymerization according to the present invention contains: the solid titanium catalyst component (I) according to the present invention; and an organometallic compound catalyst component (II) containing a metallic element selected from Groups 1, 2 and 13 of the periodic table. <Componente de catalisador de composto organometálico (II)>

[00101] A compound containing a Group 13 metal, such as an organoaluminum compound, an alkyl complex of a Group 1 metal and aluminum, or an organometallic compound of a Group 2 metal, may be used as a catalyst component of organometallic compound (II). Among these, an organoaluminum compound is preferred. Specific preferred examples of the catalyst component of organometallic compound (II) may include catalyst components of organometallic compound described in known documents, such as the aforementioned EP 585869 A1 document. <Doador de elétrons (III)>

[00102] The olefin polymerization catalyst of the present invention may contain, together with the organometallic compound catalyst component (II), an electron donor (III), as required. The electron donor (III) is preferably an organosilicon compound. Examples of organosilicon compounds include compounds represented by the following general formula (4): RSnSi(OR)4-n ... (4) where RS and R are hydrocarbon groups; en is an integer from 0 < n < 4.

[00103] Specifically, regarding the organosilicon compound represented by the general formula (4), for example, di-isopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicycloPetition 870250085949, dated 09 / 23 / 2025, page 70 / 112 59 / 97 hexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane and cyclopentyldimethylethoxysilane are used.

[00104] Among these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclopentyldimethoxysilane are preferably used.

[00105] In addition, silane compounds represented by the following formula (5), as described in WO 2004 / 016662, are preferred examples of organosilicon compounds: Si(ORa)3(NRbRc) ... (5) wherein Ra is a hydrocarbon group with 1 to 6 carbon atoms, examples of Rain include unsaturated or saturated aliphatic hydrocarbon groups with 1 to 6 carbon atoms, and particularly preferred examples include hydrocarbon groups with 2 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group and a cyclohexyl group, with an ethyl group being particularly preferred among these.

[00106] In formula (5), Rb is a hydrocarbon group with 1 to 12 carbon or hydrogen atoms, and examples of Rb include unsaturated or saturated aliphatic hydrocarbon groups with 1 to 12 carbon and hydrogen atoms. Specific examples include a hydrogen atom, a methyl group, an ethyl group, Petition 870250085949, dated 09 / 23 / 2025, pp. 71 / 112 60 / 97 an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group and an octyl group, and among these, an ethyl group is particularly preferred.

[00107] In formula (5), R is a hydrocarbon group with 1 to 12 carbon atoms, and examples of R include unsaturated or saturated aliphatic hydrocarbon groups with 1 to 12 carbon and hydrogen atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group, the ethyl group being particularly preferred among these.

[00108] Specific examples of the compound represented by formula (5) include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotrin-propoxysilane, dimethyl-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethyl-isopropylaminotriethoxysilane and methylethylaminotriethoxysilane.

[00109] Other examples of organosilicon compounds include compounds represented by the following formula (6): RNNSi(ORa)3 ... (6) where RNN is a cyclic amino group, and examples of the cyclic amino group include a perhydroquinoline group, a perhydroisoquinoline group, a 1,2,3,4-tetrahydroquinoline group, a 1,2,3,4-tetrahydroisoquinoline group and an octamethyleneimino group.

[00110] Specific examples of compounds represented by formula (6) include (perhydroquinolino)triethoxysilane, Petition 870250085949, dated 09 / 23 / 2025, pp. 72-112 61 / 97 (perhydroisoquinoline)triethoxysilane, (1,2,3,4-tetrahydroquinoline)triethoxysilane, (1,2,3,4-tetrahydroisoquinoline)triethoxysilane and octamethyleneiminotriethoxysilane.

[00111] Two or more of these organosilicon compounds may be used in combination.

[00112] Preferred examples of other compounds useful as electron donors (III) include polyether compounds described as examples of aromatic carboxylic acid esters and / or the compound with two or more ether linkages through multiple carbon atoms (the catalyst component (c)).

[00113] Among these polyether compounds, the 1,3-diethers are preferred, with 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-di-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane being particularly preferred.

[00114] One of these compounds may be used alone and two or more may be used in combination.

[00115] The concomitant use of the electron donor (III) often allows the regulation of stereoregularity and molecular weight. Specifically, when the ratio of electron donor (III) used relative to the organometallic compound catalyst component is increased, there is a tendency to obtain a highly stereoregular polymer, and a polymer with a high molecular weight. On the other hand, when the ratio of electron donor (III) used is reduced, there is a tendency to obtain a polymer with relatively low stereoregularity (e.g., the content of the decane-soluble part, which will be described later, is relatively high), and a polymer with a low molecular weight.

[00116] The catalyst for olefin polymerization of the present invention may contain, in addition to the components described Petition 870250085949, dated 09 / 23 / 2025, page 73 / 112 62 / 97 above, other components useful for olefin polymerization, as needed. Examples of other components include carriers such as silica, antistatic agents, particle aggregating agents, and storage stabilizers. [Olefin Polymerization Method]

[00117] The olefin polymerization method according to the present invention involves carrying out the polymerization of olefins using the olefin polymerization catalyst of the present invention. In this context, polymerization may include the meaning of homopolymerization as well as copolymerization, such as random copolymerization and block copolymerization.

[00118] In the olefin polymerization method of the present invention, polymerization can also be carried out in the presence of a prepolymerization catalyst obtained by prepolymerizing an α-olefin in the presence of the olefin polymerization catalyst of the present invention. This prepolymerization is carried out by prepolymerizing an α-olefin in an amount of 0.1 to 1,000 g, preferably 0.3 to 500 g, and particularly preferably 1 to 200 g per gram of olefin polymerization catalyst.

[00119] In pre-polymerization, the catalyst can be used at a higher concentration than the concentration of the catalyst in the polymerization system.

[00120] The concentration of the solid titanium (I) catalyst component in the prepolymerization, in terms of titanium atoms, is preferably in the range of about 0.001 to 200 mmol, more preferably about 0.01 to 50 mmol and, particularly, 0.1 to 20 mmol per liter of liquid medium.

[00121] It is sufficient that the amount of the organometallic compound catalyst component (II) in the prepolymerization is such that 0.1 to 1,000 g, preferably 0.3 to 500 g of a polymer are produced per gram of the component. Petition 870250085949, dated 09 / 23 / 2025, pp. 74 / 112 63 / 97 solid titanium catalyst (I), and it is desirable that the amount is generally from about 0.1 to 300 mol, preferably from about 0.5 to 100 mol, and particularly preferably from 1 to 50 mol per mol of titanium atoms in the solid titanium catalyst component (I).

[00122] In prepolymerization, for example, the electron donor (III) can also be used as needed, and, at this point, such components are used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, and even more preferably 1 to 10 mol per mol of titanium atoms in the solid titanium catalyst component (I). By regulating the amount of electron donor (III), the stereoregularity of the resulting olefinic polymer can be regulated.

