Ethylene α-olefin copolymer and method for producing the same

Abstract

According to one embodiment of the present invention, there is provided an ethylene α-olefin copolymer comprising ethylene structural units and α-olefin structural units, wherein a stress-strain curve measured according to ASTM D638 has two or more sections where the tangent slope changes, the sections including a first section where the tangent slope decreases and a second section where the tangent slope increases. According to one embodiment of the present invention, there is provided an ethylene α-olefin copolymer and a method for producing the same, which have excellent tensile elongation, impact strength, and flexural strength and excellent processability due to their structural characteristics.

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin copolymer and a method for producing the same. [Background technology]

[0002] Recently, the solar market has grown explosively alongside the expansion of the renewable energy market, with olefin materials being widely used as encapsulants for solar panels. Typically, encapsulants can be manufactured using the same material or two or more different materials. Currently, the most commonly used encapsulant is an EVA (ethylene vinyl acetate)-based material, which is used to encapsulate photovoltaic cells or photovoltaic cell arrays by attaching them to ferroelectrics. However, this material has poor adhesion to glass and other components of the module. As a result, delamination easily occurs between the layers of the module after long-term use, which can lead to problems such as reduced module efficiency and corrosion due to moisture penetration.

[0003] In addition, currently known EVA-based encapsulants have poor resistance to ultraviolet (UV) rays, which can lead to discoloration or bleaching over long periods of use, which also reduces module efficiency. Furthermore, EVA-based encapsulants also have the problem of generating stress during curing, which can damage the module.

[0004] To solve these problems, the use of ethylene α-olefin copolymers has recently been attracting attention. Ethylene α-olefin copolymer materials protect the cells that produce solar energy, and also provide adhesion to the glass and backsheet, protecting them from moisture and external impacts. To fulfill these roles perfectly, there is a need to develop ethylene α-olefin copolymers with excellent tensile elongation, impact strength, flexural strength, and processability. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an ethylene-α-olefin copolymer excellent in tensile elongation, impact strength, flexural strength, processability, etc., and a method for producing the same. [Means for solving the problem]

[0006] In an ethylene α-olefin copolymer according to an embodiment of the present invention, there are two or more sections where the tangent gradient changes in a stress-strain curve measured according to ASTM D638, and the sections where the tangent gradient changes include a first section where the tangent gradient decreases and a second section where the tangent gradient increases.

[0007] The first section may occur at a strain rate of 0 to 200%, and the second section may occur at a strain rate of 500 to 1000%.

[0008] The ethylene α-olefin copolymer may have a yield point in the first section.

[0009] The ethylene α-olefin copolymer may have an elongation of 900% or more.

[0010] The ethylene α-olefin copolymer has a spreading gradient value of 1 to 5 (×10 6 Pa / m). [Effects of the Invention]

[0011] According to an embodiment of the present invention, an ethylene-α-olefin copolymer having excellent tensile elongation, impact strength, and flexural strength due to structural characteristics and excellent processability, and a method for producing the same, can be provided. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a graph showing the analysis results of a stress-strain curve for a conventional ethylene-α-olefin copolymer (comparative example). [Figure 2]FIG. 2 is a graph showing the analysis results of stress-strain curves for ethylene-α-olefin copolymers according to examples of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, preferred embodiments of the present invention will be described with reference to Figures 1 and 2. However, the present invention may be modified in various other forms, and the scope of the present invention is not limited to the following embodiments.

[0014] FIG. 1 is a graph showing the analysis results of a stress-strain curve for a conventional ethylene-α-olefin copolymer (comparative example).

[0015] FIG. 2 is a graph showing the analysis results of the stress-strain curve for the ethylene-α-olefin copolymer according to an embodiment of the present invention.

[0016] As used herein, the term "alkyl" refers to a monovalent straight or branched chain saturated hydrocarbon radical composed solely of carbon and hydrogen atoms, and examples of such alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.

[0017] Additionally, the term "alkenyl" as used herein refers to a straight or branched chain hydrocarbon radical containing one or more carbon-carbon double bonds, including, but not limited to, ethenyl, propenyl, butenyl, pentenyl, etc.

[0018] Additionally, the term "alkynyl" as used herein refers to a straight or branched chain hydrocarbon radical containing one or more carbon-carbon triple bonds, including, but not limited to, methynyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, and the like.

[0019] The term "aryl" as used herein refers to an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, including single or fused ring systems, including, but not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.

