Olefin-based polymer

Abstract

The present invention relates to an olefin-based polymer exhibiting high mechanical rigidity due to the introduction of highly crystalline regions.

Description

Olefin polymers

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority based on Korean Patent Application No. 2024-0152390 filed on October 31, 2024, and all contents disclosed in the literature of said Korean patent applications are incorporated herein as part of this specification.

[0003]

[0004] Technology field

[0005] The present invention relates to an olefinic polymer that exhibits high mechanical strength by introducing a highly crystalline region.

[0006]

[0007] Polyolefins are widely used for extrusion, blow molding, and injection molding products due to their excellent moldability, heat resistance, mechanical properties, hygienic quality, water vapor permeability, and appearance characteristics of the molded articles. However, polyolefins, particularly polyethylene, lack polar groups within their molecules, resulting in low compatibility with polar resins such as nylon and poor adhesion to polar resins and metals. Consequently, it has been difficult to blend polyolefins with polar resins or metals, or to laminate them with these materials. Furthermore, polyolefin molded articles suffer from low surface hydrophilicity and antistatic properties.

[0008] To solve these problems and increase affinity for polar materials, a method of grafting a polar group-containing monomer onto a polyolefin via radical polymerization has been widely used. However, this method had a problem of low miscibility due to poor viscosity balance between the graft polymer and the polar resin caused by intramolecular crosslinking and molecular chain cleavage of the polyolefin during the graft reaction. In addition, there was a problem of poor appearance characteristics of the molded article due to gel components generated by intramolecular crosslinking or foreign substances generated by molecular chain cleavage.

[0009] In addition, as a method for producing olefin polymers such as ethylene homopolymers, ethylene / α-olefin copolymers, propylene homopolymers, or propylene / α-olefin copolymers, a method of copolymerizing polar monomers under a metal catalyst, such as a titanium catalyst or a vanadium catalyst, has been used. However, when copolymerizing polar monomers using such metal catalysts, there is a problem that the molecular weight distribution or composition distribution is wide and the polymerization activity is low.

[0010] In addition, another method of polymerization is known in the presence of a metallocene catalyst consisting of a transition metal compound such as zircononocene dichloride and an organoaluminum oxy compound (aluminoxane). When a metallocene catalyst is used, high molecular weight olefin polymers are obtained with high activity, and the resulting olefin polymers have a narrow molecular weight distribution and a narrow compositional distribution.

[0011] In addition, a method for producing polyolefins containing polar groups using a metallocene catalyst is also known, which uses a metallocene compound having a ligand of a non-crosslinked cyclopentadienyl group, a crosslinked or non-crosslinked bisdenyl group, or an ethylene-crosslinked unsubstituted indenyl / fluorenyl group. However, these methods have the disadvantage of very low polymerization activity. For this reason, a method of protecting polar groups with a protecting group is being implemented, but when a protecting group is introduced, the process becomes complicated because this protecting group must be removed again after the reaction.

[0012] Ansa-metallocene compounds are organometallic compounds containing two ligands connected to each other by a bridge group, wherein rotation of the ligands is prevented by the bridge group and the activity and structure of the metal center are determined.

[0013] Such anssa-metallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that anssa-metallocene compounds containing cyclopentadienyl-fluorenyl ligands can produce high molecular weight polyethylene, thereby enabling control of the microstructure of polypropylene.

[0014] In addition, anssa-metallocene compounds containing indenyl ligands are known to be capable of producing polyolefins with excellent activity and improved stereoregularity.

[0015] As such, various studies are being conducted on ansah-metallocene compounds that possess higher activity and can control the microstructure of olefinic polymers, but the extent of such research is still insufficient.

[0016] [Prior Art Literature]

[0017] [Patent Literature]

[0018] (Patent Document 1) KR 288272 B1

[0019]

[0020] The object of the present invention is to provide an olefinic polymer that exhibits high mechanical strength by introducing a highly crystalline region, obtained by polymerizing an olefinic monomer while introducing hydrogen gas using a transition metal compound catalyst.

[0021]

[0022] To solve the above problem, the present invention provides an olefin-based polymer.

[0023] (1) The present invention provides an olefinic polymer that satisfies the following conditions (a) to (d):

[0024] (a) Density: 0.855 to 0.880 g / cc

[0025] (b) Melt Index (190℃, 2.16 kg load condition; MI) 2.16): 0.1 to 35 dg / min

[0026] (c) Melt flow rate ratio (MFRR, MI) 10 / MI 2.16 ): 6.0 to 8.5

[0027] (d) When measured by differential scanning calorimetry (SSA), F(30)-F(70) > [1599.2 × density - 1354], where F(30) is the total enthalpy of melting at 30°C or higher, and F(70) is the total enthalpy of melting at 70°C or higher.

[0028] (2) The present invention provides an olefin-based polymer according to (1), wherein the density of condition (a) is 0.865 to 0.880 g / cc.

[0029] (3) The present invention provides an olefin-based polymer in which F (30) is 10.0 to 80.0 in the above (1) or (2).

[0030] (4) The present invention provides an olefin-based polymer in which F (70) is 0.1 to 12.0 in any one of (1) to (3).

[0031] (5) The present invention provides an olefin-based polymer in which, in any one of (1) to (4), the melt index is 0.5 to 30 dg / min.

[0032] (6) The present invention provides an olefin-based polymer in which, in any one of (1) to (5), the melt flow index is 6.2 to 8.3.

[0033] (7) The present invention provides an olefin polymer having a weight-average molecular weight of 10,000 to 150,000 g / mol in any one of (1) to (6).

[0034] (8) The present invention provides an olefin-based polymer having a molecular weight distribution of 1.5 to 3.0 in any one of (1) to (7).

[0035] (9) The present invention provides an olefin polymer in any one of (1) to (8), wherein the olefin polymer is a copolymer of ethylene and an alpha-olefin monomer having 3 to 12 carbon atoms.

[0036] (10) The present invention provides an olefin polymer in which the alpha-olefin monomer in (9) above is one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene and 1-dodecene.

[0037]

[0038] The olefinic polymer according to the present invention is a low-density olefinic polymer that exhibits high mechanical strength due to the introduction of highly crystalline regions.

[0039]

[0040] Figure 1 is a graph showing the results of differential scanning calorimetry (SSA) measurements for the polymers of Example 3 and Comparative Example 1.

[0041] FIG. 2 shows F(30)-F(70) according to density for the polymers of Examples 1 to 4 and Comparative Examples 1 and 2.

[0042] Figure 3 shows the tensile strength according to density for the polymers of Examples 1 to 4 and Comparative Example 1.

[0043] Figure 4 shows the tear strength according to density for the polymers of Examples 1 to 4 and Comparative Example 1.

[0044]

[0045] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0046]

[0047] Terms and words used in the description and claims of the present invention shall not be interpreted as being limited to their ordinary or dictionary meanings, and shall be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0048] In this specification, the term "polymer" means a polymer compound produced by the polymerization of the same or different types of monomers. The general term "polymer" includes the terms "homopolymer," "copolymer," "terpolymer," as well as "copolymer." Furthermore, the term "copolymer" means a polymer produced by the polymerization of two or more different types of monomers. The general term "copolymer" includes the term "copolymer" (commonly used to refer to a polymer produced from two different monomers) as well as the term "terpolymer" (commonly used to refer to a polymer produced from three different types of monomers). This includes a polymer produced by the polymerization of four or more types of monomers.

[0049]

[0050] The olefinic polymer of the present invention satisfies the following conditions (a) to (d).