[00123] Prepolymerization can be carried out under moderate conditions after adding an olefin and the above catalyst components to an inert hydrocarbon medium.

[00124] In this case, specific examples of the inert hydrocarbon medium used may include: - aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; - alicyclic hydrocarbons, such as cycloheptane, methylcycloheptane, 4-cycloheptane and methyl-4-cycloheptane; - aromatic hydrocarbons, such as benzene, toluene and xylene; - Halogenated hydrocarbons, such as ethylene chloride and chlorobenzene; and mixtures thereof.

[00125] Among these inert hydrocarbon media, aliphatic hydrocarbons are preferably used. In the case of using an inert hydrocarbon medium, prepolymerization is preferably carried out in batches.

[00126] On the other hand, prepolymerization can also be carried out using the olefin itself as a solvent, and prepolymerization can also be carried out in a substantially solvent-free state. In this case, the pre Petition 870250085949, dated 09 / 23 / 2025, pp. 75 / 112 64 / 97 polymerization is preferably carried out continuously.

[00127] The olefin used in prepolymerization may be the same as or different from the olefin used in polymerization, which will be described later, with propene being specifically preferred.

[00128] Preferably, the temperature during prepolymerization is in a range of, generally, about -20 to +100 °C, preferably about -20 to +80 °C and, even more preferably, from 0 to +40 °C.

[00129] Next, the polymerization performed by means of the pre-polymerization described above or without pre-polymerization will be described.

[00130] Examples of usable olefins (i.e., to be polymerized) in polymerization may include α-olefins with 3 to 20 carbon atoms, for example, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, and branched olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene and 3-methyl-1-butene, with propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 3-methyl-1-butene being preferred. From the standpoint that the advantages of a polymer with a wide molecular weight distribution are likely to be exhibited in a highly rigid resin, propylene, 1-butene, 4-methyl-1-pentene, and 3-methyl-1-butene are particularly preferable.

[00131] In addition to these α-olefins, ethylene, aromatic vinyl compounds such as styrene and allylbenzene, and alicyclic vinyl compounds such as vinylcyclohexane and vinylcycloheptane are also usable. Furthermore, cyclopentene, cycloheptene, norbornene, tetracyclododecene, and compounds with multiple unsaturated bonds, such as conjugated dienes and non-conjugated dienes, for example, dienes such as isoprene and butadiene, can also be used as polymerization feedstocks, along with ethylene and α-olefin. One of these compounds may be Petition 870250085949, dated 09 / 23 / 2025, pp. 76 / 112 65 / 97 used individually, or two or more of them may be used in combination (hereinafter, the olefin used with ethylene or the α-olefin with 3 to 20 carbon atoms is also called additional olefin).

[00132] Among the additional olefins, ethylene and aromatic vinyl compounds are preferred. Of the total 100% by weight of olefins, a small amount, for example, 10% by weight or less and, preferably, 5% by weight or less, of other olefins, such as ethylene, may be used in combination.

[00133] In the present invention, prepolymerization and polymerization can be carried out by any of the liquid-phase polymerization methods, such as bulk polymerization, solution polymerization and suspension polymerization, and gas-phase polymerization methods.

[00134] When polymerization takes the form of a paste polymerization reaction, an inert hydrocarbon, such as that used during the pre-polymerization described above, can be used as a reaction solvent, and an olefin that is liquid at the reaction temperature can also be used.

[00135] In the polymerization method of the present invention, the solid titanium catalyst component (I) is used in an amount, in terms of titanium atoms, generally of about 0.0001 to 0.5 mmol and, preferably, about 0.005 to 0.1 mmol per liter of polymerization volume. The organometallic compound catalyst component (II) is used in an amount generally of about 1 to 2,000 mol, preferably about 5 to 500 mol, more preferably 10 to 350 mol, even more preferably 30 to 350 mol and, particularly preferably, 50 to 350 mol per mole of titanium atoms in the prepolymerization catalyst components in the polymerization system. The electron donor (III), if used, is used in an amount of 0.001 to 50 mol, preferably from 0.01 to 30 mol, and in a manner Petition 870250085949, dated 09 / 23 / 2025, p. 77 / 112 66 / 97 particularly preferred from 0.05 to 20 mol per mol of metal atoms of the organometallic compound catalyst component (II). As described above, the stereoregularity and molecular weight can be regulated by means of the amount of electron donor (III) used.

[00136] Polymerization in the presence of hydrogen allows for the regulation of the molecular weight of the resulting polymer and provides a polymer with a high flow rate.

[00137] In the polymerization of the present invention, the polymerization temperature of the olefin is generally from about 20 to 200 °C, preferably from about 30 to 100 °C, and more preferably from 50 to 90 °C. The pressure is generally adjusted to the normal pressure of 10 MPa and, preferably, from 0.20 to 5 MPa. In the polymerization method of the present invention, polymerization can be carried out in any of the following modes: batch, semi-continuous, and continuous. Furthermore, polymerization can be carried out in two or more split stages by altering the reaction conditions. Carrying out this multi-stage polymerization allows the molecular weight distribution of the olefinic polymer to be further expanded.

[00138] The olefinic polymer thus obtained can be any one of, for example, a homopolymer, a random copolymer, and a block copolymer.

[00139] When olefin polymerization, or propylene polymerization in particular, is carried out using the olefin polymerization catalyst described above, a highly stereoregular propylene-based polymer can be obtained with a decane-insoluble moiety content of 70% or more, preferably 85% or more, and particularly preferably 90% or more.

[00140] Furthermore, according to the olefin polymerization method of the present invention, polyolefins, or in particular, polypropylene with a wide weight distribution Petition 870250085949, dated 09 / 23 / 2025, pp. 78 / 112 67 / 97 molecular weight polymers can be obtained even without multi-stage polymerization, or even through polymerization with a small number of stages, such as single-stage polymerization. A characteristic of the olefin polymerization method of the present invention is that, in particular, an olefin polymer with a higher proportion of high molecular weight components and a lower proportion of low molecular weight components (which are especially called sticky compounds) is frequently obtained than conventional olefin polymers with a comparable melt flow rate (MFR). This characteristic can be verified by gel permeation chromatography (GPC) measurement, which will be described later, and a polymer with a high Mw / Mn value and a high Mz / Mw value can be obtained.

[00141] Polypropylene obtained using conventional solid titanium catalyst components, including magnesium, titanium, halogen, and an electron donor, generally exhibits an Mw / Mn value equal to or less than 5 and an Mz / Mw value less than 4, which are indices of a molecular weight distribution determined by GPC measurement, in an MFR range of 1 to 10 g / 10 min. However, when the olefin polymerization method of the present invention is used, an olefin polymer with an Mw / Mn value of 6 to 30 and, preferably, of 7 to 20 can be obtained under the same polymerization conditions. Furthermore, an olefin polymer with an Mz / Mw value preferably of 4 to 15 and, more preferably, of 4.5 to 10 can be obtained. In particular, according to the polymerization method of an olefin of the present invention, a polymer with a high Mz / Mw value is frequently obtained.

