Organocobalt compound, catalyst composition comprising same, and olefin-based polymer prepared using same

Abstract

The present invention relates to an organocobalt compound, a catalyst composition comprising same, and an olefin-based polymer prepared using same.

Description

Organic cobalt compound, catalyst composition containing the same, and olefinic polymer prepared using the same

[0001] Cross-citation with related applications

[0002] The present application claims the benefit of priority based on Korean patent application 2024-0183885 dated December 11, 2024, Korean patent application 2024-0183886 dated December 11, 2024, and Korean patent application 2025-0195512 dated December 10, 2025, and all contents disclosed in the documents of said Korean patent applications are incorporated herein as part of the specification.

[0003]

[0004] Technology field

[0005] The present invention relates to an organic cobalt compound, a catalyst composition containing the same, and an olefin-based polymer prepared using the same.

[0006]

[0007] As global environmental and energy issues become increasingly serious, solar cells are attracting attention as a means of energy generation free from concerns regarding environmental pollution and depletion. When solar cells are used outdoors, such as on building roofs, they are generally utilized in the form of modules. To obtain a crystalline solar cell module during the manufacturing process, the layers are laminated in the following order: front glass, solar cell encapsulant, crystalline solar cell element, solar cell encapsulant, and back glass (or back protective sheet). As the solar cell encapsulant, materials such as ethylene / vinyl acetate copolymer or ethylene / alpha-olefin copolymer, which possess excellent transparency, flexibility, and adhesion, are generally used.

[0008] A solar cell module is a package in which solar cell elements such as silicon, gallium-arsenide, and copper-indium-selenium are protected by an upper transparent protective material and a lower substrate protective material, and the solar cell elements and protective materials are fixed with a sealant. Generally, the sealant for the solar cell elements in a solar cell module is produced by extruding an ethylene / alpha-olefin copolymer mixed with an organic peroxide or a silane coupling agent into a sheet, and a solar cell module is manufactured by sealing the solar cell elements using the obtained sheet-shaped sealant.

[0009] When manufacturing solar cell modules as described above, one way to improve productivity is to increase the affinity between the various raw materials included in the composition for the encapsulation film and the ethylene / alpha-olefin copolymer to increase absorption. In particular, crosslinking agents and crosslinking aids, which are essential for manufacturing encapsulation films, are polar substances and inevitably have low absorption for the non-polar ethylene / alpha-olefin copolymer, which is identified as one of the factors causing a decrease in productivity.

[0010]

[0011] [Prior Art Literature]

[0012] [Patent Literature]

[0013] (Patent Document 1) U.S. Registered Patent No. 5,064,802

[0014]

[0015] The present invention aims to provide a novel organic cobalt compound, a catalyst composition containing the same, and an olefin-based polymer prepared using the same.

[0016]

[0017] (1) The present invention provides an organic cobalt compound represented by the following chemical formula 1.

[0018] [Chemical Formula 1]

[0019]

[0020] In the above chemical formula 1,

[0021] R1 is hydrogen or an alkyl group having 1 to 20 carbon atoms, wherein two R1s bonded to one 2,2'-bipyridine can be connected to each other to form an aromatic ring together with the 2,2'-bipyridine, and

[0022] R2 and R3 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and

[0023] X - is PY6 - , Y - , BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I.

[0024] (2) The present invention provides an organic cobalt compound according to (1), wherein R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R2 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an ester group having 1 to 10 carbon atoms, and R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0025] (3) The present invention, in the above (1) or (2), wherein X - is PY6 - And, where, Y provides an organic cobalt compound selected from the group consisting of F, Cl, Br and I.

[0026] (4) The present invention provides an organic cobalt compound in any one of (1) to (3), wherein the compound represented by Formula 1 is a compound represented by Formula 1A or Formula 1B.

[0027] [Chemical Formula 1A]

[0028]

[0029] [Chemical Formula 1B]

[0030]

[0031] In the above chemical formulas 1A and 1B,

[0032] R2 is each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and X - is PY6 - , Y - , BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I.

[0033] (5) The present invention provides an organic cobalt compound in any one of (1) to (4), wherein the compound represented by Chemical Formula 1 is selected from the group consisting of Chemical Formulas 1-1 to 1-3 below.

[0034] [Chemical Formula 1-1]

[0035]

[0036] [Chemical Formula 1-2]

[0037]

[0038] [Chemical Formula 1-3]

[0039]

[0040] (6) The present invention provides a catalyst composition comprising an organic cobalt compound according to any one of (1) to (5); and a peroxide.

[0041] (7) The present invention provides a catalyst composition in which, in (6) above, the peroxide is one or more selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, propionyl peroxide, lauryl peroxide and acetyl peroxide.

[0042] (8) The present invention provides a method for oxidizing an olefin polymer, comprising the step of oxidizing the olefin polymer in the presence of the catalyst composition of (6) or (7).

[0043] (9) The present invention provides an olefinic polymer that satisfies the following conditions (a) to (d) and includes a polar functional group.

[0044] (a) Density: 0.855 g / cc to 0.915 g / cc;

[0045] (b) Melt index (MI, 190℃, 2.16 kg load condition): 0.1 g / 10 min to 100.0 g / 10 min;

[0046] (c) Molecular weight distribution: 1.5 to 3.0; and

[0047] (d) Oxidation degree: 1.2 or higher.

[0048] (10) The present invention provides an olefinic polymer in which the polar functional group in (9) is one or more selected from the group consisting of -OH, -CO- and -COO-.

[0049] (11) The present invention provides an olefinic polymer having a water contact angle of 65 to 85 degrees in (9) or (10).

[0050] (12) The present invention provides an olefin polymer in any one of (9) to (11), wherein the olefin polymer is an ethylene / alpha-olefin copolymer, and the alpha-olefin comprises 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, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicocene.