[0051] (a) Density: 0.855 to 0.880 g / cc

[0052] (b) Melt Index (190℃, 2.16 kg load condition; MI) 2.16 ): 0.1 to 35 dg / min

[0053] (c) Melt flow rate ratio (MFRR, MI) 10 / MI 2.16 ): 6.0 to 8.5

[0054] (d) When measured by differential scanning calorimetry (SSA), F(30)-F(70) > [1599.2 × density - 1354], where F(30) is the total enthalpy of melting at 30°C or higher, and F(70) is the total enthalpy of melting at 70°C or higher.

[0055]

[0056] The olefin-based polymer according to the present invention exhibits higher tensile strength and tear strength when having the same level of density and melt index, due to the introduction of a highly crystalline region compared to conventional olefin-based polymers. The olefin-based polymer is prepared by polymerizing olefin monomers while introducing hydrogen gas in the presence of an olefin polymerization catalyst composition, and exhibits excellent mechanical strength as a highly crystalline region is introduced due to the introduction of hydrogen gas during polymerization.

[0057]

[0058] Specifically, the olefinic polymer of the present invention is a low-density polymer with a density in the range of 0.855 to 0.880 g / cc as measured according to ASTM D-792. Specifically, the density may be 0.856 g / cc or higher, 0.858 g / cc or higher, 0.860 g / cc or higher, or 0.865 g / cc or higher, 0.878 g / cc or lower, 0.875 g / cc or lower, or 0.872 g / cc or lower.

[0059] Typically, the density of olefinic polymers is influenced by the type and content of monomers used during polymerization and the degree of polymerization, while in the case of copolymers, it is significantly influenced by the content of comonomers. The olefinic polymer of the present invention is polymerized using a catalyst composition containing a transition metal compound having a characteristic structure, which enables the introduction of a large amount of comonomers; thus, the olefinic polymer of the present invention can have a low density within the range described above.

[0060]

[0061] In the present invention, the olefinic polymer has a melt index (190°C, 2.16 kg load condition; MI 2.16 The melt index is in the range of 0.1 to 35 dg / min. Specifically, the melt index may be 0.5 dg / min or more, 1 dg / min or more, 2 dg / min or more, 3 dg / min or more, or 4 dg / min or more, and may be 30 dg / min or less, 25 dg / min or less, 20 dg / min or less, 15 dg / min or less, 10 dg / min or less, 7 dg / min or less, or 6 dg / min or less, for example, 0.5 to 30 dg / min.

[0062] The above melt index (MI) can be controlled by adjusting the amount of comonomer of the catalyst used in the polymerization process of the olefin polymer, and affects the mechanical properties, impact strength, and moldability of the olefin polymer.

[0063] When the melt index of the olefin-based polymer of the present invention is within the above range, the processability of the olefin-based polymer is good and the impact strength of the product is excellent when applied as a compound. If the melt index is less than 0.1, there is a problem that the processability is reduced due to the high viscosity of the polymer in the molten state, and if it is greater than 35, there is a problem that the impact strength of the product is reduced when applied as a compound.

[0064]

[0065] In the present invention, the melt flow rate ratio (MFRR, Melt flow rate ratio, MI) of an olefinic polymer 10 / MI 2.16 ) is 6.0 to 8.5. Specifically, it may be 6.2 or higher, 6.5 or higher, 6.8 or higher, or 7.0 or higher, and may be 8.3 or lower, 8.2 or lower, 8.0 or lower, or 7.9 or lower, for example, 6.2 to 8.3.

[0066] When the melt flow index of the olefin-based polymer of the present invention is within the above range, the processability of the olefin-based polymer is good and the impact strength of the product is excellent when applied as a compound. When the melt flow index is less than 6.0, there is a problem of reduced processability of the polymer, and when it is greater than 8.5, there is a problem of reduced impact strength of the product when applied as a compound.

[0067]

[0068] In the present invention, when measuring an olefin-based polymer using the differential scanning calorimetry (SSA) method, F(30) - F(70) > [1599.2 × density - 1354]. Here, F(30) is the sum of the melting enthalpies at 30°C or higher, and F(70) is the sum of the melting enthalpies at 70°C or higher. Specifically, when the temperature-heat capacity curve is integrated for each section from the results of the differential scanning calorimetry (SSA) method to fractionate the heat capacity of each section relative to the total heat capacity, F(30) is the sum of the melting enthalpies at 30°C or higher, and F(70) is the sum of the melting enthalpies at 70°C or higher.

[0069]

[0070] The above differential scanning calorimetry (SSA) measurement is a method for obtaining more precise crystal information by using a differential scanning calorimeter (DSC) to undergo a process of heating and cooling to a temperature just before the peak of the melting temperature (Tm) after the first cycle, and then repeatedly performing a process of heating and cooling to a temperature lowered by about 5°C (Eur. Polym. J. 2015, 65, 132).

[0071] When a small amount of highly crystalline region is introduced into an olefinic polymer, it does not appear when measuring the melting temperature using a general differential scanning calorimeter (DSC), but the high-temperature melting peak can be measured through the above differential scanning calorimeter precision measurement method (SSA).

[0072] The fact that the F(30)-F(70) value of the olefin polymer is greater than [1599.2 × density - 1354] means that the difference between F(30) and F(70) is greater than a certain value, and especially if the density value increases, the difference can also increase. A large F(30) indicates that the olefin polymer contains a relatively large amount of highly crystalline regions, and a small F(70) indicates that the crystallization distribution of the olefin polymer is uniform. That is, the olefin polymer of the present invention has a large amount of highly crystalline regions and a uniform crystallization distribution, and has the advantage of improved mechanical strength.

[0073] If the above F(30)-F(70) value is less than or equal to [1599.2 × density - 1354], the mechanical strength of the olefin polymer is reduced when it has an equivalent level of density.

[0074]

[0075] In the present invention, while having the value of F(30)-F(70), F(30) may be 10.0 to 80.0. Specifically, it may be 20.0 or more, 30.0 or more, 31.0 or more, 31.5 or more, or 32.0 or more, and may be 70.0 or less, 60.0 or less, 55.0 or less, 50.0 or less, or 45.0 or less.

[0076] Additionally, F(70) may be 0.1 to 12.0. Specifically, it may be 0.5 or more, 0.7 or more, 0.8 or more, 1.0 or more, or 1.5 or more, and 10.0 or less, 5.0 or less, 4.7 or less, 4.5 or less, 4.3 or less, or 4.1 or less.

[0077]

[0078] In addition, the olefin-based polymer of the present invention has a narrow molecular weight distribution (MWD) in the range of 1.5 to 3.0. As an example, the molecular weight distribution may be 1.6 or more, 1.7 or more, 1.8 or more, or 2.0 or more, and may be 2.9 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.2 or less.

[0079] Meanwhile, in the present invention, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated from the ratio of Mw / Mn.

[0080] According to one embodiment of the present invention, the olefin-based polymer may be a polymer having a weight-average molecular weight (Mw) of 10,000 to 150,000 g / mol. More specifically, the weight-average molecular weight may be 15,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, 40,000 g / mol or more, 50,000 g / mol or more, 60,000 g / mol or more, or 70,000 g / mol or more, and may be 150,000 g / mol or less, 120,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, or 80,000 g / mol or less.

[0081] When the above molecular weight distribution and weight-average molecular weight satisfy the above range, there may be advantages such as good processability and excellent impact strength of the product when applied as a compound.

[0082]

[0083] In the present invention, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin monomer having 3 to 12 carbon atoms. Specifically, the alpha-olefin monomer may be one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, and 1-dodecene.