[00142] It is common knowledge among those versed in the field that polypropylene with a high Mw / Mn value exhibits excellent moldability and rigidity. On the other hand, a high Mz / Mw value indicates a high content ratio of high-strength components. Petition 870250085949, dated 09 / 23 / 2025, pp. 79 / 112 With a molecular weight of 68 / 97, the resulting polypropylene is expected to exhibit high melt strength and excellent moldability.

[00143] The use of the olefin polymerization method of the present invention allows obtaining a polymer with a wide molecular weight distribution without the need for multi-stage polymerization and, therefore, possibly simplifying the polymer production apparatus. Furthermore, it is expected that application to a conventional multi-stage polymerization method will allow obtaining a polymer with improved melt strength and moldability.

[00144] Although other methods exist for obtaining a polymer with a wide molecular weight distribution, such as a method involving the mixing or melt kneading of polymers with different molecular weights, the polymers obtained by such methods, in some cases, do not exhibit sufficiently increased melt strength or moldability, despite the relatively complex procedure. This is probably due to the fact that polymers with different molecular weights basically mix very little. On the other hand, it is expected that the polymer obtained by the olefin polymerization method of the present invention, since polymers with different molecular weights in extremely wide ranges are mixed at the catalyst level, i.e., at the nanometer level, will exhibit high melt strength and excellent moldability.

[00145] The polymer obtained by the polymerization method of an olefin of the present invention exhibits high stereoregularity, as described above. Consequently, the olefinic polymer obtained by the method of the present invention tends to have a high melting point. The melting point is generally determined by differential scanning calorimetry (DSC).

[00146] Propylene-based polymers, as obtained by Petition 870250085949, dated 09 / 23 / 2025, pages 80 / 112 69 / 97 polymerization method of an olefin of the present invention (for example, the content of propylene-derived structural units is 99% molar or more), exhibit a high content of decane-soluble moieties, but, surprisingly, as described above, exhibit an unexpected tendency to have a high heat of fusion.

[00147] It is generally known that decane-soluble moieties in propylene homopolymers tend to exhibit not only low stereoregularity but also low molecular weight. Furthermore, it is also known that polymers with low stereoregularity, such as the decane-soluble moieties described above, are sometimes used as elastomers for shoe sole materials and the like.

[00148] The present inventors have found that, in a propylene polymer, as obtained by the polymerization method of an olefin of the present invention, the molecular weight of the decane-soluble moieties tends to be high. Consequently, there is a possibility that a propylene-based polymer, as described above (the propylene-derived structural units have 99 mol% or more, the content of decane-soluble moieties is high and the molecular weight of the decane-soluble moieties is high) is a novel polymer.

[00149] The content of propylene-derived structural units in the propylene-based polymer is preferably 99.3 mol% or more, more preferably 99.5 mol% or more, even more preferably 99.7 mol% or more, and especially 99.8 mol% or more. The upper limit value is, of course, 100 mol%.

[00150] The content of decane-soluble moieties in the propylene-based polymer is preferably 3% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more. On the other hand, the upper limiting value is preferably 15% by mass, in a Petition 870250085949, dated 09 / 23 / 2025, pp. 81 / 112 70 / 97 is more preferred (14% by mass) and even more preferred (13% by mass).

[00151] The molecular weight of the decane-soluble moieties in the propylene-based polymer is 20% or more, more preferably 25% or more, and even more preferably 27% or more of the entire propylene-based polymer as a weight-average molecular weight.

[00152] The decane-soluble moieties described above are specific components whose stereoregularity derived from the methyl group (pentate tacticity), measured by 13C NMR, shows almost similar numerical values ​​for mmmm and rrrr. The mmmm and rrrr values ​​described above are preferably from 10 to 30%. The lower limit is more preferably 13% and even more preferably 15%. Conversely, the upper limit is more preferably 27% and even more preferably 25%.

[00153] Propylene-based polymer containing such high molecular weight decane-soluble moieties can be expected to exhibit not only a high heat of fusion but also flexibility, even though its structure is composed almost entirely of propylene-derived structural units.

[00154] The propylene polymer, as described above, can be obtained, for example, by polymerizing propylene using the olefin polymerization catalyst of the present invention. Although the reason why such a propylene polymer can be obtained is not currently known, it is believed to be because the catalyst for active species that can have various conformations, such as the olefin polymer described above, can also form active species that are difficult to undergo chain transfer and have low stereospecificity.

[00155] As described above, the olefin polymer, or the propylene polymer in particular, obtained by the method of Petition 870250085949, dated 09 / 23 / 2025, pp. 82 / 112 71 / 97 The present invention tends to have a wide molecular weight distribution and, in particular, a large Mz, and therefore tends to have a distribution that extends towards the high molecular weight side. Since the molecular mobility of an olefinic polymer varies according to molecular weight, a graph obtained by DSC measurement, in the case of a polymer with a wide molecular weight distribution, may present not a unimodal shape, but rather a multimodal or wide shape. That is, since an ultra-high molecular weight component is less likely to crystallize, it is conceivable that a graph with a wide shape on the low temperature side in a DSC measurement method is possibly due to an ultra-high molecular weight component. Consequently, the Δη measured as heat of fusion (amount of heat of crystallization) may also tend to be low.

[00156] It is claimed that components in the ultra-high molecular weight region can cause problems, such as fisheye, in applications where transparency and transparency properties are emphasized, such as film applications. The olefinic polymer obtained by the method of the present invention tends to reach a finely dispersed state, which can also be termed the catalytically active species level, i.e., the nanometer level, as described above, and therefore tends to be unlikely to cause such problems. Furthermore, the selection of the amide compound structure used in the catalyst of the present invention allows for regulating the balance between the molecular weight and the content of components in the ultra-high molecular weight region, as well as the molecular weight and melt flow rate (MFR) of the entire polymer.

[00157] The propylene polymer obtained by the method of the present invention can be used in various known applications. In particular, as the propylene polymer is expected to exhibit high heat resistance and rigidity, it is Petition 870250085949, dated 09 / 23 / 2025, page 83 / 112 72 / 97 is suitable for, for example, various applications in injection-molded articles and, more specifically, automotive components and household appliance components. Furthermore, propylene polymer can be used in various sheets and films due to its wide molecular weight distribution. In particular, propylene polymer is suitable for, for example, separator applications in lithium-ion batteries and capacitors. Additionally, propylene polymer can be suitable for use in, for example, stamped articles, calendered articles, and rotationally molded articles. Examples

[00158] The present invention will now be described by means of the Examples below, but the present invention is not limited to them.