[0051]

[0052] By promoting the oxidation reaction of an olefin-based polymer using the organic cobalt compound of the present invention, it is possible to introduce polar groups with high efficiency. In addition, the olefin-based polymer prepared using the organic cobalt compound can exhibit improved adhesion properties by introducing polar functional groups and having excellent affinity with polar molecules and interfaces.

[0053]

[0054] Figure 1 is of Example 7. 1 This shows the H NMR graph.

[0055] Figure 2 is of Example 8 1 This shows the H NMR graph.

[0056] Figure 3 is of Example 9. 1 This shows the H NMR graph.

[0057] Figure 4 is of Example 10 1 This shows the H NMR graph.

[0058] Figure 5 is of Example 11 1 This shows the H NMR graph.

[0059]

[0060] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0061]

[0062] 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.

[0063]

[0064] In the present invention, "alkyl group" may refer to a straight-chain or branched hydrocarbon residue, and specific examples may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a hexyl group, depending on the number of carbon atoms defined.

[0065] In the present invention, "aryl group" refers to an optionally substituted benzene ring or a ring system that can be formed by fusing one or more optional substituents. Exemplary optional substituents include a substituted alkyl group having 1 to 2 carbon atoms, a substituted alkenyl group having 2 to 3 carbon atoms, a substituted alkynyl group having 2 to 3 carbon atoms, a heteroaryl group, a heterocyclic group, an aryl group, an alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxyamide, aminocarbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen, or ureido. These rings or ring systems may optionally be fused to an aryl ring (e.g., a benzene ring), a carbon ring, or a heterocyclic ring having one or more optional substituents. They may include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthryl and their substituted derivatives.

[0066] In the present invention, the "alkoxy group" is a group having the structure -OA (wherein A is an alkyl group as described above), and non-limiting examples thereof include methoxy, ethoxy, propoxy, isopropyloxy, butoxy, pentoxy, etc. At least one hydrogen atom among these alkoxy groups can be substituted with a substituent similar to that of the alkyl group described above.

[0067] In the present invention, "ester group" refers to a functional group formed by bonding, for example, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, etc., through an ester bond.

[0068] In the present invention, the term "polymer" refers to a polymer compound produced by polymerizing monomers of the same or different types. Thus, the general term "polymer" encompasses "homopolymer," a term commonly used to refer to a polymer produced from only one type of monomer, and "interpolymer," a term defined below.

[0069] In the present invention, the term "copolymer" refers to a polymer produced by the polymerization of at least two different monomers. Thus, the general term "copolymer" includes "copolymer," a term commonly used to refer to a polymer produced from two different monomers, and a polymer produced from two or more different monomers.

[0070]

[0071] organic cobalt compounds

[0072] The organic cobalt compound of the present invention is characterized by being represented by the following chemical formula 1.

[0073] [Chemical Formula 1]

[0074]

[0075] In the above chemical formula 1,

[0076] R1 is hydrogen or an alkyl group having 1 to 20 carbon atoms, wherein two R1s bonded to one 2,2'-bipyridine can be connected to each other to form an aromatic ring together with the 2,2'-bipyridine, and

[0077] R2 and R3 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and

[0078] X - is PY6 - , Y - , BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I.

[0079]

[0080] The organic cobalt compound of the present invention has a hexacoordinate structure in which all three chelating ligands are coordinated to cobalt metal, and since cobalt is a low-toxicity metal compared to conventional transition metals, it can suppress negative environmental effects. Accordingly, when the organic cobalt compound of the present invention is used in an oxidation reaction, metal contamination in the finally produced oxide can be minimized.

[0081]

[0082] In the above chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 20 carbon atoms, specifically, it may be hydrogen or an alkyl group having 1 to 10 carbon atoms. Here, two R1s bonded to one 2,2'-bipyridine may be connected to each other to form an aromatic ring together with the 2,2'-bipyridine.

[0083] Specifically, the R1 may be hydrogen or an alkyl group having 1 to 6 carbon atoms, and more specifically, may be hydrogen. In addition, for example, when two R1s bonded to one 2,2'-bipyridine are alkyl groups having 1 carbon atom, such as methyl groups, they can form an aromatic ring, namely phenanthrene, together with the biphenyl bonded to the two R1s.

[0084] In the above chemical formula 1, R2 may be hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an ester group having 1 to 10 carbon atoms. Specifically, R2 may be hydrogen. Additionally, R2 may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 4 carbon atoms, such as a tert-butyl group. Additionally, R2 may be an aryl group having 6 to 10 carbon atoms, such as a phenyl group. Additionally, R2 may be an ester group having 1 to 6 carbon atoms, an ester group having 1 to 4 carbon atoms, such as a methyl ester group.

[0085] In the above chemical formula 1, R3 may be hydrogen or an alkyl group having 1 to 10 carbon atoms. Specifically, R3 may be hydrogen or an alkyl group having 1 to 6 carbon atoms, may be hydrogen or an alkyl group having 1 to 3 carbon atoms, and more specifically, may be hydrogen.

[0086] In the above chemical formula 1, X - Specifically, PY6 - It could be.

[0087]

[0088] Specifically, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 1A or chemical formula 1B.

[0089] [Chemical Formula 1A]

[0090]

[0091] [Chemical Formula 1B]

[0092]

[0093] In the above chemical formulas 1A and 1B,

[0094] R2 is each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and

[0095] X - is PY6 - , Y - , BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I.

[0096]

[0097] In the present invention, the compound represented by the above chemical formula 1 may be one selected from the group consisting of the following chemical formulas 1-1 to 1-3.

[0098] [Chemical Formula 1-1]

[0099]

[0100] [Chemical Formula 1-2]

[0101]

[0102] [Chemical Formula 1-3]

[0103]

[0104]

[0105] According to one embodiment of the present invention, the organic cobalt compound can be implemented in various combinations within the range satisfying the conditions described above, in addition to the specific example, and any compound represented by Chemical Formula 1 can be applied as the organic cobalt compound of the present invention.