[0084] Specifically, the olefin-based polymer of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene, and more specifically, may be a copolymer of ethylene and 1-butene.

[0085] When the above olefin-based polymer is a copolymer of ethylene and alpha-olefin, the content of the alpha-olefin comonomer can be appropriately selected within a range that satisfies the above physical property requirements, specifically, it can be greater than 0 and less than or equal to 99 mol%, or 10 to 50 mol%.

[0086] The olefin-based polymer of the present invention can be prepared through a continuous solution polymerization reaction in which olefin monomers are polymerized in a single reactor while introducing hydrogen gas in the presence of a metallocene catalyst composition containing one or more transition metal compounds. Accordingly, in the olefin-based polymer according to one embodiment of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer are connected linearly. That is, the olefin-based polymer according to the present invention does not include a block copolymer and may be selected from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer, and more specifically, may be a random copolymer.

[0087]

[0088] The olefin-based polymer of the present invention can be manufactured by a manufacturing method comprising the step of polymerizing an olefin-based monomer while introducing hydrogen at a rate of 30 to 130 cc / min in the presence of a catalyst composition comprising a transition metal compound represented by the following chemical formula 1.

[0089] [Chemical Formula 1]

[0090]

[0091] In the above chemical formula 1,

[0092] M is Hf or Zr, and

[0093] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0094] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0095] A1 and A2 are each independently substituted or unsubstituted cycloalkyl groups having 5 to 10 carbon atoms or N(Ra)(Rb), and

[0096] The above Ra and Rb are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0097] The substituents of A1 and A2 are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and

[0098] R1 to R 24Each is independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.

[0099]

[0100] In the above chemical formula 1, M is Hf or Zr.

[0101] In the above chemical formula 1, L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen. Specifically, it may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and, for example, a methyl group.

[0102] In the above chemical formula 1, Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms. Specifically, it may be an alkylene group having 2 to 30 carbon atoms, an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 6 carbon atoms, and, for example, a propylene group.

[0103] In the above chemical formula 1, A1 and A2 are each independently substituted or unsubstituted cycloalkyl groups having 5 to 10 carbon atoms or N(Ra)(Rb).

[0104] When the above A1 and A2 are substituted cycloalkyl groups having 5 to 10 carbon atoms, the substituents of A1 and A2 are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, specifically, they may be alkyl groups having 1 to 15 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or alkyl groups having 1 to 6 carbon atoms, and for example, may be methyl groups, ethyl groups, propyl groups, or butyl groups.

[0105] More specifically, A1 and A2 may each independently be structures represented by the following chemical formula 2.

[0106] [Chemical Formula 2]

[0107]

[0108] In the above chemical formula 2,

[0109] R 25 to R 29 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0110] More specifically, R 25 , R 26 , R 28 and R 29 is hydrogen, and R 27 It may be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and, for example, a methyl group, an ethyl group, a propyl group, or a butyl group.

[0111]

[0112] When A1 and A2 are N(Ra)(Rb), Ra and Rb are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms. Specifically, each may independently be an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 40 carbon atoms, more specifically, an alkyl group having 1 to 20 carbon atoms, and even more specifically, an alkyl group having 4 to 20 carbon atoms. When Ra and Rb are long-chain alkyl groups having 4 or more carbon atoms, the solubility for hexane, which was rarely observed in conventional catalyst compounds, can be significantly increased. In addition, the amine group at the para position and the long chain play a role in raising the melting temperature, which can improve the mechanical strength of the olefin polymer produced using the above compound as a catalyst.

[0113]

[0114] In the above Chemical Formula 1, R1 to R 24 Each is independently hydrogen, a halogen, a cyano group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Specifically, it may be hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. For example, it may be hydrogen, F, or a tert-butyl group. More specifically, R1 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R 18 and R 23It may be a halogen group, e.g., F. Or, R1, R2, R4, R5, R7 to R 10 , R 12 , R 13 , R 15 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R3, R6, R 11 and R 14 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, for example, a tert-butyl group, and R 18 and R 23 It can be a halogen group, such as F.

[0115]

[0116] The transition metal compound represented by the above chemical formula 1 may be represented by the following chemical formula 1A or 1B.

[0117] [Chemical Formula 1A]

[0118]

[0119] In the above chemical formula 1A,

[0120] M is Hf or Zr, and

[0121] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0122] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0123] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0124] R 30 and R 31 Each is independently hydrogen or an alkyl group having 1 to 20 carbon atoms.

[0125] [Chemical Formula 1B]

[0126]

[0127] In the above chemical formula 1B,

[0128] M is Hf or Zr, and

[0129] L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and

[0130] Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and

[0131] R1 to R 24 Each is independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and

[0132] Ra and Rb are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.

[0133]

[0134] Specifically, in the above chemical formula 1A, M is Hf or Zr, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R 18and R 23 is a halogen group, and R 30 and R 31 Each can independently be an alkyl group having 1 to 20 carbon atoms.

[0135] Additionally, specifically, in the above Chemical Formula 1A, M is Hf, L is an alkyl group having 1 to 20 carbon atoms, Y is an alkylene group having 2 to 40 carbon atoms, and R1, R2, R4, R5, R7 to R 10 , R 12 , R 13 , R 15 to R 17 , R 19 to R 22 and R 24 is hydrogen, and R3, R6, R 11 and R 14 is an alkyl group having 1 to 20 carbon atoms, and R 18 and R 23 is a halogen group, and R 30 and R 31 Each can independently be an alkyl group having 1 to 20 carbon atoms.

[0136]

[0137] For example, the transition metal compound represented by the above chemical formula 1 may be one selected from the group consisting of the following chemical formulas 1-1 to 1-10.

[0138] [Chemical Formula 1-1]

[0139]

[0140] [Chemical Formula 1-2]

[0141]

[0142] [Chemical Formula 1-3]

[0143]

[0144] [Chemical Formula 1-4]

[0145]

[0146] [Chemical Formula 1-5]

[0147]

[0148] [Chemical Formula 1-6]

[0149]

[0150] [Chemical Formula 1-7]

[0151]

[0152] [Chemical Formula 1-8]

[0153]

[0154] [Chemical Formula 1-9]

[0155]

[0156] [Chemical Formula 1-10]

[0157]

[0158] In the above chemical formulas 1-7 to 1-10, the alkyl group connected to N, namely hexyl, dodecyl, and C 12 H 25 It is a straight hydrocarbon chain without branches.

[0159]

[0160] In the present invention, by using the aforementioned transition metal compound and introducing hydrogen in an optimized amount during the polymerization reaction, an olefin-based polymer having characteristics such as a narrow molecular weight distribution and a uniform crystallinity distribution can be produced as described above. If the amount of hydrogen introduced is less than 30 cc / min, the molecular weight distribution and crystallinity distribution of the olefin-based polymer become wide, causing a problem of reduced mechanical strength; and if the amount of hydrogen introduced exceeds 130 cc / min, the molecular weight of the olefin-based polymer is low, which may cause a problem of reduced impact strength of the product when applied to a compound.

[0161]

[0162] The transition metal compound of Chemical Formula 1 above can be used as a catalyst for a polymerization reaction in the form of a composition that additionally includes one or more of the co-catalyst compounds represented by Chemical Formulas 3, 4, and 5 below.