[00159] In the following examples, the apparent density, melt flow rate, amount of soluble (insoluble) component in decane, molecular weight distribution, final melting point, melting point, crystallization temperature, and amount of heat of fusion of propylene polymers were measured by the following methods. (1) Apparent density:

[00160] The apparent density was measured according to the JIS K-6721 standard. (2) Melt flow rate (MFR):

[00161] According to ASTM D1238E standard, the load was set at 2.16 kg and the measurement temperature for a propylene polymer was set at 230 °C. (3) Amount of soluble (insoluble) component in decane:

[00162] Approximately 3 g of a propylene polymer (measured in a unit of 10-4 g, and this weight was denoted as b(g) in the following equation), 500 ml of decane and a small amount of a heat-resistant stabilizer soluble in decane were added to a glass measuring container, and the polymer Petition 870250085949, dated 09 / 23 / 2025, page 84 / 112 73 / 97 of propylene was dissolved by heating to 150 °C for 2 hours while being stirred with a stirrer in a nitrogen atmosphere, then held at 150 °C for 2 hours and gradually cooled to 23 °C over 8 hours. The resulting liquid, containing propylene polymer precipitates, was filtered under reduced pressure through a standard 25G-4 glass filter manufactured by Tokyo Garasu Kikai Co., Ltd. Then, 100 ml of the filtrate were collected and dried under reduced pressure to provide a decane-soluble fraction, and its weight was accurately weighed to the nearest 10⁻⁴ g (this weight was denoted as (g) in the following equation). After this operation, the amount of decane-soluble fraction was determined by the following equation. Soluble decane content = 100 x (500 xa) / (100 xb) Insoluble decane content = 100 - 100 x (500 xa) / (100 xb)<Método para recuperação da parte solúvel em decano: Exemplo 7 e Exemplo Comparativo 2>

[00163] To the filtrate described above, 5 times the volume of acetone (weak solvent) at room temperature was added to precipitate the dissolved polymer, which was then filtered through a 350 mesh metal filter to obtain the precipitates. Subsequently, the recovered precipitates were dried under reduced pressure at 80 °C for 1 hour to obtain the decane-soluble parts of the propylene polymer.

[00164] The molecular mass of these decane-soluble parts was measured by the GPC method described later, and the stereoregularity was measured by the 13C NMR method. (4) Molecular weight distribution (MWD):

[00165] Gel permeation chromatograph: model HLC-8321 GPC / HT manufactured by Tosoh Corporation. Detector: Differential refractometer. Column: TSKgel GMH6-HT x 2 and TSKgel GMH6-HTL x 2 manufactured Petition 870250085949, dated 09 / 23 / 2025, page 85 / 112 74 / 97 units by Tosoh Corporation were connected in series. Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measuring temperature: 140 °C

[00166] Method for creating the calibration curve: A standard sample of polystyrene was used.

[00167] Sample concentration: 0.1% (w / w)

[00168] Sample solution quantity: 0.4 ml. The measurement was performed under the above conditions, and the resulting chromatogram was analyzed by a known method to calculate the weight-average molecular weight (Mw), the number-average molecular weight (Mn), the Z-average molecular weight (Mz), and the Mw / Mn and Mz / Mw values, which are indices of the molecular weight distribution (MWD). The measurement time per sample was 60 minutes. (5) Melting point (Tm) of the polymer:

[00169] The melting point (Tm), crystallization temperature (Tc), and amount of heat of fusion (Δη) of the polymers of the present invention were measured using a differential scanning calorimeter (DSC) in a DSC8000 apparatus manufactured by PerkinElmer Co., Ltd. First, 3 to 10 mg of a sample were sealed in an aluminum pan and heated from room temperature to 200 °C at 100 °C / min. The sample was held at 200 °C for 5 minutes and then cooled to 30 °C at 10 °C / min. The maximum temperature observed in this cooling test was considered the crystallization temperature (Tc), and the amount of heat produced, specified by the peak area, was considered Δη. Subsequently, the sample was left to stand for 5 minutes at 30 °C and then heated a second time to 200 °C at 10 °C / min. The maximum temperature observed in this second heating test was considered the melting point (Tm).

[00170] The final melting point (Tmf) of a polymer in the present invention was measured using a scanning calorimeter. Petition 870250085949, dated 09 / 23 / 2025, p. 86 / 112 75 / 97 differential (DSC) assay was performed on a DSC 8000 apparatus manufactured by PerkinElmer Co., Ltd. First, 3 to 10 mg of a sample were sealed in an aluminum pan and heated from room temperature to 240 °C at 80 °C / min. The sample was held at 240 °C for 1 minute and then cooled to 0 °C at 80 °C / min. After being held at 0 °C for 1 minute, the sample was heated to 150 °C at 80 °C / min and held for 5 minutes. Finally, the sample was heated to 180 °C at 1.35 °C / min, and the intersection between the baseline and the tangent of the inflection point on the high-temperature side of the peak obtained in this final heating test was considered the final melting point (Tmf).

[00171] Tmf can be considered a parameter for evaluating the crystalline structure of a component that exhibits extremely high stereoregularity, as well as the ease of crystallization and the crystalline structure, for example, of a polymer in the ultra-high molecular weight region, which is considered to have a tendency to be unlikely to crystallize. More specifically, it can be considered that, as this Tmf value is higher, the ultra-high molecular weight polymeric component has a greater probability of forming crystals with high heat resistance. (6) Stereoregularity of propylene polymer (measured by 13C NMR):

[00172] The measurement was performed by dissolving 50 mg of a sample in 0.6 ml of a 4 / 1 mixed solvent of o-dichlorobenzene and deuterated benzene (o-dichlorobenzene / deuterated benzene; volumetric ratio), using an AVANCE NEO cryo-500 nuclear magnetic resonance instrument, manufactured by Bruker Biospin KK, at 120 °C, with a 45 ° pulse, a repetition time of 5.5 seconds, and an integrated frequency of 256 times. The reference value for the chemical shift was set at 21.59 ppm for the signal of the methyl groups derived from mmmm.

[00173] The peak of the propylene-derived methyl group was Petition 870250085949, dated 09 / 23 / 2025, page 87 / 112 76 / 97 assigned using a conventional method to determine the ratio of various stereostructures.

[00174] Some structural formulas of compounds used in the Examples and Comparative Examples below exhibit stereoisomeric structures. The structural formulas showing the stereoisomers of the exemplified compounds show the major isomers of the compounds used in the Examples and Comparative Examples. In the present invention, the major component refers to a component representing more than 50 molar percent, and preferably 70 molar percent or more. [Example 1]<Preparação do componente catalítico de titânio sólido [α1]>

[00175] After a 1-liter glass container was sufficiently purged with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane, and 352 g of 2-ethylhexyl alcohol were placed in it and subjected to a heating reaction at 130 °C for 3 hours to obtain a homogeneous solution. Then, 241 g of this solution and 6.43 g of ethyl benzoate were added to the glass container and mixed under stirring at 50 °C for 1 hour.