[0020] Furthermore, the term "alkylaryl" as used herein means an organic group in which one or more hydrogen atoms of an aryl group are replaced by an alkyl group, including, but not limited to, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, t-butylphenyl, etc.

[0021] Additionally, the term "arylalkyl" as used herein refers to an organic group in which one or more hydrogen atoms of an alkyl group are replaced by an aryl group, including, but not limited to, phenylpropyl, phenylhexyl, and the like.

[0022] Furthermore, the term "amide" as used herein means an amino group (-NH2) bonded to a carbonyl group (C=O), "alkylamide" means an organic group in which at least one hydrogen atom in the -NH2 of the amide group is substituted with an alkyl group, and "arylamide" means an organic group in which at least one hydrogen atom in the -NH2 of the amide group is substituted with an aryl group. The alkyl group in the alkylamide group and the aryl group in the arylamide group may be the same as the examples of the alkyl group and aryl group described above, but are not limited thereto.

[0023] Additionally, the term "alkylidene" as used herein means a divalent aliphatic hydrocarbon group formed by removing two hydrogen atoms from the same carbon atom of an alkyl group, including, but not limited to, ethylidene, propylidene, isopropylidene, butylidene, pentylidene, and the like.

[0024] Furthermore, the term "acetal" as used herein refers to an organic group formed by the bond between an alcohol and an aldehyde, i.e., a substituent having two ether (-OR) bonds on one carbon, and includes, but is not limited to, methoxymethoxy, 1-methoxyethoxy, 1-methoxypropyloxy, 1-methoxybutyloxy, 1-ethoxyethoxy, 1-ethoxypropyloxy, 1-ethoxybutyloxy, 1-(n-butoxy)ethoxy, 1-(iso-butoxy)ethoxy, 1-(sec-butoxy)ethoxy, 1-(tert-butoxy)ethoxy, 1-(cyclohexyloxy)ethoxy, 1-methoxy-1-methylmethoxy, 1-methoxy-1-methylethoxy, etc.

[0025] Furthermore, the term "ether" as used herein refers to an organic group having at least one ether bond (-O-), including, but not limited to, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-(2-methoxyethoxy)ethyl, 3-methoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 2-methoxy-1-methylethyl, 2-methoxy-2-methylethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, etc.

[0026] Furthermore, the term "silyl" used in the present invention refers to a -SiH radical derived from silane, in which at least one hydrogen atom may be substituted with various organic groups such as alkyl or halogen. More specifically, the term "silyl" includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimethoxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, and triphenoxysilyl.

[0027] Additionally, the term "alkoxy" as used herein refers to an -O-alkyl radical, where "alkyl" is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

[0028] Also, the term "halogen" according to the present invention means a fluorine, chlorine, bromine, or iodine atom.

[0029] In addition, the term "C n " means that the number of carbon atoms is n.

[0030] The catalyst for polymerizing ethylene α-olefin copolymers and the method for producing ethylene α-olefin copolymers will be described below.