[0106]

[0107] In the present invention, the organic cobalt compound can be prepared by a plurality of methods. Specifically, it can be prepared by a method comprising: (S1) a step of reacting a compound represented by the following chemical formula 2 and a compound represented by the following chemical formula 3; and (S2) a step of reacting the reaction product of the step (S1) with a compound represented by the following chemical formula 4.

[0108] [Chemical Formula 2]

[0109]

[0110] [Chemical Formula 3]

[0111]

[0112] [Chemical Formula 4]

[0113]

[0114] In the above chemical formula 2,

[0115] R1 is hydrogen or an alkyl group having 1 to 20 carbon atoms, wherein two R1s bonded to one 2,2'-bipyridine can be connected to each other to form an aromatic ring together with the 2,2'-bipyridine, and

[0116] R2 and R3 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and

[0117] In the above chemical formula 3,

[0118] A is a halogen group, and

[0119] In the above chemical formula 4,

[0120] B + is NH4 + , Ag + or Na + And,

[0121] X - is PY6 - , Y -, BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I.

[0122]

[0123] In the present invention, the compound represented by the chemical formula 3 may specifically be Br-Co-Br(CoBr2), and the compound represented by the chemical formula 4 may specifically be NH4PF6.

[0124]

[0125] In the present invention, the step (S1) may be performed in a reaction solvent at a temperature of 40°C or higher and 120°C or lower. Specifically, it may be performed at 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 110°C or lower, 100°C or lower, 90°C or lower, or 80°C or lower.

[0126] Additionally, the above step (S1) may be performed for 0.5 hours or more and 4 hours or less. Specifically, it may be performed for 1 hour or more, 1.5 hours or more, 2 hours or more, 3.5 hours or less, 3 hours or less, 2.5 hours or less, or 2 hours or less.

[0127] In the present invention, the molar ratio of the compound represented by Formula 2 and the compound represented by Formula 3 may be 1:1 to 5:1, and specifically, 1.5:1 to 4.5:1, 2.0:1 to 4.0:1, or 2.5:1 to 3.5:1.

[0128]

[0129] In the present invention, the step (S2) may be performed in a reaction solvent at a temperature of 10°C or higher and 40°C or lower. Specifically, it may be performed at 15°C or higher, 20°C or higher, 25°C or higher, 35°C or lower, 30°C or lower, or 25°C or lower.

[0130] Additionally, the above step (S2) may be performed for 0.5 hours or more and 4 hours or less. Specifically, it may be performed for 1 hour or more, 1.5 hours or more, 2 hours or more, 3.5 hours or less, 3 hours or less, 2.5 hours or less, or 2 hours or less.

[0131] In the present invention, the molar ratio of the compound represented by Formula 2 and the compound represented by Formula 4 may be 0.1:1 to 1:1, and specifically, 0.2:1 to 0.9:1, 0.3:1 to 0.8:1, 0.4:1 to 0.7:1, or 0.5:1 to 0.6:1.

[0132]

[0133] The molar ratio of the compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 4 (compound represented by Chemical Formula 2 / compound represented by Chemical Formula 4) may be 0.1 or more and 1 or less. Specifically, it may be 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, or 0.6 or more, 1.0 or less, 0.9 or less, 0.8 or less, 0.7 or less, or 0.6 or less.

[0134] The above reaction solvent may use organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate, and isopropyl ether, and purified water, but is not limited thereto.

[0135]

[0136] Catalyst composition

[0137] In addition, the present invention relates to a catalyst composition comprising the aforementioned organic cobalt compound and a peroxide.

[0138] In the present invention, the "composition" includes reaction products and decomposition products formed from the materials of the composition, as well as a mixture of materials comprising the composition.

[0139]

[0140] In the present invention, the organic cobalt compound may exhibit peroxidase-like activity. For example, the catalyst composition may catalyze any one reaction selected from the group consisting of oxidative dehydrogenation, oxidative halogenation, H2O2 dismutation, and oxygen-transfer reaction.

[0141]

[0142] In the present invention, the peroxide may be one or more selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, propionyl peroxide, lauryl peroxide, and acetyl peroxide, and more specifically, may be cumene hydroperoxide.

[0143]

[0144] In the present invention, the molar ratio of the organic cobalt compound and the peroxide may be 1:20 to 1:20,000, and specifically, 1:25 to 1:18,000, 1:30 to 1:15,000, 1:35 to 1:13,000, 1:45 to 1:11,000, or 1:50 to 1:10,000.

[0145]

[0146] Oxidation method of olefinic polymers

[0147] In addition, the present invention provides a method for oxidizing an olefin polymer, comprising the step of oxidizing the olefin polymer in the presence of the aforementioned catalyst composition.

[0148] The step of oxidizing the above olefin-based polymer can be performed at a temperature of 50°C or higher and 200°C or lower, and specifically, at a temperature of 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher, 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, 150°C or lower, 140°C or lower, 130°C or lower, or 120°C or lower.

[0149] In addition, it can be performed for 1 to 10 hours within the above temperature range, and specifically, for 2 hours or more, 3 hours or more, 4 hours or more, 5 hours or more, or 6 hours or more, 9 hours or less, 8 hours or less, 7 hours or less, or 6 hours or less.

[0150] In the present invention, when an olefin-based polymer is oxidized in the presence of a catalyst composition, the molar ratio of the olefin-based polymer to the organic cobalt compound in the catalyst composition may be 100:1 to 10,000:1. Specifically, it may be 150:1 to 7,000:1, 170:1 to 6,000:1, 200:1 to 5,000:1, and more specifically 220:1 to 4,500:1.

[0151]

[0152] According to the above oxidation method, an oxidized olefin-based polymer containing a large amount of polar functional groups can be produced as described below.

[0153] In the present invention, the oxidation reaction for the preparation of an oxidized olefin-based polymer can be carried out in the presence of a reaction solvent.