[00176] After cooling the homogeneous solution thus obtained to room temperature, 38.3 ml of the homogeneous solution were added dropwise to 100 ml of titanium tetrachloride, maintained at -20 °C for 45 minutes, under stirring. After the addition was complete, the temperature of the mixed liquid was raised to 80 °C for 3.8 hours and, when the temperature reached 80 °C, 1.77 g of compound 1 was added to the mixed liquid. The temperature was again raised to 120 °C for 40 minutes, and the mixture was maintained at the same temperature for 35 minutes, under stirring. After the reaction was complete, the solid portion was recovered by hot filtration, resuspended in 100 ml of titanium tetrachloride and again subjected to thermal reaction at 120 °C for 35 minutes, under stirring. After the reaction was complete, Petition 870250085949, dated 09 / 23 / 2025, pages 88 / 112 77 / 97 The solid portion was recovered again by hot filtration and thoroughly washed with decane at 100 °C and decane at room temperature until no free titanium compounds were detected in the washing liquid. The solid titanium catalyst component [ocl] prepared by the above operations was preserved as a decane paste, and a portion of the paste was dried to verify the catalyst composition. The composition of the solid titanium catalyst component [ocl] thus obtained contained 0.42% by mass of titanium, 1.2% by mass of magnesium, and 0.07% by mass of residual 2-ethylhexyl alcohol. [Chemical Formula 41] (Compound 1)<Polimerização>

[00177] After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a polymerization apparatus with an internal volume of 2 liters, a mixed liquid was obtained by mixing 7 ml of heptane, 0.50 mmol of triethylaluminum, 0.10 mmol of cyclohexylmethyldimethoxysilane, and 0.0040 mmol (in terms of titanium atoms) of the solid titanium catalyst component [ocl] at 25 °C for 10 minutes, and the temperature inside the polymerization apparatus was immediately raised to 70 °C under stirring. After polymerization at 70 °C for 1.5 hours, the reaction was stopped with a small amount of methanol, and the propylene was purged. Furthermore, the resulting polymer particles were dried under reduced pressure at 80 °C overnight. Table 1 shows the activity, apparent specific gravity, MFR, amount of insoluble parts in decane, Tm, Tmf, and MWD. Petition 870250085949, dated 09 / 23 / 2025, pp. 89 / 112 78 / 97 [Example 2]<Preparação do componente catalítico de titânio sólido [α2]>

[00178] After a 1-liter glass container was sufficiently purged with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane, and 352 g of 2-ethylhexyl alcohol were placed in it and subjected to a heating reaction at 130 °C for 3 hours to obtain a homogeneous solution. Then, 241 g of this solution and 6.43 g of ethyl benzoate were added to the glass container and mixed under stirring at 50 °C for 1 hour.

[00179] After the homogeneous solution thus obtained had been cooled to room temperature, 30.6 ml of the homogeneous solution were added dropwise to 80 ml of titanium tetrachloride, maintained at -20 °C for 45 minutes, under stirring. After the addition was complete, the temperature of the mixed liquid was raised to 80 °C for 3.8 hours and, when the temperature reached 80 °C, 0.63 g of compound 2 was added to the mixed liquid. The temperature was again raised to 120 °C for 40 minutes, and the mixture was maintained at the same temperature for 35 minutes, under stirring. After the reaction was complete, the solid portion was recovered by hot filtration, resuspended in 80 ml of titanium tetrachloride and again subjected to thermal reaction at 120 °C for 35 minutes, under stirring.After the reaction was complete, the solid portion was recovered again by hot filtration and thoroughly washed with decane at 100 °C and decane at room temperature until no free titanium compounds were detected in the washing fluid. The solid component of the titanium [α2] catalyst prepared by the above operations was preserved as a decane paste, and a portion of the paste was dried to verify the catalyst composition. The composition of the solid component of the titanium [α2] catalyst thus obtained contained 0.36% by mass of titanium, 1.7% by mass of magnesium, and 0.11% by mass of residual 2-ethylhexyl alcohol. Petition 870250085949, dated 09 / 23 / 2025, pp. 90-112 79 / 97 [Chemical Formula. 42] (Compound 2)<Polimerização>

[00180] After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a polymerization apparatus with an internal volume of 2 liters, a mixed liquid was obtained by mixing 7 ml of heptane, 0.40 mmol of triethylaluminum, 0.08 mmol of cyclohexylmethyldimethoxysilane, and 0.0032 mmol (in terms of titanium atoms) of the solid titanium catalyst component [0t2] at 25 °C for 10 minutes, and the temperature inside the polymerization apparatus was immediately raised to 70 °C under stirring. After polymerization at 70 °C for 1.5 hours, the reaction was stopped with a small amount of methanol, and the propylene was purged. Furthermore, the resulting polymer particles were dried under reduced pressure at 80 °C overnight. Table 1 shows the activity, apparent specific gravity, MFR, amount of insoluble parts in decane, Tm, Tmf and MWD. [Example 3]<Preparação do componente de catalisador de titânio sólido [oc3]>

[00181] A solid titanium catalyst component [a3] was obtained in the same manner as in Example 1, except that 1.64 g of the following compound 3 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [a3] thus obtained showed 0.44 wt% titanium, 1.4 wt% magnesium and 0.02 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 43] Petition 870250085949, dated 09 / 23 / 2025, pp. 91 / 112 80 / 97 (Compound 3)<Polimerização>

[00182] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [oc3] was used in place of the solid titanium catalyst component [ocl]. The results are shown in Table 1. [Example 4]<Preparação do componente de catalisador de titânio sólido [oc4]>

[00183] A solid titanium catalyst component [0C4] was obtained in the same manner as in Example 1, except that 1.74 g of compound 4 below was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0C4] thus obtained showed 0.33 wt% titanium, 1.5 wt% magnesium and 0.02 wt% residual 2-ethylhexyl alcohol. [Chemical Formula. (Compound 4)<Polimerização>

[00184] The polymerization of propene was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [oc4] was used in place of the solid titanium catalyst component [ocl]. The results are shown. Petition 870250085949, dated 09 / 23 / 2025, pp. 92-112 81 / 97 in Table 1. [Example 5]<Preparação do componente de catalisador de titânio sólido [a5] >

[00185] A solid titanium catalyst component [0C5] was obtained in the same manner as in Example 1, except that 1.47 g of compound 5 below was used instead of 1.77 g of compound 1. The composition of the solid titanium catalyst component [oc5] thus obtained was 0.28 wt% titanium, 1.7 wt% magnesium and 0.06 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 45] (Compound 5)<Polimerização>