[0031] <Catalyst for Polymerization of Ethylene α-Olefin Copolymer and Method for Producing Ethylene α-Olefin Copolymer> The ethylene α-olefin copolymer provided by the present invention can be polymerized in a composition containing the catalyst for polymerization of ethylene α-olefin copolymer described below. Specifically, the catalyst for polymerization of ethylene α-olefin copolymer can include a main catalyst compound represented by the following Chemical Formula 1, which is a transition metal compound having a symmetric structure, and one or more co-catalyst compounds selected from the group consisting of compounds represented by the following Chemical Formula 2 or 3: [ka] In the above Chemical Formula 1, M is a Group 4 transition metal; Q 1 and Q 2 are each independently halogen, (C1-C 20 ) alkyl, (C2-C 20 ) alkenyl, (C2-C 20 ) alkynyl, (C6-C 20 ) aryl, (C1-C 20 ) Alkyl(C6-C 20 ) aryl, (C6-C 20)Aryl(C1-C 20 ) alkyl, (C1-C 20 ) Alkylamide, (C6-C 20 ) arylamide, or (C1-C 20 ) alkylidene; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently hydrogen; with or without acetal, ketal, or ether groups (C-C 20 ) alkyl; with or without acetal, ketal, or ether groups (C2-C 20 ) alkenyl; (C1-C2) with or without acetal, ketal, or ether groups 20 ) Alkyl(C6-C 20 ) aryl; with or without acetal, ketal, or ether groups (C6-C 20 )Aryl(C1-C 20 ) alkyl; or (C1-C2) with or without acetal, ketal, or ether groups 20 ) alkylsilyl; 1 and R 2 may be linked to each other to form a ring, and said R 3 and R 4 may be linked to each other to form a ring, and said R 5 ~R 10 two or more of which may be linked together to form a ring; R 11 , R 12 , and R 13 are each independently hydrogen; with or without acetal, ketal, or ether groups (C-C 20 ) alkyl; with or without acetal, ketal, or ether groups (C2-C 20 ) alkenyl; (C1-C2) with or without acetal, ketal, or ether groups 20) Alkyl(C6-C 20 ) aryl; with or without acetal, ketal, or ether groups (C6-C 20 )Aryl(C1-C 20 ) alkyl; with or without acetal, ketal, or ether groups (C1-C 20 ) alkylsilyl; (C1-C 20 ) alkoxy; or (C6-C 20 ) aryloxy; 11 and R 12 or R 12 and R 13 can be linked to each other to form a ring. [Chemical formula 2] [LH] + [Z(A)4] - [Chemical formula 3] [L] + [Z(A)4] - In Formula 2 and Formula 3, L is a neutral or cationic Lewis acid, Z is a Group 13 element, and A is (C6-C 20 ) aryl or (C1-C 20 ) alkyl, and the (C-C 20 ) aryl or (C1-C 20 )Alkyl is halogen, (C1-C 20 ) hydrocarbyl, (C1-C 20 ) alkoxy, or (C6-C 20 ) substituted or unsubstituted aryloxy.

[0032] The promoter compound represented by the formula 2 or 3 has a strong electrophilicity, and Q bonded to the central metal M of the main catalyst compound represented by the formula 1. 1 and / or Q 2 At this time, Q 1 and / or Q 2The more rapidly the dissociation of M occurs, the higher the polymerization activity becomes, and the longer the central metal M is stabilized, the longer the stabilized M is coordinated with the double bonds contained in ethylene and α-olefin, resulting in a high molecular weight ethylene-α-olefin copolymer.

[0033] The transition metal compound represented by Chemical Formula 1 contains a ligand with a new structure in which an amide ligand and an o-phenylene form a fused ring, and the pentagonal ring π-ligand bonded to the o-phenylene is fused with a thiophene heterocycle. As a result, the transition metal compound has the advantage of having higher ethylene-α-olefin copolymerization activity than transition metal compounds without a fused thiophene heterocycle.

[0034] According to the present invention, in the transition metal compound represented by the chemical formula 1, 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 may each be independently substituted with a substituent containing an acetal, ketal, or ether group, and when substituted with such a substituent, it may be more advantageous to load it onto the surface of a support.

[0035] In the compound represented by Chemical Formula 1, M is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0036] In addition, in the transition metal compound represented by the chemical formula 1, the Q 1 and Q 2 are each independently a halogen or (C1-C 20 ) alkyl, more preferably chlorine or methyl.

[0037] In addition, in the transition metal compound represented by the chemical formula 1, 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or (C1-C 20 ) alkyl, preferably each independently hydrogen or methyl. More preferably, the R 1 , R 2 , R 3 , R 4 , and R 5 may each independently be hydrogen or methyl, provided that R 3 and R 4 At least one of the groups is methyl, and R 5 can be methyl.

[0038] In addition, in the transition metal compound represented by the chemical formula 1, 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is preferably each hydrogen.

[0039] The transition metal compound represented by the formula 1 preferably contains the above-mentioned substituents in order to control the electronic and steric environment around the metal.

[0040] Meanwhile, the transition metal compound represented by Chemical Formula 1 can be obtained from a precursor compound represented by Chemical Formula 4: [ka] In the above formula 4, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11, R 12 , and R 13 are as defined in Chemical Formula 1.