[0163] [Chemical Formula 3]

[0164] -[Al(Rb)-O] a -

[0165] [Chemical Formula 4]

[0166] A(Rb)3

[0167] [Chemical Formula 5]

[0168] [LH] + [W(D)4] - or [L] + [W(D)4] -

[0169] In the above chemical formulas 3 to 5,

[0170] Rb may be identical or different from one another and are each independently selected from the group consisting of a halogen, a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms substituted with a halogen, and

[0171] A is aluminum or boron, and

[0172] D is an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms, each of which can independently be substituted with one or more hydrogen atoms as substituents, wherein the substituent is at least one selected from the group consisting of a halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, and an aryloxy having 6 to 20 carbon atoms.

[0173] H is a hydrogen atom, and

[0174] L is a neutral or cationic Lewis base, and

[0175] W is a Group 13 element, and

[0176] a is an integer greater than or equal to 2.

[0177] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxans such as methylaluminoxan (MAO), ethylaluminoxan, isobutylaluminoxan, and butylaluminoxan, and also modified alkylaluminoxans in which two or more of the above alkylaluminoxans are mixed, specifically methylaluminoxan and modified methylaluminoxan (MMAO).

[0178] Examples of compounds represented by the above chemical formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc., and specifically, may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0179] Examples of compounds represented by the above chemical formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethylanilinium tetrakis(pentafluorophenyl)boron, triethylammonium tetraphenylalumin, tributylammonium tetraphenylalumin. Trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentaphentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,p-dimethylphenyl)boron, Examples include triphenylcarbonium tetra(p-trifluoromethylphenyl)boron or triphenylcarbonium tetrapentafluorophenylboron.

[0180] The catalyst composition may be prepared by a first method comprising: 1) contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 3 or Formula 4 to obtain a mixture; and 2) adding a compound represented by Formula 5 to the mixture.

[0181] In addition, the catalyst composition can be prepared as a second method by contacting a compound represented by the chemical formula 5 with a transition metal compound represented by the chemical formula 1.

[0182] In the case of the first method among the methods for preparing the catalyst composition above, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 3 or Formula 4 may be 1 / 5,000 to 1 / 2, specifically 1 / 1,000 to 1 / 10, and more specifically 1 / 500 to 1 / 20. If the molar ratio exceeds 1 / 2, there is a problem that the amount of alkylating agent is very small and the alkylation of the metal compound does not proceed completely, and if the molar ratio is less than 1 / 5,000, the alkylation of the metal compound occurs, but there is a problem that the activation of the alkylated metal compound does not occur completely due to side reactions between the remaining excess alkylating agent and the activator, which is the compound of Formula 5. In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 5 may be 1 / 25 to 1, specifically 1 / 10 to 1, and more specifically 1 / 5 to 1. If the molar ratio of the transition metal compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 5 exceeds 1, the amount of activator is relatively small, so the activation of the metal compound is not fully achieved, and the activity of the resulting catalyst composition may decrease. If the molar ratio is less than 1 / 25, the activation of the metal compound is fully achieved, but the unit cost of the catalyst composition may not be economical due to the remaining excess activator, or the purity of the resulting polymer may decrease.

[0183] In the case of the second method among the methods for preparing the catalyst composition above, the molar ratio of the transition metal compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 5 may be 1 / 10,000 to 1 / 10, specifically 1 / 5,000 to 1 / 100, and more specifically 1 / 3,000 to 1 / 500. If the molar ratio exceeds 1 / 10, the amount of activator is relatively small, so the activation of the metal compound is not fully achieved, and the activity of the catalyst composition produced may decrease. If the ratio is less than 1 / 10,000, the activation of the metal compound is fully achieved, but the unit cost of the catalyst composition may not be economical due to the remaining excess activator, or the purity of the polymer produced may decrease.

[0184] In the preparation of the above catalyst composition, hydrocarbon solvents such as pentane, hexane, heptane, etc., or aromatic solvents such as benzene, toluene, etc., may be used as reaction solvents.

[0185] In addition, the catalyst composition may include the transition metal compound and the co-catalyst compound in a form supported on a carrier.

[0186] The above-mentioned carrier may be used without special restrictions as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina, or silica-magnesia, and any one or more of these may be used.

[0187] Among these, when the carrier is silica, the functional group of the metallocene compound of Formula 1 forms a chemical bond with the silica carrier, so there is almost no catalyst released from the surface during the olefin polymerization process. As a result, fouling that occurs when polymer particles stick together on the reactor walls or to each other can be prevented during the manufacturing process of the olefin polymer. In addition, the olefin polymer manufactured in the presence of a catalyst containing the silica carrier has excellent polymer particle shape and apparent density.

[0188] More specifically, the carrier may be high-temperature dried silica or silica-alumina, etc., containing highly reactive siloxane groups on its surface through a method such as high-temperature drying.

[0189] The above carrier may additionally include oxide, carbonate, sulfate, or nitrate components such as Na2O, K2CO3, BaSO4, or Mg(NO3)2.

[0190] The polymerization reaction for polymerizing the above olefin monomer can be carried out by conventional processes applied to the polymerization of olefin monomers, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

[0191] The polymerization reaction of the above olefin monomer can be carried out under an inert solvent, and examples of the inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, and 1-octene.

[0192] The polymerization of the above olefin-based polymer can be carried out at a temperature of about 25°C to about 500°C, specifically at a temperature of 80°C to 250°C, more preferably at a temperature of 100°C to 200°C. In addition, the reaction pressure during polymerization is 1 kgf / cm² 2 Up to 150 kgf / cm² 2 , preferably 1 kgf / cm² 2Up to 120 kgf / cm² 2 , more preferably 5 kgf / cm² 2 Up to 100 kgf / cm² 2 It could be.

[0193] Since the olefin-based polymer of the present invention has improved physical properties, it is useful for blow molding, extrusion molding, or injection molding in various fields and applications such as packaging, construction, and household goods, as well as materials for automobiles, wires, toys, textiles, and medical products, and can be particularly useful for automobiles where excellent impact strength is required.

[0194] In addition, the olefin-based polymer of the present invention can be usefully used in the manufacture of molded articles.

[0195] The above-mentioned molded body may specifically be a blow-molded body, an inflation-molded body, a cast-molded body, an extrusion-laminate-molded body, an extrusion-molded body, a foam-molded body, an injection-molded body, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric, etc.

[0196]

[0197] Examples

[0198] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

[0199]

[0200] Preparation Example 1

[0201] [Chemical Formula 1-4]

[0202]

[0203] The above compound was prepared as follows.

[0204]

[0205] 1 eq. of 4-(trans-4-butylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with distilled water and MC (Dimethyl Chloride), and slurried with hexane to obtain the product.

[0206] 1 H NMR (500 MHz, CDCl3): 7.16(2H, d), 6.98(2H, d), 5.4(1H, t), 3.98(1H, m), 3.61(1H, m), 2.42(1H, t), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0207]

[0208] 1 eq. of 2-(4-((1s,4r)-4-butylcyclohexyl)phenoxy)tetrahydro-2H-pyran was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 21.3 eq. of I was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a saturated sodium thiosulfate solution was added and stirred for 10 minutes. After EA (Ethyl Acetate) extraction, the mixture was vacuum dried. The generated solid was dissolved in hexane, filtered through a celite filter, and dried in hexane to obtain the product.