[00186] The polymerization of propylene was carried out in the same manner as in Example 1, except that 0.0032 mmol (in terms of titanium atoms) of the solid titanium catalyst component [oc5] was used in place of the solid titanium catalyst component [ocl], the amount of triethylaluminum used was changed from 0.50 mmol to 0.40 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.10 mmol to 0.08 mmol. The results are presented in Table 1. [Example 6]<Preparação do componente catalítico de titânio sólido [oc6]>

[00187] A solid titanium catalytic component [0C6] was obtained in the same manner as in Example 1, except that 1.88 g of compound 6 below was used instead of 1.77 g of compound 6. Petition 870250085949, dated 09 / 23 / 2025, pp. 93-112 82 / 97 1. The composition of the solid titanium catalytic component [0t6] thus obtained showed 0.43% by mass of titanium, 1.6% by mass of magnesium and 0.04% by mass of 2-ethylhexyl alcohol residues. [Chemical Formula 46] Ph. HI\L .Ph Ph O (Compound 6)<Polimerização>

[00188] The polymerization of propylene was carried out in the same manner as in Example 1, except that the solid titanium catalytic component [0C6] was used instead of the solid titanium catalytic component [ocl]. The results are presented in Table 1. [Example 7]<Preparação do componente catalítico de titânio sólido [oc7] >

[00189] A solid titanium catalytic component [0C7] was obtained in the same manner as in Example 1, except that 1.71 g of compound 7 below was used in place of 1.77 g of compound 1. The composition of the solid titanium catalytic component [0C7] thus obtained showed 0.66 wt% titanium, 1.3 wt% magnesium and 0.05 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 47] PK A .Ph (Compound 7)<Polimerização> Petition 870250085949, dated 09 / 23 / 2025, pp. 94 / 112 83 / 97

[00190] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [0C7] was used in place of the solid titanium catalyst component [al]. The results are presented in Table 1. Separately, the decane-soluble moieties were recovered and subjected to GPC and 13C NMR measurements. The results are presented in Table 2. [Example 8]<Preparação do componente catalisador de titânio sólido [a8]>

[00191] A solid titanium catalyst component [a8] was obtained in the same manner as in Example 1, except that 1.37 g of compound 8 below was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [a8] thus obtained showed 0.64 wt% titanium, 1.4 wt% magnesium and 0.07 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 48] (Compound 8)<Polimerização>

[00192] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [a8] was used in place of the solid titanium catalyst component [al]. The results are shown in Table 1. [Comparative Example 1]<Preparação do componente de catalisador de titânio sólido [β1]>

[00193] A solid titanium catalyst component [βΐ] was obtained in the same manner as in Example 1, except that 1.12 g of the following compound cl was used instead of 1.77 g of Petition 870250085949, dated 09 / 23 / 2025, pp. 95-112 84 / 97 compound 1. The composition of the solid titanium catalyst component [βΐ] thus obtained showed 0.57% by mass of titanium, 1.5% by mass of magnesium and 0.03% by mass of residual 2-ethylhexyl alcohol. [Chemical Formula 49] (Compound cl)<Polimerização>

[00194] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [βΐ] was used in place of the solid titanium catalyst component [ocl]. The results are shown in Table 1. [Comparative Example 2]<Preparação do componente de catalisador de titânio sólido [β2]>

[00195] A solid titanium catalyst component [β2] was obtained in the same manner as in Example 1, except that 1.60 g of the following compound c2 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [β2] thus obtained showed 0.25 wt% titanium, 1.9 wt% magnesium and 0.08 wt% residual 2-ethylhexyl alcohol. [Chemical Formula. 50] (Compound c2) Petition 870250085949, dated 09 / 23 / 2025, pp. 96 / 112 85 / 97<Polimerização>

[00196] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [β2] was used in place of the solid titanium catalyst component [ocl]. The results are presented in Table 1. Separately, the decane-soluble moieties were recovered and subjected to GPC and 13C NMR measurements. The results are presented in Table 2. [Comparative Example 3]<Preparação do componente catalítico de titânio sólido [β3]>

[00197] A solid titanium catalytic component [β3] was obtained in the same manner as in Example 1, except that 1.85 g of the following compound c3 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalytic component [β3] thus obtained showed 0.77 wt% titanium, 1.1 wt% magnesium and 0.18 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 51] (Compound c3)<Polimerização>

[00198] The polymerization of propylene was carried out in the same manner as in Example 1, except that the solid titanium catalytic component [β3] was used instead of the solid titanium catalytic component [ocl]. The results are presented in Table 1. Table 1 Example Activities (kg of PP / g Specific gravity MFR (g / 10 min) Amount of insoluble parts Mw Mw / Mn Mz / Mw Petition 870250085949, dated 09 / 23 / 2025, pages 97 / 112 86 / 97 Apparent calorie (g / mL) in decane (% by weight) Example 1 16.0 0.46 5.9 5.8 431,000 10.8 7.7 Example 2 28.8 0.48 0.7 3.8 797,000 13.5 6.0 Example 3 14.0 0.47 7.8 7.8 378,000 10.5 8.1 Example 4 13.6 0.47 10.8 7.1 364,000 10.2 9.4 Example 5 17.0 0.48 8.7 6.7 361,000 8.7 8.5 Example 6 14.5 0.47 17.3 8. Example 7: 13.4 0.38 10.1 9.0 345.000 9.1 8.8 Example 8: 14.6 0.47 13.0 8.0 309.000 8.8 8.3 Comparative Example 1: 5.8 0.42 32.0 10.6 211.000 9.3 5.4 Comparative Example 2: 11.2 0.45 23.6 9.1 222.000 9.3 5.6 Comparative Example 3: 21.6 0.47 9.7 6.6 289.000 9.1 4.7 Table 1 (continued) Example Mw / Mn + Mz / Mw Tmf (°C) Tm (°C) Tc (°C) δη (J / g) Example 1 18.5 169.8 159.9 116.4 98.4 Example 2 19.5 171.0 161.8 117.2 97.3 Example 3 18.6 169.4 158.9 115.1 90.6 Example 4 19.6 169.7 159.3 116.5 95.3 Example 5 17.2 169.4 159.0 114.4 97.2 Example 6 16.7 169.4 158.2 115.7 Example 7: 91.6 17.9 169.0 163.0 157.6 112.6 89.7 Example 8: 17.1 169.2 158.7 114.4 90.3 Comparative Example 1: 14.7 169.2 164.0 157.1 111.3 73.8 Comparative Example 2: 14.9 169.3 164.6 157.8 110.9 78.8 Comparative Example 3: 13.7 169.5 164.8 158.8 110.2 80.2 Table 2 Soluble parts in decane / % by weight (recovery) GPC measurement results 13C NMR measurement results Mw Mw / Mn Mz / Mw mmmm mmrr rrrr Petition 870250085949, dated 09 / 23 / 2025, pages 98 / 112 87 / 97 (by acetone precipitation) Example 7 7.7 101000 4.9 3.9 19.2 15.6 16.3 Comparative example 2 7.7 79200 4.4 3.8 21.5 15.1 18.2 [Example 9]<Preparação do componente catalítico de titânio sólido [oc9]>