[0041] Here, the precursor compound represented by Chemical Formula 4 can be prepared by a method including the steps of: (i) reacting a tetrahydroquinoline derivative represented by Chemical Formula 5 below with an alkyllithium, followed by adding carbon dioxide to prepare a compound represented by Chemical Formula 6; and (ii) reacting a compound represented by Chemical Formula 6 below with an alkyllithium, followed by adding a compound represented by Chemical Formula 7 below, and treating with an acid. [ka] [ka] [ka] In the above formulas 5, 6, and 7, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are as defined in Chemical Formula 1. However, in the above Chemical Formula 5, Chemical Formula 6, and Chemical Formula 7, the R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or (C1-C 20 ) alkyl, preferably each independently hydrogen or methyl. More preferably, the R 1 , R 2 , R 3 , R 4 , and R 5 may each independently be hydrogen or methyl, provided that R 3 and R4 At least one of the groups is methyl, and R 5 may be methyl. 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are preferably each hydrogen, which can ensure the accessibility and reactivity of the starting materials and is advantageous in controlling the electronic and steric environment of the transition metal compound of Formula 1 to be produced.

[0042] Step i is a reaction in which the tetrahydroquinoline derivative represented by Chemical Formula 5 is reacted with an alkyllithium, and then carbon dioxide is added to convert it into the compound represented by Chemical Formula 6. This reaction can be carried out by a method described in known literature (Tetrahedron Lett. 1985, 26, 5935; Tetrahedron 1986, 42, 2571; J. Chem. SC. Perkin Trans. 1989, 16).

[0043] In addition, in step i, the compound represented by Chemical Formula 6 is reacted with alkyllithium to induce a deprotonation reaction to generate an o-lithium compound, which is then reacted with the compound represented by Chemical Formula 7 and treated with an acid to obtain a precursor of the transition metal compound represented by Chemical Formula 4.

[0044] The reaction of reacting alkyllithium with the compound represented by Chemical Formula 6 to produce an o-lithium compound can be understood from known literature (Organometallics 2007,27,6687; Korean Antibody Patent No. 2008-0065868). In the present invention, the compound represented by Chemical Formula 7 is reacted with alkyllithium to produce an o-lithium compound, and the resulting mixture is treated with an acid to obtain a precursor of the transition metal compound represented by Chemical Formula 7.

[0045] The compound represented by Formula 7 can be prepared by various known methods, one of which is shown in Reaction Scheme 1 below. This method not only allows for preparation in a single reaction step, but also uses inexpensive starting materials, allowing for economical and easy preparation of the precursor of the transition metal compound of the present invention (J. Organomet. Chem., 2005, 690, 4213). [ka]

[0046] Meanwhile, various known methods can be used to synthesize the transition metal compound represented by Chemical Formula 1 from the precursor compound represented by Chemical Formula 4 obtained by the above method. Approximately 2 equivalents of alkyllithium are added to the precursor compound represented by Chemical Formula 4 to induce a deprotonation reaction, thereby preparing a dilithium compound of cyclopentadienyl anion and amide anion, and then (Q 1 )(Q 2 ) It can be prepared by adding MCl2 and removing about 2 equivalents of LiCl.

[0047] In addition, the compound represented by the formula 2 is reacted with a M(NMe2)4 compound to remove about 2 equivalents of HNMe2, and Q 1 and Q 2 The transition metal compound represented by formula 1 is obtained in which NMe2 is simultaneously reacted with Me3SiCl or Me2SiCl2 to convert the NMe2 ligand into a chlorine ligand.

[0048] The catalyst of the present invention includes a co-catalyst together with the transition metal compound represented by Chemical Formula 1. The co-catalyst serves to activate the transition metal compound, and is a compound represented by Chemical Formula 2 or 3, which activates the main catalyst compound represented by Chemical Formula 1.

[0049] According to the present invention, in the co-catalyst compound represented by the chemical formula 2, the [LH] + is a dimethylanilinium cation, and the [Z(A)4] - is [B(C6F5)4]- In addition, in the promoter compound represented by the chemical formula 3, the [L] + is [(C6H5)3C] + and the above [Z(A)4] - is [B(C6F5)4] - It is preferable that:

[0050] Here, the co-catalyst compound represented by Chemical Formula 2 is not particularly limited, and non-limiting examples include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate), N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsiiyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-triisopropylsilyl)-2,3,5,N,N-dimethylanilinium tetrakis(4-(triisopropysilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorphenyl)borate, N,N-diethylanilinium tetrakis(pentafluorphenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylammonium tetrakis(pentafluorophenyl)borate, tetrakis(2,3,4,6-tetrafluorophenyl)borate), N,N-diethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,Preferably, the ammonium salt is at least one selected from the group consisting of N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, and dialkylammonium.

[0051] Non-limiting examples of the dialkylammonium include di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetrakis(pentafluorophenyl)borate.