[0209] 1H NMR (500 MHz, CDCl3): 7.60(1H, s), 7.11(2H, d), 6.99(2H, d), 5.48(1H, t), 3.90(1H, t), 3.60(1H, m), 2.37(1H, t), 2.15(1H, m), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0210]

[0211] 1 eq. of 2-(4-((1r,4r)-4-butylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of carbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out at 115°C for two nights. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0212] 1 H NMR (500 MHz, CDCl3): 8.16(2H, d), 7.41(2H, m), 7.36(2H, m), 7.27(4H, m), 7.20(1H, d), 5.24(1H, m), 3.63(1H, m), 3.46(1H, m), 2.55(1H, t), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0213]

[0214] 1 eq. of 9-(5-((1s,4r)-4-butylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. At -10°C, 1.25 eq. of n-BuLi was added, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of dissolved methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, the product was obtained by EA (Ethyl Acetate) extraction followed by vacuum drying.

[0215] 1 H NMR (500 MHz, CDCl3): 8.23(1H, d), 8.13(1H, d), 7.82(1H, d), 7.45(1H, t), 7.35(2H, m), 7.25(3H, m), 7.10(1H, d), 3.5(1H, s), 2.68(1H, t), 1.95-1.81(4H, d), 1.65(2H, m), 1.29(2H, m), 1.20(11H, m), 1.02(2H, m), 0.89(3H, t)

[0216]

[0217] 1,3-bis(2-bromo-4-fluorophenoxy)propane 1 eq., (5-((1s,4r)-4-butylcyclohexyl)-3-(9H-carbazol-9-yl)-2-hydroxyphenyl)boronic acid 2.5 eq., K2CO3 6 eq., and 45 mol% Pd(PPh3) were added to a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The reaction was carried out overnight at 95°C. After the reaction was completed, the mixture was cooled to room temperature, extracted with EA (Ethyl Acetate), and vacuum dried. The resulting solid was dissolved in hexane and passed through a column, and the resulting solution was vacuum dried. The dried solid was slurried with hexane to obtain the product.

[0218] 1 H NMR (500 MHz, CDCl3): 8.18(4H, d), 7.33(3H, t), 7.26(3H, t), 7.16(4H, d), 7.08(4H, d), 6.76(4H, d), 6.62(2H, t), 6.2(2H, m), 5.57(2H, s), 3.83(4H, t), 2.46(2H, t), 2.39(2H, t), 1.94-1.86(8H, dd), 1.41(10H, m), 1.34-1.04(12H, m), 1.04(6H, t)

[0219]

[0220] 1 eq of HfCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and toluene was added to the dried solid, followed by stirring for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0221] 1 H NMR (500 MHz, CDCl3): 8.37(2H, d), 8.16(2H, d), 7.49(6H, d), 7.34(6H, m), 7.17(4H, m), 7.09(2H, s), 6.99(2H, d), 6.37(2H, t), 4.41(2H, t), 3.81(2H, m), 3.41(2H, m), 2.48(2H, t), 1.96-1.93(8H, dd), 1.41(5H, m), 1.34(12H, m), 1.04(4H, m), 1.04(6H, t), -1.78(6H, s)

[0222]

[0223] Preparation Example 2

[0224] [Chemical Formula 1-5]

[0225]

[0226] The above compound was prepared as follows.

[0227]

[0228] 1 eq. of 4-(trans-4-butylcyclohexyl)phenol, 8 mol% of PPTS, and 2 eq. of DHP dissolved in 1 M dichloromethane were added to a 100 ml round flask. The reaction was carried out overnight at 35°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with distilled water and MC (Dimethyl Chloride), and slurried with hexane to obtain the product.

[0229] 1 H NMR (500 MHz, CDCl3): 7.16(2H, d), 6.98(2H, d), 5.4(1H, t), 3.98(1H, m), 3.61(1H, m), 2.42(1H, t), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0230]

[0231] 1 eq. of 2-(4-((1s,4r)-4-butylcyclohexyl)phenoxy)tetrahydro-2H-pyran was added to 0.3 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature while stirring for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 21.3 eq. of I was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was complete, a saturated sodium thiosulfate solution was added and stirred for 10 minutes. After EA (Ethyl Acetate) extraction, the mixture was vacuum dried. The generated solid was dissolved in hexane, filtered through a celite filter, and dried in hexane to obtain the product.

[0232] 1H NMR (500 MHz, CDCl3): 7.60(1H, s), 7.11(2H, d), 6.99(2H, d), 5.48(1H, t), 3.90(1H, t), 3.60(1H, m), 2.37(1H, t), 2.15(1H, m), 1.96(1H, m), 1.85(4H, d), 1.70(2H, m), 1.39(2H, m), 1.27(11H, m), 1.02(2H, m), 0.89(3H, t)

[0233]

[0234] 1 eq. of 2-(4-((1r,4r)-4-butylcyclohexyl)-2-iodophenoxy)tetrahydro-2H-pyran, 1.1 eq. of 3,6-di-tert-butylcarbazole, 20 mol% of CuI, 3.8 eq. of K3PO4, and 50 mol% of N-methylimidazole were added to a 100 ml flask in 0.2 M toluene. The reaction was carried out overnight at 115°C. After the reaction was complete, the mixture was cooled to room temperature, extracted with EA, and vacuum dried. The resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0235] 1 H NMR (500 MHz, CDCl3): 8.11(2H, s), 7.41(2H, td), 7.32(1H, d), 7.24(2H, td), 7.18(1H, d), 7.11(1H, m), 5.2(1H, t), 3.71(1H, td), 3.48(1H, dt), 2.48(1H, tt), 1.95-1.85(4H, dd), 1.70(2H, m), 1.46(18H, s), 1.36(2H, m), 1.25(11H, m), 1.02(2H, m), 0.90(3H, t)

[0236]

[0237] 1 eq. of 3,6-di-tert-butyl-9-(5-((1r,4r)-4-butylcyclohexyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole was added to 0.2 M THF in a 100 ml Schrenk flask. 1.25 eq. of n-BuLi was added at -10°C, and the temperature was slowly raised to room temperature and stirred for 4 hours. After 4 hours, the temperature was lowered back to -10°C, and a THF solution containing 1.3 eq. of methyl borate was slowly added. The process was carried out overnight at room temperature while slowly raising the temperature. After the reaction was completed, EA (Ethyl Acetate) extraction was performed, followed by vacuum drying. The resulting solid was slurried with methanol, filtered, and the obtained solid was dried to obtain the product.

[0238] 1 H NMR (500 MHz, CDCl3): 8.19(2H, s), 8.10(2H, d), 7.47(2H, d), 7.40(2H, dd), 7.13(2H, d), 2.61(1H, t), 2.03-1.91(4H, dd), 1.46-1.34(22H, m), 1.24(2H, m), 1.2-1.11(3H, m), 1.05(2H, m), 0.9(3H, t)

[0239]

[0240] 1,3-bis(2-bromo-4-fluorophenoxy)propane 1 eq., (3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-((1r,4r)-4-butylcyclohexyl)-2-hydroxyphenyl)-boronic acid 2.5 eq., K2CO3 6 eq., and Pd(PPh3)45 mol% were added to a 50 ml vial in 0.2 M 1,4-dioxane and 0.5 M H2O. The process was carried out at 95°C overnight. After the reaction was complete, it was cooled to room temperature, vacuum dried after EA (Ethyl Acetate) extraction, and the resulting solid was dissolved in hexane and processed through a column to obtain the product.