[00199] A solid titanium catalytic component [0C9] was obtained in the same manner as in Example 1, except that 1.57 g of compound 9 below was used instead of 1.77 g of compound 9 below. 1. The composition of the solid titanium catalytic component [oc9] thus obtained contained 0.58% by mass of titanium, 1.3% by mass of magnesium and 0.04% by mass of residual 2-ethylhexyl alcohol. [Chemical Formula 52] (Compound 9)<Polimerização>

[00200] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalytic component [0C9] was used in place of the solid titanium catalytic component [ocl]. The results are presented in Table 3. [Example 10]<Preparação do componente de catalisador de titânio sólido [oclO] >

[00201] A solid titanium catalyst component [OC10] was obtained in the same manner as in Example 1, except that 1.28 g of the following compound 10 was used instead of 1.77 g of Petition 870250085949, dated 09 / 23 / 2025, pp. 99 / 112 88 / 97 compound 1. The composition of the solid titanium catalyst component [AlO] thus obtained showed 0.61% by mass of titanium, 1.4% by mass of magnesium and 0.15% by mass of residual 2-ethylhexyl alcohol. [Chemical Formula 53] (Compound 10)<Polimerização>

[00202] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [AlO] was used in place of the solid titanium catalyst component [Al]. The results are presented in Table 3. [Example 11]<Preparação do componente catalítico de titânio sólido [all]>

[00203] A solid titanium catalytic component [all] was obtained in the same manner as in Example 1, except that 1.77 g of compound 1 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalytic component [all] thus obtained showed 0.87 wt% titanium, 1.1 wt% magnesium and 0.15 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 54] (Compound 11) Petition 870250085949, dated 09 / 23 / 2025, pp. 100 / 112 89 / 97<Polimerização>

[00204] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalytic component [all] was used in place of the solid titanium catalytic component [al]. The results are presented in Table 3. [Example 12]<Preparação do componente de catalisador de titânio sólido [al2]>

[00205] A solid titanium catalyst component [Al2] was obtained in the same manner as in Example 1, except that 1.64 g of the following compound 12 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [Al2] thus obtained showed 0.64 wt% titanium, 1.5 wt% magnesium and 0.09 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 55] (Compound 12)<Polimerização>

[00206] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [al2] was used in place of the solid titanium catalyst component [al]. The results are presented in Table 3. [Example 13]<Preparação do componente catalítico de titânio sólido [al3]>

[00207] A solid titanium [Al3] catalyst component was obtained in the same manner as in Example 1, except that 1.64 g of compound 13 below was used instead of 1.77 g of compound 1. The composition of the titanium catalyst component Petition 870250085949, dated 09 / 23 / 2025, pp. 101 / 112 The 90 / 97 solid [α13] thus obtained contained 0.91% by mass of titanium, 1.0% by mass of magnesium and 0.04% by mass of 2-ethylhexyl alcohol residues. [Chemical Formula 56] IH PhxAχ-A YPh (Compound 13)<Polimerização>

[00208] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [Al3] was used in place of the solid titanium catalyst component [OCl]. The results are presented in Table 3. [Example 14]<Preparação do componente de catalisador de titânio sólido [al4]>

[00209] A solid titanium catalyst component [0C14] was obtained in the same manner as in Example 1, except that 1.94 g of the following compound 14 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0C14] thus obtained showed 0.67 wt% titanium, 1.2 wt% magnesium and 0.04 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 57] (Compound 14)<Polimerização>

[00210] Propene polymerization was carried out in the same way Petition 870250085949, dated 09 / 23 / 2025, pp. 102 / 112 91 / 97 in the same way as in Example 1, except that the solid titanium catalyst component [0C14] was used in place of the solid titanium catalyst component [ocl]. The results are presented in Table 3. [Example 15]<Preparação do componente de catalisador de titânio sólido [ocl5]>

[00211] A solid titanium catalyst component [0C15] was obtained in the same manner as in Example 1, except that 2.17 g of the following compound 15 were used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0C15] thus obtained had 0.29 wt% titanium, 1.4 wt% magnesium, and 0.02 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 58] H Ph, .N (Compound 15<Polimerização>

[00212] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [0C15] was used in place of the solid titanium catalyst component [ocl]. The results are shown in Table 3. [Example 16]<Preparação do componente de catalisador de titânio sólido [ocl6]>

[00213] A solid titanium catalyst component [0C16] was obtained in the same manner as in Example 1, except that 2.43 g of the following compound 16 were used in place of 1.77 g of compound 1. The composition of the titanium catalyst component Petition 870250085949, dated 09 / 23 / 2025, pp. 103 / 112 The 92 / 97 solid [α16] thus obtained contained 0.28% by mass of titanium, 1.3% by mass of magnesium and 0.03% by mass of 2-ethylhexyl alcohol residues. [Chemical Formula. 59] (Compound 16)<Polimerização>

[00214] Propene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [oc! 6] was used in place of the solid titanium catalyst component [ocl]. The results are shown in Table 3. Table 3 Example Activity (kg PP / g cat.) Apparent specific gravity (g / mL) MFR (g / 10 min) Amount of insoluble parts in decane (% by weight) Mw Mw / Mn Example 9 10.8 0.43 20.5 9.1 265,000 8.2 Example 10 16.3 0.46 13.2 8.3 286,000 7.6 Example 11 15.7 0.44 10.8 7.1 307,000 7.7 Example 12 16.9 0.47 14.8 8.4 275,000 7.5 Example 13 8.3 0.37 19.9 8.7 252,000 6.9 Example Example 14: 8.0 0.40 14.3 8.4 354,000 9.8 Example 15: 15.6 0.41 15.0 7.7 267,000 8.7 Example 16: 15.1 0.48 13.2 7.7 294,000 7.4 Table 3 (continued) Example Mz / Mw Mw / Mn + Mz / Mw Tm (°C) Tc (°C) ΔH (J / g) Example 9 7.7 15.9 163.1 / 157.6 114.3 91.6 Example 10 7.3 14.9 162.8 / 157.6 113.3 89.3 Example 11 6.5 14.2 158.3 / 144.5 113.6 93.2 Example 12 6.4 13.9 163.2 / 157.4 112.4 90.9 Example 13 6.7 13.6 163.3 / 157.2 113.1 85.4 Example 14 12.9 22.7 170.0 / 157.1 112.6 90.9 Example 15 5.8 14.5 163.8 / 158.6 113.6 91.5 Petition 870250085949, dated 09 / 23 / 2025, pages 104 / 112 93 / 97 Example 16 8, 3 15, 7 163.6 / 157.8 112.5 94.3 [Example 17]<Preparação do componente de catalisador de titânio sólido [al7]>