[0052] The co-catalyst compound represented by Chemical Formula 3 is not particularly limited, but is preferably at least one selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salts, as a non-limiting example.

[0053] Non-limiting examples of the trialkylphosphonium include triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

[0054] Non-limiting examples of the dialkyloxonium include diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl)borate.

[0055] Non-limiting examples of the dialkylsulfonium include diphenylsulfonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate.

[0056] Non-limiting examples of the carbonium salt include tropylium tetrakis(pentafluorophenyl)borate, triphenylmethylcarbenium tetrakis(pentafluorophenyl)borate, and benzene(diazonium)tetrakis(pentafluorophenyl)borate.

[0057] Such cocatalyst compounds may further include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like.

[0058] Meanwhile, the amount of the promoter compound added can be determined taking into consideration the amount of the main catalyst compound added and the amount necessary to sufficiently activate the main catalyst compound. According to the present invention, the promoter compound can be included in a molar ratio of 1:1 to 100,000, preferably 1:1 to 10,000, and more preferably 1:1 to 5,000, relative to the main catalyst compound. More specifically, the promoter compound represented by Chemical Formula 2 or 3 can be included in a molar ratio of 1:1 to 100, preferably 1:1 to 10,000, and more preferably 1:1 to 5,000, relative to the transition metal compound serving as the main catalyst compound, for example, the main catalyst compound represented by Chemical Formula 1, relative to the transition metal compound serving as the main catalyst compound, for example, the main catalyst compound represented by Chemical Formula 1.

[0059] On the other hand, the catalyst of the present invention containing the main catalyst compound and the co-catalyst compound may further contain a support.

[0060] Here, the carrier may be any inorganic or organic carrier used in the manufacture of catalysts in the technical field to which the present invention pertains, without any limitations.

[0061] According to one embodiment of the present invention, the carrier may be SiO2, Al2O3, MgO, MgCl2, CaCl2, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, SiO2-Al2O3, SiO2-MgO, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, bauxite, zeolite, starch, cyclodextrine, or a synthetic polymer.

[0062] Preferably, the support contains hydroxy groups on the surface, and may be one or more selected from the group consisting of silica (SiO2), silica-alumina (SiO2-Al2O3), and silica-magnesia (SiO2-MgO).

[0063] The main catalyst compound and the promoter compound may be supported on the support by, for example, directly supporting the main catalyst compound on a dehydrated support, pretreating the support with the promoter compound and then supporting the main catalyst compound, supporting the main catalyst compound on the support and then post-treating the promoter compound, or reacting the main catalyst compound with the promoter compound and then adding the support to the reaction.

[0064] The solvent that can be used in the deposition method can be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, or a mixture thereof.

[0065] Non-limiting examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane.

[0066] Non-limiting examples of the aromatic hydrocarbon solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene.

[0067] Non-limiting examples of the halogenated aliphatic hydrocarbon solvent include dichloromethane, trichloromethane, dichloroethane, and trichloroethane.

[0068] Furthermore, the above-mentioned supporting method is advantageous in terms of efficiency of the supporting step if it is carried out at a temperature of -70 to 200°C, preferably -50 to 150°C, and more preferably 0 to 100°C.

[0069] The ethylene α-olefin copolymer according to the present invention is produced by copolymerizing ethylene with an α-olefin, and the α-olefin is a C3-C 12 Or, the α-olefin may be a C3-C8 aliphatic olefin. More specifically, the α-olefin may be propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, or 3,4-dimethyl-1-hexene, and any one or a mixture of two or more of these may be used.

[0070] The ratio of ethylene and α-olefin fed into the reactor during polymerization is not particularly limited, but it is preferable that the weight ratio of ethylene to α-olefin is 1:0.5 to 1:1.3. When ethylene and α-olefin are fed in this weight ratio, an olefin copolymer having a high molecular weight and a high comonomer content can be obtained.

[0071] Meanwhile, the polymerization reaction of ethylene and α-olefins of the present invention can be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase.

[0072] When the polymerization reaction is carried out in a liquid or slurry phase, a solvent or the ethylene, α-olefin monomer itself may be used as the medium.

[0073] The solvent that can be used in the polymerization reaction may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, or a mixture thereof.

[0074] Non-limiting examples of the aliphatic hydrocarbon solvent include butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, and cyclohexane.

[0075] Non-limiting examples of the aromatic hydrocarbon solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, and chlorobenzene.