[0154] Specifically, the reaction solvent may be a substituted or unsubstituted aliphatic hydrocarbon solvent, a substituted or unsubstituted aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, or a mixture thereof; more specifically, it may be a mixture of a substituted or unsubstituted aromatic hydrocarbon solvent and a halogenated aromatic hydrocarbon solvent; and more specifically, it may be a mixture of a substituted aromatic hydrocarbon solvent and an aromatic hydrocarbon solvent substituted with three halogen elements.

[0155] The above-mentioned substituted or unsubstituted aromatic hydrocarbon solvent may be benzene, toluene, xylene, styrene, naphthalene, phenol, cresol, nitrobenzene, etc., and specifically, may be xylene. The above-mentioned xylene may be ortho-xylene, meta-xylene, or para-xylene, but more specifically, may be ortho-xylene.

[0156] The halogenated aromatic hydrocarbon solvent may be one in which three or more halogen elements are substituted into the aforementioned aromatic hydrocarbon solvent, and more specifically, may be trichlorobenzene.

[0157]

[0158] Oxidized olefin polymer

[0159] In addition, the present invention relates to an oxidized olefin-based polymer comprising a polar functional group and satisfying the following conditions (a) to (d).

[0160] (a) Density: 0.855 g / cc to 0.915 g / cc;

[0161] (b) Melt index (MI, 190℃, 2.16 kg load condition): 0.1 g / 10 min to 100.0 g / 10 min;

[0162] (c) Molecular weight distribution: 1.5 to 3.0; and

[0163] (d) Oxidation degree: 1.2 or higher.

[0164]

[0165] In the present invention, the oxidized olefin-based polymer includes a polar functional group. At this time, the polar functional group may be one or more selected from the group consisting of -OH, -CO- and -COO-.

[0166] When the above-mentioned polar functional group is included in an oxidized olefin-based polymer, the polar functional group can form hydrogen bonds with other functional groups, such as -OH, -NH2, -NH, -F, etc., thereby enhancing physical bonding with other polymers having such functional groups.

[0167] The oxidized olefin-based polymer of the present invention may be prepared according to the oxidation method of an olefin-based polymer using the catalyst composition of the present invention described above, and thereby may include a high content of polar functional groups as described above.

[0168]

[0169] The oxidized olefin-based polymer of the present invention has an oxidation degree of 1.2 or higher. The oxidation degree is 1 This indicates the content of the polar functional group contained in the oxidized olefin-based polymer, as measured by H-NMR.

[0170] Specifically, the degree of oxidation can be derived by the following method.

[0171] Oxidized olefin polymers are derived from alpha-olefin monomers and possess terminal CH3 functional groups linked to branched chains branched from the main chain.

[0172]

[0173] Since the above terminal CH3 exhibits a specific chemical shift distinct from carbons at other positions, 1 The integral value of the peak exhibited by the terminal CH3 is converted to 10 and calculated through H NMR measurement, and the integral value of the peak exhibited by the hydrogen located adjacent to the polar functional group is calculated based on this to determine the oxidation degree.

[0174] In the case of -OH, since alpha hydrogen peaks appear at around 3.43 ppm and 3.32 ppm, the sum of the integral values ​​of the peaks at around 3.43 ppm and 3.32 ppm is calculated as the oxidation degree of -OH.

[0175]

[0176] In the case of -CO-, the alpha hydrogen peak appears around 2.63 ppm, and since four alpha hydrogens are in the same position, the oxidation degree of -CO- is calculated by dividing the integral of the peak around 2.63 ppm by 4.

[0177]

[0178] In the case of -COO-, hydrogen peaks appear at around 2.53 ppm and 4.15 ppm, respectively. Therefore, the average of the integral values ​​of the peaks at around 2.53 ppm and 4.15 ppm is calculated and divided by 2. That is, the integral value of the peaks at around 2.53 ppm and 4.15 ppm is added and divided by 4 to calculate the oxidation degree of -COO-.

[0179]

[0180] In the present invention, the degree of oxidation is the sum of the respective degrees of oxidation of -OH, -CO-, and -COO- calculated as above.

[0181]

[0182] Specifically, the degree of oxidation may be 1.22 or higher, 1.25 or higher, 1.27 or higher, or 1.29 or higher, and may be 3.00 or lower, 2.90 or lower, 2.80 or lower, or 2.70 or lower.

[0183] The oxidized olefin-based polymer of the present invention has a high content of polar functional groups and exhibits an oxidation degree of at least 1.2 or higher. Within this range, the affinity of the oxidized olefin-based polymer with polar molecules and interfaces can be increased, and it is easy to introduce other functional groups within the polymer, and adhesive properties are improved.

[0184]

[0185] In addition, the oxidized olefin-based polymer of the present invention may have a water contact angle of 65 to 85 degrees. Specifically, it may be 66.0 degrees or more, 66.5 degrees or more, 67.0 degrees or more, or 67.5 degrees or more, and 84.0 degrees or less, 83.5 degrees or less, 83.0 degrees or less, 82.5 degrees or less, or 82.0 degrees or less.

[0186] The above water contact angle can be measured by mounting a glass substrate coated with an olefin-based polymer on a measuring device, dropping distilled water from a height (about 3 to 4 cm) where the shape is not damaged when liquid is dropped from a syringe, and taking a picture within 2 minutes.

[0187] The fact that the water contact angle appears within the above range means that the oxidized olefin-based polymer contains a large amount of polar functional groups, and the high affinity between the polar molecules of the oxidized olefin-based polymer and the interface results in excellent adhesion properties.

[0188]

[0189] The oxidized olefin-based polymer of the present invention has a density of 0.855 g / cc to 0.915 g / cc, wherein the density may refer to the density measured according to ASTM D-792. Specifically, the density may be 0.860 g / cc or higher or 0.865 g / cc or higher, and may be 0.910 g / cc or lower, 0.900 g / cc or lower, 0.890 g / cc or lower, or 0.880 g / cc or lower.