[0241] 1 H NMR (500 MHz, CDCl3): 8.19(4H, s), 7.40(4H, d), 7.2(2H, m), 7.04(6H,t), 7.00(2H, d), 6.55(2H, t), 6.07(2H, m), 5.43(2H, s), 3.82(4H, t), 2.43(2H, t), 2.02(2H, t), 1.92-1.81(8H, dd), 1.70(4H, m), 1.46(36H, s), 1.36(4H, m), 1.25-1.19(22H, m), 1.02(4H, m), 0.90(6H, t)

[0242]

[0243] 1 eq of HfCl4 was added to a cold (-25°C) slurry state with 0.05 M toluene, and 4.1 eq. of 3.0 M MeMgBr was added. The mixture was stirred for 2 minutes, 1 eq. of ligand was added as a solid, and washed with toluene. The temperature was gradually increased, and the reaction mixture was stirred overnight at room temperature. The black mixture was concentrated under high vacuum, and hexane was added to the dried solid and stirred for about 10 minutes. The solid was filtered and collected, and the colorless filtrate was concentrated under high vacuum to obtain a white product.

[0244] 1 H NMR (500 MHz, CDCl3): 8.29(2H, d), 8.06(2H, d), 7.45(2H, dd), 7.41(2H, dd), 7.36(2H, dd), 7.33(2H, d), 7.236(2H, d), 7.05(2H, d), 6.99(2H, dd), 6.28(2H, m), 4.56(2H, dd), 3.80(2H, m), 3.38(2H, m), 2.45(2H, tt), 1.93-1.82(8H, dd), 1.70(4H, m), 1.46(36H, s), 1.36(4H, m), 1.25-1.19(22H, m), 1.02(4H, m), 0.90(6H, t), -1.75(6H, s)

[0245]

[0246] Preparation Example 3

[0247] [Chemical Formula 1-8]

[0248]

[0249] The above compound was prepared as follows.

[0250] (1) Preparation of ligand compound (2-bromo-4-(didodecylamino)phenol)

[0251] 12 g (63.82 mmol) of 4-amino-2-bromophenol reagent, 31.813 g (127.64 mmol) of 1-bromododecane, 43.35 mL (255.28 mmol) of DiPEA, and 160 mL of DMF were weighed into a 250 mL two-neck flask, and the mixture was refluxed overnight at 150 °C. After confirming the NMR, the mixture was worked up with water, EA, and magnesium sulfate, and the organic layer was concentrated to obtain a red liquid product with a yield of 18 g, or 53.8%.

[0252] 1 H-NMR (500 MHz, CDCl3): 6.88 (d, 1H), 6.74 (d, 1H), 6.57 (d, 1H), 4.88 (s, 1H), 3.14 (t, 4H), 1.50-1.52 (m, 4H), 1.32-1.27 (m, 40H), 0.88 (s, 6H)

[0253]

[0254] (2) Preparation of ligand compound (3-bromo-N,N-didodecyl-4(methoxymethoxy)aniline)

[0255] 5 g (9.53 mmol) of the product obtained above was weighed into a 100 mL one-neck container, and 19.06 mL of DMF was added. 457.4 mg (11.406 mmol) of NaH was added gradually at room temperature (RT) and reacted for 30 minutes, after which 860.5 μl (11.436 mmol) of chloromethylmethylether was added and reacted overnight. After confirming the NMR, workup was performed with water and ethyl acetate / magnesium sulfate. 5.3 g of a red liquid product was obtained with a yield of 97.8%.

[0256] 1H-NMR (in CDCl3 500 MHz): 6.99(d, 1H), 6.79(d, 1H), 6.51(d,1H), 5.10(s, 2H), 3.54(s, 3H), 3.17(t, 4H), 1.54-1.51(m, 4H), 1.30-1.26(m, 40H), 0.88(t, 6H)

[0257]

[0258] (3) Preparation of ligand compound (3-(9H-carbazol-9-yl)-N,N-didodecyl-4-(methoxymethoxy)aniline)

[0259] After weighing 4.66 mg (8.2 mmol) of the product obtained above, 1.25 mg (7.45 mmol) of carbazole, 1.42 g (7.45 mmol) of CuI, 1.78 mL (22.35 mmol) of methylimidazole, and 46 g (28.31 mmol) of K3PO into a 250 mL two-neck container, 37.25 mL of toluene was added and refluxed at 120°C overnight. Workup with water and ethyl acetate yielded 4.81 g of a white solid product with a yield of 94%.

[0260] 1 H-NMR (500 MHz, CDCl3): 8.13(d, 2H), 7.40(t, 2H), 7.29-7.24(m, 4H), 6.72(d, 1H), 6.69(d, 1H), 4.71(s, 2H), 3.21(t, 4H), 3.02(s, 3H), 1.60-1.56(m, 4H), 1.30-1.25(m, 40H), 0.89(t, 6H)

[0261]

[0262] (4) Preparation of ligand compound (3-(9H-carbazol-9-yl)-N,N-didodecyl-4-(methoxymethoxy)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline)

[0263] 4.81 g (7.34 mmol) of the product obtained above and 9.6 mL of THF were weighed into a 100 mL one-neck container, followed by the addition of 5.87 mL (14.67 mmol) of 2.5 M n-BuLi(in hexane) dropwise, and the mixture was reacted overnight at room temperature. 3.74 mL (18.35 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise, and the mixture was reacted overnight at room temperature. After workup with ethyl acetate and water, a yellow liquid product was obtained.

[0264] 1 H-NMR (500 MHz, CDCl3): 8.10(d, 2H), 7.39(t, 2H), 7.31(d, 2H), 7.23(t, 2H), 7.19(s, 1H), 6.73(d, 1H), 4.59(s, 2H), 3.23(t, 4H), 2.25(s, 3H), 1.56(s, 4H), 1.36(s, 12H), 1.25(m, 12H), 1.88(t, 6H)

[0265]

[0266] (5) Preparation of ligand compound (6',6'''-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5-(didodecylamino)-3'-fluoro-[1,1'-biphenyl]-2-ol)

[0267] In a 50 mL vial, 1.34 g (1.72 mmol) of the product obtained above, 299.2 mg (0.68 mmol) of 1,3-bis(2-bromo-4-fluorophenoxy)propane, 6.9 mL of diionic acid, and 11 mL of K3PO4758.5 ​​mg in H2O were weighed and heated to 100 °C. 40 mg of Tetrakis(triphenylphosphine)palladium was added and heated overnight. After working up with water and ethyl acetate, 20 mL of MeOH + 5 mL of concentrated HCl was added and heated to 70 °C for 4 hours to obtain a yellow liquid product.

[0268] 1 H-NMR (500 MHz, CDCl3): 8.17(d, 4H), 7.33(t, 4H), 7.26(t, 4H), 7.19(d, 4H), 7.04(d,2H), 6.70(s, 2H), 6.61(m, 2H), 6.57(s, 2H), 6.17-6.15(m, 2H), 5.19(s, 1H), 3.87(t, 4H), 3.18(t, 8H), 2.05-2.02(m, 2H), 1.55(m, 8H), 1.23(s, 80H), 0.89(t, 12H)

[0269]

[0270] (6) ((3-(9H-carbazol-9-yl)-5-(didodecylamino)-5'-fluoro-2'-hydroxy-[1,1'-biphenyl]-2-yl)oxy)((3-(9H -carbazol-9-yl)-5-(didodecylamino)-5'-fluoro-2'-propoxy-[1,1'-biphenyl]-2-yl)oxy)dimethylhafnium manufacturing

[0271] After quantifying HfCl4 in a 10 ml vial, toluene was added, and MMB (3-methoxy-3-methyl-1-butanol) was added dropwise. After reacting for 5 minutes, 204 mg (0.138 mmol) of the ligand obtained above was dissolved in toluene and added dropwise to the reaction mixture. After reacting overnight at room temperature, the toluene was completely evaporated, and the mixture was extracted with hexane to obtain 216 mg of a bright yellow solid product with a yield of 92.7%.