[0076] Non-limiting examples of the halogenated aliphatic hydrocarbon solvent include dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, and 1,2-dichloroethane.

[0077] Meanwhile, in the polymerization reaction of the present invention, the amount of the catalyst added is not particularly limited, and can be determined within a range in which the polymerization reaction of the monomers can be sufficiently carried out in a slurry phase, liquid phase, gas phase, or bulk phase process.

[0078] However, according to the present invention, the amount of the catalyst added is 10 times the concentration of the central metal M in the main catalyst compound per unit volume L of the monomer. -8 to 1 mol / L, preferably 10 -7 〜10 -1 mol / L, more preferably 10-7 〜10 -2 It can be mol / L.

[0079] The polymerization reaction of the present invention may be carried out in a batch type, semi-continuous type, or continuous type, and preferably in a continuous type.

[0080] The temperature conditions for the polymerization reaction of the present invention may be determined in consideration of the efficiency of the polymerization reaction depending on the type of reaction to be applied and the type of reactor, and the polymerization temperature may be 120° C. or higher, preferably 150 to 200° C. Since the reactivity increases as the polymerization temperature increases in the polymerization process, the catalyst for the polymerization of ethylene α-olefin copolymers has the advantage of being able to polymerize at a high temperature of 150° C. or higher.

[0081] The pressure conditions for the polymerization reaction of the present invention can be determined in consideration of the efficiency of the polymerization reaction depending on the type of reaction to be applied and the type of reactor, and the polymerization pressure can be 1 to 100 atmospheres, preferably 5 to 50 atmospheres.

[0082] For the polymerization reaction of the present invention, a catalyst and reactants may be continuously added, and the reactants may be a solvent, ethylene, an α-olefin monomer, or a mixture thereof.

[0083] Meanwhile, in the polymerization reaction of the present invention, a scavenger may be added to remove water and impurities from the catalyst-containing solution, thereby further enhancing the formation of catalytically active species in the polymerization reactor.

[0084] The scavenger is not particularly limited, but may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formula 8: [Chemical formula 8] D(R 31 )3 In the above formula 8, D is aluminum or boron, and R 31 are each independently a halogen radical, (C1-C 20) hydrocarbyl radical, or halogen-substituted (C1-C 20 ) hydrocarbyl radical.

[0085] The compound represented by Chemical Formula 8 is not particularly limited, and non-limiting examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum methoxide, and dibutylaluminum methoxide; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride; methylaluminum dimethoxide, ethylaluminum dimethoxide, and the like. alkylaluminum dialkoxides such as butylaluminum dimethoxide, butylaluminum dimethoxide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride; trialkylborons such as trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron;Or tris pentafluorophenyl boron, etc.;

[0086] The amount of the scavenger used can be determined depending on the amount and activity of the main catalyst compound represented by Formula 1.

[0087] In addition, when a compound represented by Chemical Formula 8 in which D is boron is used, it may be used in a molar ratio of 1:1 to 1:100, preferably 1:1 to 1:10, more preferably 1:1 to 1:3 relative to the main catalyst compound.

[0088] In the compound represented by Chemical Formula 8, when a compound in which D is aluminum is used, it may be used in a molar ratio of 1:1 to 1:1,000, preferably 1:1 to 1:500, more preferably 1:1 to 1:100, relative to the main catalyst compound.

[0089] Meanwhile, the position where the scavenger is introduced into the polymerization reactor is not particularly limited. For example, the scavenger may be introduced together with the catalyst and reactants, or may be introduced into the first or second polymerization reactor through a line separate from the line into which the catalyst and reactants are introduced.

[0090] <Ethylene α-olefin copolymer> The present invention provides an ethylene α-olefin copolymer produced by the above-mentioned catalyst for polymerizing an ethylene α-olefin copolymer and the above-mentioned method for producing an ethylene α-olefin copolymer.

[0091] The ethylene α-olefin copolymer according to the present invention has two or more sections where the tangent slope changes in a stress-strain curve measured according to ASTM D638 at a strain rate of 0 to 1000%. Specifically, the sections where the tangent slope changes include a first section where the tangent slope decreases and a second section where the tangent slope increases. The first section may appear at a strain rate of 0 to 200%, and the second section may appear at a strain rate of 500 to 1000%.

[0092] The ethylene α-olefin copolymer according to the present invention may have a yield point in the first region. When an external force acting on an object increases and the stress value reaches a specific value exceeding the elastic limit, the external force hardly increases but the permanent strain begins to increase rapidly, and the specific value exceeding the elastic limit represents the yield point, which may appear in the first region.