[0190] When the oxidized olefin-based polymer of the present invention has a density within the above range, articles such as adhesive films with excellent optical properties and mechanical properties can be manufactured using the oxidized olefin-based polymer.

[0191]

[0192] The oxidized olefin-based polymer of the present invention has a melt index (MI, under conditions of 190°C and a 2.16 kg load) of 0.1 g / 10 min to 100.0 g / 10 min. Specifically, the melt index may be 1.0 g / 10 min or more, 5.0 g / 10 min or more, 6.0 g / 10 min or more, 7.0 g / 10 min or more, or 8.0 g / 10 min or more, and may be 70.0 g / 10 min or less, 60.0 g / 10 min or less, 50.0 g / 10 min or less, or 40.0 g / 10 min or less, for example, 1.0 g / 10 min to 70.0 g / 10 min.

[0193] When the oxidized olefin-based polymer of the present invention has a melt index within the above range, it exhibits appropriate processability and can be usefully utilized in the manufacture of articles such as adhesive films.

[0194]

[0195] The oxidized olefin-based polymer of the present invention has a molecular weight distribution (MWD) of 1.5 to 3.0. Specifically, the molecular weight distribution may be 1.7 or more, 1.8 or more, 2.0 or more, 2.7 or less, 2.5 or less, or 2.3 or less.

[0196] In addition, the oxidized olefin-based polymer of the present invention may have a weight-average molecular weight (Mw) of 30,000 to 150,000 g / mol. Specifically, the weight-average molecular weight may be 32,000 g / mol or more, 35,000 g / mol or more, 40,000 g / mol or more, 130,000 g / mol or less, 100,000 g / mol or less, 80,000 g / mol or less, or 75,000 g / mol or less.

[0197] The above weight-average molecular weight (Mw) and 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.

[0198] As described above, the oxidized olefin-based polymer of the present invention contains polar functional groups and exhibits a high degree of oxidation while having a narrow molecular weight distribution. This effect is achieved by using a novel catalyst in the present invention to efficiently carry out the oxidation reaction while suppressing the dissociation of the polymer chains, and when the above molecular weight distribution is satisfied while exhibiting the degree of oxidation within the aforementioned range, it has the effect of excellent adhesive properties.

[0199]

[0200] The oxidized olefin-based polymer of the present invention may have a melting temperature (Tm) of 30°C to 65°C. Specifically, the melting temperature may be 35°C or higher, 40°C or higher, 45°C or higher, 60°C or lower, 58°C or lower, or 56°C or lower.

[0201] The melting temperature is measured using a differential scanning calorimeter (DSC). Specifically, the copolymer is heated to 150°C and maintained for 5 minutes, then lowered to 20°C and then increased again. At this time, the rate of increase and decrease in temperature are each controlled to 10°C / min, and the result measured during the second temperature increase can be determined as the melting temperature.

[0202]

[0203] The olefin-based polymer of the oxidized olefin-based polymer of the present invention may be an olefin homopolymer or an olefin / alpha-olefin copolymer depending on the type of olefin monomer, and preferably an ethylene / alpha-olefin copolymer. In this case, the content of the alpha-olefin monomer, which is the comonomer, can be appropriately selected by a person skilled in the art according to the use, purpose, etc. of the olefin-based polymer.

[0204] The above alpha-olefins may include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-eicocene, and may be one of these alone or a mixture of two or more.

[0205] Among these, the alpha-olefin may be 1-butene, 1-hexene, or 1-octene, and preferably may be 1-butene, 1-hexene, or a combination thereof.

[0206] In addition, the content of alpha-olefin in the oxidized olefin-based polymer can be appropriately selected within a range that satisfies the physical property requirements described above, specifically greater than 0 and less than or equal to 99 mol%, or 10 to 50 mol%, but is not limited thereto.

[0207]

[0208] Examples

[0209] 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.

[0210] Preparation of catalysts

[0211] Preparation Example 1

[0212] [Chemical Formula 1-1]

[0213]

[0214] (1) Preparation of ligand compounds

[0215] Dimethyl[2,2'-bipyridine]-4,4'-dicarboxylate (purchased from TCI, B1876) was purchased and used without purification or pretreatment.

[0216]

[0217] (2) Preparation of organic cobalt compounds

[0218] A 20 mL vial was used as the reaction vessel, and CoBr2 (0.5 mmol, 109 mg) and the dimethyl[2,2'-bipyridine]-4,4'-dicarboxylate prepared above (1.5 mmol, 409 mg) were added to 10 mL of MeOH. The reaction mixture was stirred at 80°C for 2 hours and cooled to 25°C. NH4PF6 (2.5 mmol, 407 mg) was added to the reaction mixture and stirred at 25°C for 2 hours. The precipitated complex was washed three times with MeOH and collected in a vial (4 mL). The collected complex was further dried under vacuum conditions.

[0219] According to the above procedure, an organic cobalt compound (462 mg, 0.40 mmol) was obtained as a yellow solid using dimethyl [2,2'-bipyridine]-4,4'-dicarboxylate (1.5 mmol, 409 mg) (yield 80%).

[0220] - HRMS m / z (FAB+) calcd. for [C 42 H 36 CoF 12 N6O 12 P2] 1165.1007, found 1165.1001; elemental analysis (%) calcd. for C 42 H 36 CoF 12 N6O 12 P2: C 43.28, H 3.11, N 7.21, found C 43.38, H 3.22, N 7.49.

[0221]

[0222] Preparation Example 2

[0223] [Chemical Formula 1-2]

[0224]

[0225] (1) Preparation of ligand compounds

[0226] 4,4-di-tert-butyl-2,2-bipyridine (purchased from TCI, D3134) was purchased and used without purification or pretreatment.