[0272] 1 H-NMR (500 MHz, CDCl3): 8.32(d, 2H), 8.11(d, 2H), 7.52(d, 2H), 7.40-7.32(m, 8H), 7.18(t, 2H), 6.97(d, 2H), 6.92(d, 2H), 6.56(s, 2H), 6.32(t, 2H), 4.40-4.37(m, 2H), 3.90-3.86(m, 2H), 3.46-3.43(m, 2H), 3.28(t, 8H), 1.59-1.54(m, 8H), 1.22(s, 80H), 0.88(t, 12H), -1.83(s, 6H)

[0273]

[0274] Comparative Manufacturing Example 1

[0275]

[0276] It was manufactured according to the method disclosed in KR 10-2021-0038235 A.

[0277]

[0278] Comparative Manufacturing Example 2

[0279]

[0280] It was manufactured according to the method disclosed in KR 10-2023-0078560 A.

[0281]

[0282] Comparative Manufacturing Example 3

[0283]

[0284] It was manufactured according to the method disclosed in KR 10-2021-0038235 A.

[0285]

[0286] Comparative Manufacturing Example 4

[0287]

[0288] It was manufactured according to the method disclosed in US 2017-0267796 A1 and KR 10-2100142 B1.

[0289]

[0290] Comparative Manufacturing Example 5

[0291]

[0292] 2 g of 9H-carbazol-4-ol, 1 eq of 1-iodohexane, and 2 eq of K2CO3 were added to 0.3 M acetone and refluxed at 80°C for 12 hours (overnight). Afterward, 0.5 eq of 1-iodohexane was added to terminate the reaction. After the reaction was terminated, all the acetone was vacuum-dried, and extraction with ethyl acetate was performed. The mixture was slurried with methanol to obtain 2 g of 4-(hexyloxy)-9H-carbazole with a yield of 68%.

[0293] 1 H NMR (500 MHz, DMSO): 11.23(1H,s), 8.13(1H,d), 7.45(1H, d), 7.32(1H, t), 7.28(1H, t), 7.13(1H, t), 7.06(1H, d), 6.67(1H, d), 4.19(2H, t), 3.33(12H, s), 1.9(2H, m), 1.57(2H, m), 1.37(2H, m), 0.9(3H, t)

[0294] Subsequently, regarding the 4-(hexyloxy)-9H-carbazole obtained by the above-described manufacturing method, a catalyst was synthesized and prepared by referring to the manufacturing method disclosed in US Patent 2004 / 0014950 A1.

[0295]

[0296] Comparative Manufacturing Example 6

[0297]

[0298] 2 g (2.0 eq) of 1,4-dibromobutane, 1.0 eq of 2-bromo-4-fluorophenol, and 2.0 eq of K2CO3 were added to 0.3 M acetone, and the reaction was terminated after refluxing at 80°C overnight. After the reaction was terminated, all the acetone was vacuum-dried, and then extraction with ethyl acetate was carried out. The mixture was slurried with hexane to obtain 1,4-bis(2-bromo-4-fluorophenoxy)butane with an 87% yield.

[0299] 1 H NMR (500 MHz, CDCl3): 7.29 (2H, d), 6.97 (2H, m), 4.09 (4H, s), 2.08 (4H, s)

[0300] Subsequently, regarding the 1,4-bis(2-bromo-4-fluorophenoxy)butane obtained by the above-described manufacturing method, a catalyst was synthesized and prepared by referring to the manufacturing method disclosed in US Patent 2004 / 0014950 A1.

[0301]

[0302] Example 1

[0303] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.68 kg / h), the reactor was preheated (temperature: 176.0°C). Triisobutylaluminum compound (200 mmol / min), the transition metal compound obtained in Preparation Example 1 (0.20 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (1.50 μmol / min) were simultaneously introduced into the reactor. Subsequently, hydrogen gas (49 cc / min) and ethylene (0.68 kg / h) were introduced into the reactor, and the copolymerization reaction was carried out in a continuous process at a pressure of 89 bar and maintained at 178.5°C for at least 30 minutes to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0304]

[0305] Example 2

[0306] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.60 kg / h), the reactor was preheated (temperature: 174.2°C). Triisobutylaluminum compound (60 mmol / min), the transition metal compound obtained in Preparation Example 2 (0.14 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (0.42 μmol / min) were simultaneously introduced into the reactor. Subsequently, hydrogen gas (57 cc / min) and ethylene (0.87 kg / h) were introduced into the reactor, and the copolymerization reaction was carried out in a continuous process at 174.2°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0307]

[0308] Example 3

[0309] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.82 kg / h), the reactor was preheated (temperature: 170.8°C). Triisobutylaluminum compound (60 mmol / min), the transition metal compound obtained in Preparation Example 3 (0.10 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (0.25 μmol / min) were simultaneously introduced into the reactor. Subsequently, hydrogen gas (100 cc / min) and ethylene (0.87 kg / h) were introduced into the reactor, and the copolymerization reaction was carried out in a continuous process at 170.8°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0310]

[0311] Example 4

[0312] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.82 kg / h), the reactor was preheated (temperature: 170.0°C). Triisobutylaluminum compound (60 mmol / min), the transition metal compound obtained in Preparation Example 3 (0.10 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (0.25 μmol / min) were simultaneously introduced into the reactor. Subsequently, hydrogen gas (100 cc / min) and ethylene (0.87 kg / h) were introduced into the reactor, and the copolymerization reaction was carried out in a continuous process at 170.0°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0313]

[0314] Comparative Example 1

[0315] After filling a 1.5 L continuous process reactor with hexane solvent (5.0 kg / h) and 1-butene (0.85 kg / h), the reactor was preheated (temperature: 170.0°C). Triisobutylaluminum compound (60 mmol / min), the transition metal compound obtained in Comparative Preparation Example 1 (0.60 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (1.80 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the continuous process at 170.0°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0316]

[0317] Comparative Example 2

[0318] After filling a 1.5 L continuous process reactor with hexane solvent (5.0 kg / h) and 1-butene (0.95 kg / h), the reactor was preheated (temperature: 169.5°C). Triisobutylaluminum compound (60 mmol / min), the transition metal compound obtained in Comparative Preparation Example 1 (0.40 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (1.20 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the temperature at 169.5°C for at least 30 minutes under a continuous process at a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0319]

[0320] Comparative Example 3

[0321] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.82 kg / h), the reactor was preheated (temperature: 177.1°C). Triisobutylaluminum compound (100 mmol / min), the transition metal compound obtained in Preparation Example 2 (0.10 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (1.38 μmol / min) were simultaneously introduced into the reactor. Subsequently, hydrogen gas (147 cc / min) and ethylene (0.87 kg / h) were introduced into the reactor, and the copolymerization reaction was carried out in a continuous process at 177.1°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0322]

[0323] Comparative Example 4

[0324] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (1.08 kg / h), the reactor was preheated (temperature: 160.5°C). Triisobutylaluminum compound (50 mmol / min), the transition metal compound obtained in Comparative Preparation Example 2 (0.45 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (1.60 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the temperature at 160.5°C for at least 30 minutes under a continuous process at a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0325]

[0326] Comparative Example 5

[0327] After filling a 1.5 L continuous process reactor with hexane solvent (5.0 kg / h) and 1-octene (1.92 kg / h), the reactor was preheated (temperature: 146.0°C). A triisobutylaluminum compound (50 mmol / min), a mixture of the transition metal compounds of Comparative Preparation Example 1 and Comparative Preparation Example 3 (molar ratio 1:2.5) (0.66 μmol / min), and a dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (1.98 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the continuous process at 146.0°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0328]