[0093] The ethylene α-olefin copolymer of the present invention has a density of 0.857 to 0.910 g / cm 3 Specifically, the ethylene α-olefin copolymer according to the present invention may have a viscosity of 0.860 g / cm 3 or more than 0.865g / cm 3 It can be more than 0.900 g / cm 3 or less than 0.870g / cm 3 It can be the following:

[0094] The ethylene α-olefin copolymer according to the present invention may have an elongation of 900% or more. Specifically, the ethylene α-olefin copolymer according to the present invention may have an elongation of 1,000% or more. The upper limit of the elongation of the ethylene α-olefin copolymer may be, for example, 2,000%, but is not limited thereto, and measurement may be difficult in practice when considering measurement conditions and equipment.

[0095] The ethylene α-olefin copolymer according to the present invention may exhibit a melt index (MI) of 0.1 to 40 g / 10 min. Specifically, the ethylene α-olefin copolymer according to the present invention may exhibit a melt index (MI) of 4.8 to 5.1 g / 10 min.

[0096] The ethylene α-olefin copolymer of the present invention has a spreading gradient value of 1 to 5 (×10 6 Specifically, the ethylene α-olefin copolymer according to the present invention may have a spreading gradient value of 1.2 to 2.1 (×10 6The spreading gradient value may be the average gradient within the strain hardening section where permanent elongation occurs in a stress-strain curve measured according to ASTM D638, and may be the average gradient between the minimum point and the second maximum point. In this case, the upper limit of the measurement range of the second maximum point may be the point where the strain rate is 1,000%.

[0097] The ethylene α-olefin copolymer according to the present invention may have a molecular weight distribution (MWD) value of 1 to 10. Specifically, the ethylene α-olefin copolymer according to the present invention may have a molecular weight distribution (MWD) of 1.5 or more, 2.1 or more, 2.2 or more, 2.3 or more, or 2.4 or more, and may be 8 or less, or 6 or less. The molecular weight distribution (MWD) value may be calculated as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn). [Example]

[0098] Examples and Comparative Examples <Synthesis Example> Synthesis of main catalyst compound 2 Transition metal compound 2 was synthesized according to the following reaction formula 2. The specific synthesis process is as follows. [ka]

[0099] First, methyllithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) was added dropwise to a diethyl ether solution (10 mL) of compound 1 (0.58 g, 1.79 mmol) at −30° C. (Step i).

[0100] The solution obtained in step i was stirred at room temperature overnight, then cooled to -30°C, and 0.37 g (1.79 mmol) of Ti(NMe2)2Cl2 was added in one portion (step ii).

[0101] The solution obtained in step ii was stirred for 3 hours, and then the solvent was completely removed using a vacuum pump to give red solid compound 2 (0.59 g, 75% yield).

[0102] 1 1 H NMR spectrum confirmed the presence of two stereocompounds in a ratio of 1:0.8.

[0103] 1 H NMR(C6D6):d7.12 and 7.09(d,J=7.2Hz,1H),6.96 and 6.94(d,J=7.2Hz,1H),6.82 and 6.80(t,J=7.2Hz,1H),6.47 and 6.46(d,J =7.2Hz,1H),6.45 and 6.44(d,J=7.2Hz,1H),5.44(m,1H,NCH),2.76-2.60(m,1H,CH2),2.44-2.18(m,1H,CH2),2.28 and 2.22(s,3H),2.09(s,3H),1.74 and 1.65(s,3H),1.88-1.48(m,2H,CH2),1.20 and 1.18(d,J=7.2Hz,3H),0.77 and 0.71(s,3H,TiMe),0.49 and 0.40(s,3H,TiMe)ppm.

[0104] 13 C{1H} NMR(C6D6):d159.83,159.52,145.93,144.90,140.78,139.93,139.21,138.86,135.26,131.5 6,129.69,129.57,127.50,127.46,127.38,127.24,121.29,121.16,120.05,119.96,118.90, 118.74,117.99,117.74,113.87,110.38,57.91,55.31,54.87,51.68,50.27,50.12,34.77,27 .58,27.27,23.10,22.05,20.31,19.90,16.66,14.70,13.11,12.98,12.68ppm.Anal.Calc.(C 22 H 27 NSTi):C,68.56;H,7.06;N,3.63.Found:C,68.43;H,7.24;N,3.52%.