[0227]

[0228] (2) Preparation of organic cobalt compounds

[0229] A 20 mL vial was used as the reaction vessel, and CoBr2 (0.5 mmol, 109 mg) and the 4,4-di-tert-butyl-2,2-bipyridine prepared above (1.5 mmol, 403 mg) were added to 10 mL of MeOH. The reaction mixture was stirred at 80°C for 2 hours and cooled to 25°C. NH4PF6 (2.5 mmol, 407 mg) was added to the reaction mixture and stirred at 25°C for 2 hours. The precipitated complex was washed three times with MeOH and collected in a vial (4 mL). The collected complex was further dried under vacuum conditions.

[0230] According to the above procedure, an organic cobalt compound (472 mg, 0.41 mmol) was obtained as a yellow solid using 4,4-di-tert-butyl-2,2-bipyridine (1.5 mmol, 403 mg) (yield 82%).

[0231] - HRMS m / z (FAB+) calcd. for [C 54 H 72 CoF 12 N6P2] 1153.4434, found 1153.4430; elemental analysis (%) calcd. for C 54 H 72 CoF 12N6P2: C 56.20, H 6.29, N 7.28, found C 56.31, H 6.01, N 7.30.

[0232]

[0233] Preparation Example 3

[0234] [Chemical Formula 1-3]

[0235]

[0236] (1) Preparation of ligand compounds

[0237] 4,7-diphenyl-1,10-phenanthroline (purchased from TCI, B2695) was purchased and used without purification or pretreatment.

[0238]

[0239] (2) Preparation of organic cobalt compounds

[0240] A 20 mL vial was used as a reaction vessel, and CoBr2 (0.5 mmol, 109 mg) and the 4,7-diphenyl-1,10-phenanthroine prepared above (1.5 mmol, 498 mg) were added to 10 mL of MeOH. The reaction mixture was stirred at 80°C for 2 hours and cooled to 25°C. NH4PF6 (2.5 mmol, 407 mg) was added to the reaction mixture and stirred at 25°C for 2 hours. The precipitated complex was washed three times with MeOH and collected in a vial (4 mL). The collected complex was further dried under vacuum conditions.

[0241] According to the above procedure, an organic cobalt compound (484 mg, 0.36 mmol) was obtained as a yellow solid using 4,7-diphenyl-1,10-phenanthroine (1.5 mmol, 498 mg) (yield 72%).

[0242] - HRMS m / z (FAB+) calcd. for [C 72 H48 CoF 12 N6P2] 1345.2556, found 1345.2549; elemental analysis (%) calcd. for C 72 H 48 CoF 12 N6P2: C 64.25, H 3.59, N 6.24, found C 64.00, H 3.71, N 6.33.

[0243]

[0244] <Oxidation reaction using catalyst composition>

[0245] Example 1

[0246] Octadecane (1143 mg, 4.5 mmol) and 1,2-chlorobenzene (6 mL) were added to a 20 mL vial and the mixture was dissolved for 0.5 hours. Subsequently, the compound of Preparation Example 1 (0.02 mmol) and cumene hydroperoxide (152 mg, 1.0 mmol) were added to the mixture. The reaction was carried out at 120°C for 6 hours while stirring, and then cooled to room temperature. Afterward, all reaction solvent was removed, and the mixture of octadecanol and octadecanone was separated using silica gel-filled column chromatography. The solvent was dried under vacuum conditions to obtain a liquid mixture of octadecanol and octadecanone. An olefinic polymer containing polar functional groups was obtained as a solid product.

[0247]

[0248] Example 2

[0249] The procedure was performed in the same manner as Example 1, except that 0.01 mmol of the compound from Preparation Example 1 was used.

[0250]

[0251] Example 3

[0252] The procedure was performed in the same manner as Example 1, except that 0.005 mmol of the compound from Preparation Example 1 was used.

[0253]

[0254] Example 4

[0255] The procedure was performed in the same manner as Example 1, except that 0.001 mmol of the compound from Preparation Example 1 was used.

[0256]

[0257] Example 5

[0258] The procedure was performed in the same manner as Example 1, except that 0.001 mmol of the compound of Preparation Example 2 was used instead of the compound of Preparation Example 1.

[0259]

[0260] Example 6

[0261] The procedure was performed in the same manner as Example 1, except that 0.001 mmol of the compound of Preparation Example 3 was used instead of the compound of Preparation Example 1.

[0262]

[0263] Comparative Example 1

[0264] Octadecane (1143 mg, 4.5 mmol) and 1,2-chlorobenzene (6 mL) were added to a 20 mL vial, and the mixture was dissolved for 0.5 hours. Subsequently, CoBr2 (0.02 mmol, 4.2 mg), dimethyl[2,2'-bipyridine]-4,4'-dicarboxylate (0.06 mmol, 16.3 mg), NH4PF6 (0.04 mmol, 6.5 mg), and cumene hydroperoxide (152 mg, 1.0 mmol) were added to the mixture. The reaction was carried out at 120°C for 6 hours with stirring, and then cooled to room temperature. Subsequently, all reaction solvent was removed, and the mixture of octadecanol and octadecanone was separated using silica gel-packed column chromatography. The solvent was then dried under vacuum conditions to obtain the liquid mixture of octadecanol and octadecanone. An olefinic polymer containing polar functional groups was obtained as a solid product.

[0265]

[0266] Experimental Example 1

[0267] For the above examples and comparative examples, the yield (%) was calculated based on the product separated after the oxidation reaction of the olefin-based polymer was completed, and the TON (turnover number, number of moles of product formed per mole of catalyst) was analyzed using this.

[0268] In addition, of the product 1 The ratio of octadecanol to octadecanone was calculated by analyzing H-NMR.

[0269]

[0270] As shown in the results of Table 1 above, the oxidation reaction of an olefin-based polymer was carried out with excellent yield using an organic cobalt compound according to the present invention as a catalyst. More specifically, in Examples 1 to 5, high TON was achieved, confirming that the catalyst was efficiently utilized to promote the oxidation reaction. In addition, analysis of the oxidation reaction results showed high selectivity for octadecanol.