[0329] Comparative Example 6

[0330] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (1.00 kg / h), the reactor was preheated (temperature: 159.4°C). Triisobutylaluminum compound (50 mmol / min), the transition metal compound obtained in Comparative Preparation Example 4 (0.10 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl) borate co-catalyst (0.22 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the temperature at 159.4°C for at least 30 minutes under a continuous process at a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0331]

[0332] Comparative Example 7

[0333] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.80 kg / h), the reactor was preheated (temperature: 176.0°C). Triisobutylaluminum compound (70 mmol / min), the transition metal compound obtained in Comparative Preparation Example 5 (0.11 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (0.66 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the continuous process at 176°C for at least 30 minutes under a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0334]

[0335] Comparative Example 8

[0336] After filling a 1.5 L continuous process reactor with hexane solvent (7.0 kg / h) and 1-butene (0.75 kg / h), the reactor was preheated (temperature: 175.2°C). Triisobutylaluminum compound (70 mmol / min), the transition metal compound obtained in Comparative Preparation Example 6 (0.40 μmol / min), and dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst (2.40 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the reactor, and the copolymerization reaction was carried out by maintaining the temperature at 175.2°C for at least 30 minutes under a continuous process at a pressure of 89 bar to obtain a copolymer. Afterward, the physical properties were measured after drying in a vacuum oven for at least 12 hours.

[0337]

[0338] Experimental Example 1

[0339] The physical properties of the above copolymer were evaluated according to the following method.

[0340]

[0341] Polymer density

[0342] Measured using ASTM D-792.

[0343]

[0344] * Melt Index (MI) of a polymer 2.16 )

[0345] It was measured according to ASTM D-1238 (condition E, 190℃, 2.16 kg load).

[0346]

[0347] * Melt Flow Ratio (MFRR)

[0348] MI according to ASTM D-1238 2.16 (190℃, 2.16 kg load) and MI 10 After measuring (190℃, 10 kg load), MI 10 to MI 2.16 The melt flow index was calculated by dividing by .

[0349]

[0350] * Weight-average molecular weight (Mw, g / mol) and molecular weight distribution (MWD)

[0351] Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

[0352] - Column: PL Olexis

[0353] - Solvent: TCB (Trichlorobenzene)

[0354] - Flow rate: 1.0 ml / min

[0355] - Sample concentration: 1.0 mg / ml

[0356] - Injection volume: 200 µl

[0357] - Column temperature: 160℃

[0358] - Detector: Agilent High Temperature RI detector

[0359] - Standard: Polystyrene (corrected by a cubic function)

[0360]

[0361] * F(30), F(70)

[0362] It was obtained using the SSA (Successive self-nucleation / annealing) measurement method with a Differential Scanning Calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments.

[0363] Specifically, in the first cycle, the temperature was increased to 150°C, maintained at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120°C, maintained at that temperature for 30 minutes, and then cooled to -100°C. In the third cycle, the temperature was increased to 110°C, maintained at that temperature for 30 minutes, and then cooled to -100°C. This process of raising the temperature in 10°C increments and cooling to -100°C was repeated down to -60°C to allow crystallization to occur in each temperature range. During this process, the rate of temperature increase and decrease were each controlled to 10°C.

[0364] In the last cycle, the heat capacity was determined by increasing the temperature to 150°C. The temperature-heat capacity curve obtained in this way was integrated for each interval to fractionate the heat capacity of each interval relative to the total heat capacity.

[0365] In addition, when measuring SSA, the sum of the melting enthalpy (△H) at 30°C or higher is defined as F (30), and the sum of the melting enthalpy (△H) at 70°C or higher is defined as F (70).

[0366]

[0367] As shown in Table 1 above, in Examples 1 to 4, olefinic polymers were prepared that satisfy all of conditions (a) to (d) defined in the present invention. On the other hand, it was confirmed that the olefinic polymers of Comparative Examples 1 to 8 did not satisfy one or more of conditions (a) to (d).

[0368]

[0369] Experimental Example 2

[0370] Tensile strength, tear strength

[0371] Each olefin copolymer was extruded into pellet form, and then the tensile strength and tear strength at break were measured according to ASTM D638 (50 mm / min).

[0372]

[0373] When comparing Examples 1 to 4 with Comparative Examples 1, 3, and 7, it was confirmed that the Examples contain a large amount of highly crystalline regions, which increases mechanical strength and results in high tensile strength and tear strength.

[0374] In particular, when comparing Examples 1 to 3 and Comparative Example 7, which have similar levels of density and melt index, Examples 1 to 3 showed a significant improvement effect compared to Comparative Example 7, with tensile strengths 1.4 times, 2.9 times, and 2.7 times, respectively, and tear strengths 1.2 times, 1.6 times, and 1.6 times.

[0375] In addition, when comparing Example 4 and Comparative Example 1, which have similar levels of density and melt index, Example 4 showed a significant improvement effect with tensile strength 2.3 times and tear strength 1.3 times compared to Comparative Example 1.

[0376] Meanwhile, FIG. 1 is a graph showing the results of differential scanning calorimetry (SSA) measurements for the polymers of Example 3 and Comparative Example 1. As shown in FIG. 1, in the case of Example 3, which is an olefin-based polymer according to the present invention, it can be seen that F (30) (peak area in the region of temperature above 30°C) is larger than that of Comparative Example 1, but F (70) is smaller. This is because Example 3 has more highly crystalline regions and a relatively uniform crystallinity distribution than Comparative Example 1.

[0377] In addition, looking at FIG. 2, it can be seen that for the olefin-based polymers of Examples 1 to 4, F(30)-F(70) increases with increasing density. Also, as shown in FIG. 3 and FIG. 4, tensile strength and tear strength also increased with increasing density, showing a linear relationship. That is, it can be seen that the mechanical strength of the olefin-based polymer of the present invention improves as the density increases.

Claims

1. An olefinic polymer satisfying the following conditions (a) to (d): (a) Density: 0.855 to 0.880 g / cc (b) Melt Index (190℃, 2.16 kg load condition; MI) 2.16 ): 0.1 to 35 dg / min (c) Melt flow rate ratio (MFRR, MI) 10 / MI 2.16 ): 6.0 to 8.5 (d) When measured by differential scanning calorimetry (SSA), F(30)-F(70) > [1599.2 × density - 1354], where F(30) is the total enthalpy of melting at 30°C or higher, and F(70) is the total enthalpy of melting at 70°C or higher.

2. In Claim 1, The above condition (a) olefinic polymer having a density of 0.865 to 0.880 g / cc.

3. In Claim 1, The above F (30) is an olefinic polymer with a value of 10.0 to 80.

0.

4. In Claim 1, The above F (70) is an olefinic polymer with a value of 0.1 to 12.

0.

5. In Claim 1, The above olefinic polymer has a melt index of 0.5 to 30 dg / min.

6. In Claim 1, The above olefinic polymer has a melt flow index of 6.2 to 8.

3.

7. In Claim 1, The above olefinic polymer is an olefinic polymer having a weight-average molecular weight of 10,000 to 150,000 g / mol.

8. In Claim 1, The above olefinic polymer is an olefinic polymer having a molecular weight distribution of 1.5 to 3.

0.

9. In Claim 1, The above olefinic polymer is an olefinic polymer that is a copolymer of ethylene and an alpha-olefinic monomer having 3 to 12 carbon atoms.

10. In Claim 9, The above alpha-olefin monomer is an olefin polymer that is one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, and 1-dodecene.

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