[00215] A solid titanium catalyst component [0C17] was obtained in the same manner as in Example 1, except that 1.57 g of the following compound 17 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0C17] thus obtained contained 0.95 wt% titanium, 1.0 wt% magnesium and 0.03 wt% residual 2-ethylhexyl alcohol. [Chemical Formula. 60] O o (Compound 17) [Example 18]<Preparação do componente de catalisador de titânio sólido [al8]>

[00216] A solid titanium catalyst component [al8] was obtained in the same manner as in Example 1, except that 1.50 g of the following compound 18 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [al8] thus obtained contained 0.85 wt% titanium, 1.1 wt% magnesium and 0.04 wt% residual 2-ethylhexyl alcohol. [Chemical Formula] 61] (Compound 18) [Example 19]<Preparação do componente catalítico de titânio sólido [al9]> Petition 870250085949, dated 09 / 23 / 2025, pp. 105 / 112 94 / 97

[00217] A solid titanium catalytic component [0C19] was obtained in the same manner as in Example 1, except that 0.98 g of the following compound 19 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalytic component [0Cl9] thus obtained contained 0.57 wt% titanium, 1.2 wt% magnesium and 0.16 wt% residual 2-ethylhexyl alcohol. [Chemical Formula. 62] o3—' o (Compound 19) [Example 20]<Preparação do componente de catalisador de titânio sólido [oc20]>

[00218] A solid titanium catalyst component [O20] was obtained in the same manner as in Example 1, except that 1.77 g of the following compound 20 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [O20] thus obtained had 0.80 wt% titanium, 1.0 wt% magnesium and 0.14 wt% residual 2-ethylhexyl alcohol. [Chemical Formula. (Compound 20) [Example 21]<Preparação do componente de catalisador de titânio sólido [a21]>

[00219] A solid titanium catalyst component [0C21] was obtained in the same manner as in Example 1, except that 1.49 g of the following compound 21 was used in place of 1.77 g of compound 1. The composition of the titanium catalyst component Petition 870250085949, dated 09 / 23 / 2025, pp. 106 / 112 The 95 / 97 solid [0C21] thus obtained had 0.71% by mass of titanium, 1.2% by mass of magnesium and 0.18% by mass of residual 2-ethylhexyl alcohol. [Chemical Formula. 64] (Compound 21) [Example 22]<Preparação do componente de catalisador de titânio sólido [oc22] >

[00220] A solid titanium catalyst component [0í22] was obtained in the same manner as in Example 1, except that 1.20 g of the following compound 22 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0í22] thus obtained had 0.38 wt% titanium, 1.6 wt% magnesium and 0.07 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 65] (Compound 22) [Example 23]<Preparação do componente de catalisador de titânio sólido [oc23]>

[00221] A solid titanium catalyst component [0í23] was obtained in the same manner as in Example 1, except that 1.64 g of the following compound 23 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0í23] thus obtained had 0.47 wt% titanium, 1.2 wt% magnesium and 0.02 wt% residual 2-ethylhexyl alcohol. Petition 870250085949, dated 09 / 23 / 2025, pp. 107 / 112 96 / 97 [Chemical Formula. 66] (Compound 23) [Example 24]<Preparação do componente de catalisador de titânio sólido [oc24]>

[00222] A solid titanium catalyst component [O24] was obtained in the same manner as in Example 1, except that 1.68 g of the following compound 24 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [O24] thus obtained had 0.57 wt% titanium, 1.3 wt% magnesium and 0.02 wt% residual 2-ethylhexyl alcohol. [Chemical Formula. 67] H H [Example 25]<Preparação do componente de catalisador de titânio sólido [oc25] >

[00223] A solid titanium catalyst component [0í25] was obtained in the same manner as in Example 1, except that 1.94 g of the following compound 25 was used in place of 1.77 g of compound 1. The composition of the solid titanium catalyst component [0í25] thus obtained had 0.47% by mass of titanium, 1.3% by mass of magnesium and 0.02% by mass of alcohol residues. 2Petition 870250085949, dated 23 / 09 / 2025, p. 108 / 112 97 / 97 ethylhexyl. [Chemical Formula 68] (Compound 25 [Example 26]<Preparação do componente catalítico de titânio sólido [oc26]>

[00224] A solid titanium catalytic component [Oi26] was obtained in the same manner as in Example 2, except that 2.43 g of the following compound 26 were used instead of 0.63 g of compound 1. The composition of the solid titanium catalytic component [Oi26] thus obtained contained 0.55 wt% titanium, 1.5 wt% magnesium and 0.04 wt% residual 2-ethylhexyl alcohol. [Chemical Formula 69] (Compound 26) Petition 870250085949, dated 09 / 23 / 2025, pages 109 / 112

Claims

1 / 2 CLAIMS 1. Solid titanium catalyst component, characterized in that it comprises magnesium, titanium, halogen and an amide compound specified by the following formula (1): [Chemical Formula 1] wherein C, C1 and C2 are carbon atoms; N is a nitrogen atom; R1 and R2 are each a hydrocarbon group; R3 to R6 are each a group containing an element selected from carbon, hydrogen and elements of Groups 15, 16 and 17 of the periodic table; R11 and R12 are each a hydrogen atom or a hydrocarbon group; m is an integer from 0 to 10; and A is a linking group selected from an aliphatic group, an alicyclic group and an aromatic group, and a plurality of A, when present, are all groups with the same structure or are groups with structures that differ partially or totally from each other.

2. Solid titanium catalyst component according to claim 1, characterized in that the amide compound is specified by the following formula (2): [Chemical Formula 2] Petition 870250085949, 2025 / 09 / 23, p. 110 / 112 2 / 2 R5 xAR6 (CRx2) m I XN R11 R12 XC R2 (2) where R1 to R6, R11, R12, C, C1, C2 and N are as defined for formula (1); m is an integer from 1 to 10; a plurality of Rx are groups containing an element selected from carbon, hydrogen and elements from Groups 15, 16 and 17 of the periodic table; and Rx are optionally connected to each other to form a ring structure.

3. Solid titanium catalyst component, according to claim 1, characterized in that R11 and R12 are hydrogen atoms.

4. Solid titanium catalyst component, according to claim 1, characterized in that R3, R4, R5 and R6 are hydrogen atoms.

5. Catalyst for olefin polymerization, characterized in that it comprises a solid titanium catalytic component (I), as defined in claim 1, and an organometallic compound catalytic component (II), containing a metallic element selected from Groups 1, 2 and 13 of the periodic table.

6. Catalyst for olefin polymerization, according to claim 5, characterized in that it further comprises an electron donor (III).

7. Method for polymerizing olefins, characterized by comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization, as defined in claim 5 or 6. Petition 870250085949, dated 09 / 23 / 2025, pp. 111 / 112