[0271] Meanwhile, Comparative Example 1 did not use a catalyst coordinated with cobalt and a ligand, but used them in the form of a simple mixture in the oxidation reaction, and it was confirmed that the TON was lower and the reactivity of the oxidation reaction was poor compared to the example.

[0272]

[0273] Preparation of Oxidized Olefin Polymers

[0274] Example 7

[0275] An olefinic polymer (LC 670, 238 mg) and a mixed solvent (6 mL: ortho-xylene (3 mL) / 1,2,4-trichlorobenzene (3 mL)) were added to a 20 mL vial and the mixture was dissolved for 0.5 hours. Subsequently, the compound prepared in Preparation Example 1 (0.001 mmol) and 152 mg (1.0 mmol) of cumene hydroperoxide were added to the mixture. The reaction was carried out at 120°C for 6 hours while stirring, and then cooled to room temperature. Afterward, the mixture was slowly added to methanol to precipitate, the precipitate was washed with methanol, and dried under vacuum conditions to obtain an oxidized olefinic polymer containing polar functional groups as a solid product.

[0276]

[0277] Example 8

[0278] The procedure was performed in the same manner as in Example 7, except that 380 mg (2.5 mmol) of cumene hydroperoxide was used.

[0279]

[0280] Example 9

[0281] The procedure was performed in the same manner as Example 7, except that 760 mg (5.0 mmol) of cumene hydroperoxide was used.

[0282]

[0283] Example 10

[0284] The procedure was performed in the same manner as Example 7, except that 1,140 mg (7.5 mmol) of cumene hydroperoxide was used.

[0285]

[0286] Example 11

[0287] The procedure was performed in the same manner as Example 7, except that 1,520 mg (10.0 mmol) of cumene hydroperoxide was used.

[0288]

[0289] Comparative Example 2

[0290] An olefin-based polymer (LC 670, 238 mg) was prepared and used.

[0291]

[0292] Comparative Example 3

[0293] An olefinic polymer (LC 670, 238 mg) and 1,2-dichlorobenzene (6 mL) were added to a 20 mL vial, and the mixture was dissolved for 0.5 hours. Subsequently, the compound prepared in Preparation Example 1 (0.001 mmol) and cumene hydroperoxide (152 mg, 1.0 mmol) were added to the mixture. The reaction was carried out at 120°C for 8 hours while stirring, and then cooled to room temperature. Afterward, the mixture was slowly added to methanol to precipitate, and the precipitate was washed with methanol and dried under vacuum conditions to obtain an oxidized olefinic polymer containing polar functional groups as a solid product.

[0294]

[0295] Comparative Example 4

[0296] An olefinic polymer (LC 670, 238 mg) and 1,2,4-trichlorobenzene (6 mL) were added to a 20 mL vial, and the mixture was dissolved for 0.5 hours. Subsequently, the compound prepared in Preparation Example 1 (0.001 mmol) and cumene hydroperoxide (152 mg) were added to the mixture. The reaction was carried out at 130°C for 8 hours while stirring, and then cooled to room temperature. Afterward, the mixture was slowly added to methanol to precipitate, and the precipitate was washed with methanol and dried under vacuum conditions to obtain an oxidized olefinic polymer containing polar functional groups as a solid product.

[0297]

[0298] Comparative Example 5

[0299] An olefinic polymer (LC 670, 238 mg) and a mixed solvent (6 mL: ortho-xylene (3 mL) / 1,2-dichlorobenzene (3 mL)) were added to a 20 mL vial and the mixture was dissolved for 0.5 hours. Subsequently, the compound prepared in Preparation Example 1 (0.001 mmol) and cumene hydroperoxide (152 mg) were added to the mixture. The reaction was carried out at 140°C for 4 hours while stirring, and then cooled to room temperature. Afterward, the mixture was slowly added to methanol to precipitate, and the precipitate was washed with methanol and dried under vacuum conditions to obtain an oxidized olefinic polymer containing polar functional groups as a solid product.

[0300]

[0301] Experimental Example 2

[0302] * Oxidation level

[0303] 1 The degree of oxidation was calculated by analyzing the number of polar functional groups introduced into the oxidized olefin polymer using H NMR, and 1 The results of the ¹H NMR analysis are shown in Figures 1 to 6. 20 mg of an oxidized olefin polymer was added to 81.0 ml of toluene-d and stirred in an oil bath maintained at 90°C for approximately 10 minutes until completely dissolved and no solids remained, and the sample was prepared by slowly cooling to 25°C. After transferring the prepared sample to a 5 mm NMR tube, a nuclear magnetic resonance spectrometer (500 MHz NMR spectrometer, Varian UNITY INOVA 500 NMR spectrometer) was used 1 The H NMR spectrum was measured.

[0304] The oxidation degree of -OH was calculated by summing the integral values ​​of the peaks near 3.43 ppm and near 3.32 ppm, the oxidation degree of -CO- was calculated by dividing the integral value of the peak near 2.63 ppm by 4 (the number of α-protons of ketones having the same position peak), and the oxidation degree of -COO- was calculated by finding the average of the integral values ​​of the peaks near 2.53 ppm and near 4.15 ppm and dividing it by 2 (the number of ester protons). The sum of the oxidation degrees of -OH, -CO-, and -COO- was derived as the oxidation degree of the oxidized olefin-based polymer.

[0305]

[0306] * Density (g / cm²) 3 )

[0307] Measured according to ASTM D-792.

[0308]

[0309] * Melt Index (MI) 2.16 , dg / min)

[0310] It was measured according to ASTM D-1238 (condition E, 190℃, 2.16 kg load).

[0311]

[0312] * Weight-average molecular weight (Mw, g / mol) and molecular weight distribution (MWD)

[0313] 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.

[0314] - Column: PL Olexis

[0315] - Solvent: TCB (Trichlorobenzene)

[0316] - Flow rate: 1.0 ml / min

[0317] - Sample concentration: 1.0 mg / ml

[0318] - Injection volume: 200 µl

[0319] - Column temperature: 160℃

[0320] - Detector: Agilent High Temperature RI detector

[0321] - Standard: Polystyrene (corrected by a cubic function)

[0322]

[0323] * Melting Temperature (Tm)

[0324] This can be obtained using a Differential Scanning Calorimeter (DSC 6000) manufactured by PerkinElmer. Specifically, using DSC, the temperature of the copolymer was increased to 150°C and maintained for 1 minute under a nitrogen atmosphere, then cooled to -100°C, and the temperature was increased again to 150°C while observing the DSC curve. At this time, the heating rate and cooling rate were each set to 10°C / min.

[0325]

[0326] As shown in Table 2 above, it was confirmed that the oxidized olefin-based polymer according to the present invention has an oxidation degree of 1.2 or higher and a molecular weight distribution of 1.5 to 3.0.

[0327]

[0328] Experimental Example 3

[0329] * Number of contact angles

[0330] A contact angle meter (SEO, Phoenix Mini) was used as the measuring instrument, and Surfaceware 9 (SEO, Surface Electro Optics) was used as the measuring program.

[0331] 1.0 mL of toluene and 50 mg of the oxidized olefin polymer were placed in a 4 mL vial and heated at 100°C for 10 minutes. Afterward, the mixture was uniformly coated onto a glass substrate using a pipette and allowed to naturally evaporate for one day in a fume hood.

[0332] After mounting a glass substrate on the above measuring device, distilled water was dropped from a height (about 3-4 cm) where the shape is not damaged when liquid is dropped from a syringe, and the water contact angle was confirmed by taking a picture within 2 minutes.

[0333]

[0334] As shown in Table 3 above, the oxidized olefin-based polymer of the present invention has a large amount of polar functional groups introduced, and the water contact angle was smaller compared to the comparative example.

[0335]

[0336] Experimental Example 4

[0337] slip test

[0338] The oxidized olefin-based polymers of Examples 7 to 11 and Comparative Examples 2 to 5 were each cut into sheet-like specimens with a thickness of 0.5 T (0.5 mm) and an area of ​​10 cm × 10 cm. A heat-resistant film was applied to one side, and the opposite side was covered with a back sheet (LB-PVP, Lotte Aluminum) of 10 cm × 10 cm. Then, lamination was performed at 110°C for 15 minutes. The laminated samples were cut into 1 cm × 1 cm pieces to prepare specimens.

[0339] Each specimen was placed on an inclined surface with a certain angle on which a PET film coated with silicone was placed, and slipping was checked. It was evaluated as Fail if it slid completely down, and Pass if it did not slide or stopped in the middle while sliding. The measurement was repeated 5 times, and results were recorded where the same evaluation was obtained 3 or more times.

[0340]

[0341] As shown in Table 4 above, it can be confirmed that the oxidized olefin-based polymer of the present invention, in which a large amount of polar functional groups are introduced to increase the degree of oxidation, exhibits increased adhesion and excellent slip characteristics. This effect can be predicted to be due to the increased physical bonding resulting from the interaction with silicon on the surface of the PET film by polar functional groups, such as -OH, -CO, or -COO, introduced into the oxidized olefin-based polymer of the present invention. Meanwhile, in the case of Comparative Example 2, in which polar functional groups were not introduced, it was confirmed that it easily slides down the film surface even at a low angle.

Claims

Organic cobalt compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 is hydrogen or an alkyl group having 1 to 20 carbon atoms, wherein two R1s bonded to one 2,2'-bipyridine can be connected to each other to form an aromatic ring together with the 2,2'-bipyridine, and R2 and R3 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and X - is PY6 - , Y - , BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I. In claim 1, The above R1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and The above R2 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an ester group having 1 to 10 carbon atoms, and The above R3 is an organic cobalt compound that is hydrogen or an alkyl group having 1 to 10 carbon atoms. In claim 1, The above X - is PY6 - And, where, Y is an organic cobalt compound selected from the group consisting of F, Cl, Br and I. In claim 1, The compound represented by the above chemical formula 1 is an organic cobalt compound that is a compound represented by the following chemical formula 1A or chemical formula 1B: [Chemical Formula 1A] [Chemical Formula 1B] In the above chemical formulas 1A and 1B, R2 is each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, or an ester group having 1 to 30 carbon atoms, and X - is PY6 - , Y - , BY4 - , SO3 - , (CY3SO3) - , SbY6 - or AsY6 - And, where, Y is one or more selected from the group consisting of F, Cl, Br and I. In claim 1, The compound represented by the above chemical formula 1 is an organic cobalt compound selected from the group consisting of the following chemical formulas 1-1 to 1-3. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] A catalyst composition comprising the organic cobalt compound of claim 1; and a peroxide. In claim 6, The above peroxide is a catalyst composition comprising one or more selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, propionyl peroxide, lauryl peroxide, and acetyl peroxide. A method for oxidizing an olefinic polymer comprising the step of oxidizing the olefinic polymer in the presence of the catalyst composition of claim 6. Olefinic polymer satisfying conditions (a) to (d) below and containing polar functional groups: (a) Density: 0.855 g / cc to 0.915 g / cc; (b) Melt index (MI, 190℃, 2.16 kg load condition): 0.1 g / 10 min to 100.0 g / 10 min; (c) Molecular weight distribution: 1.5 to 3.0; and (d) Oxidation degree: 1.2 or higher. In claim 9, An olefinic polymer in which the above polar functional group is one or more selected from the group consisting of -OH, -CO- and -COO-. In claim 9, The above olefinic polymer is an olefinic polymer having a water contact angle of 65 to 85 degrees. In claim 9, The above olefin-based polymer is an ethylene / alpha-olefin copolymer, and Herein, the alpha-olefin is an olefin-based polymer comprising 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, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicocene.

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