[0105] Example 1 An ethylene / 1-octene copolymer was produced by carrying out the following continuous polymerization process using a 2.5 L reactor equipped with a stirrer.

[0106] A solution of 8.5 kg / hr of normal hexane, 1.5 kg / hr of ethylene, and 0.7 kg / hr of 1-butene was passed through a primary heat exchanger and injected into a high-pressure blender to produce a first mixture. The resulting first mixture was then passed through a secondary heat exchanger and then introduced into the bottom of the polymerization reactor. The transition metal compound obtained in the previous synthesis example (0.114 mmol / hr) and the cocatalyst compound N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (0.3 mmol / hr) were injected into the bottom of the reactor. The scavenger triisobutylaluminum was injected through a separate line from the line through which the first mixture was injected. The injection rate of triisobutylaluminum was 23 mmol / hr. The polymerization pressure was set at 90 bar, and the temperature at the bottom of the polymerization reactor was 135°C, while the temperature at the top rose to 150°C due to the heat of the polymerization reaction. The reaction was carried out continuously, with the estimated polymerization time from catalyst addition until completion and discharge of the reaction being approximately 10 minutes. After passing through the polymerization reactor, the collected reactants were passed through a high-temperature, high-pressure primary recovery unit to recover the solvent, and then passed through a high-temperature, low-pressure secondary recovery unit to recover residual n-hexane and unreacted ethylene. A pelletizer was then used to obtain a solidified ethylene / 1-octene copolymer.

[0107] <Example 2> An ethylene / 1-octene copolymer was produced by carrying out the following continuous polymerization process using a 2.5 L reactor equipped with a stirrer.

[0108] An ethylene / 1-octene copolymer was obtained in the same manner as in Example 1, except that the flow rates of the solution were changed to normal hexane 8.5 kg / hr, ethylene 1.3 kg / hr, and 1-butene 0.9 kg / hr.

[0109] <Comparative Examples 1 to 4> As the copolymers of Comparative Examples 1 to 4, those manufactured by LG Chem (trade name: LC565), those manufactured by Mitsui (trade name: DF640), and two types manufactured by Dow Chemical (trade names: EG7447 and EG8200) were used, respectively.

[0110] Analysis of physical properties of ethylene α-olefin copolymer The ethylene α-olefin copolymer samples of the Examples and Comparative Examples were placed in a mold having a thickness of 3 mm and a width and length of 8 cm, and were melted by compression at 125°C for 7 minutes using a press molding machine, and then cooled for 5 minutes to prepare test specimens. The physical properties of the test specimens were measured and are listed in Table 1 below.

[0111] (1) Melt index (MI): Measured according to ASTM D-1238 (condition E, 190°C, 2.16 kg load) using an instrument (manufacturer: Mirage, model name: SD-120L). (2) Density (g / mL): The antioxidant-treated copolymer was compressed at 180°C to produce a specimen with a thickness of 3 mm and a radius of 2 cm. It was then cooled to room temperature and measured according to ASTM D-792. (Manufacturer: Toyoseiki, Model: T-001) (3) Molecular weight distribution (MWD): Measured by GPC (Gel Permeation Chromatography, device name: PL-GPC220, manufacturer: Agilent) analysis at 160°C using 1,2,4-trichlorobenzene solvent. (4) Spreading gradient: Measurements were made using a Zwick Z010 Universal Testing Machine at a speed of 200 mm / min. The spreading gradient was calculated using the method described above, and the average value of a total of five tests was displayed as the result. (5) Stress-strain curve analysis: The number of sections where the slope of the tangent line changes between 0 and 1000% strain rate in the stress versus length curve measured for the specimen according to ASTM D638 was counted and the results were displayed. (6) Elongation: After cutting into a pattern of a test piece for tensile strength measurement according to ASTM D638, the strain rate until the test piece broke was measured according to ASTM D638 at a tension speed of 5 mm / min.

[0112] [Table 1]

[0113] Referring to Table 1 and FIGS. 1 and 2, in the stress-strain curve analysis, in Examples 1 and 2 where two or more sections where the tangent gradient changes are present in the graph of the stress versus strain rate curve (more specifically, both the first section where the tangent gradient decreases and the second section where the tangent gradient increases are present), no failure occurred at a strain rate of 1000%, indicating an elongation of 1000% or more. However, in Comparative Examples 1 to 4 where only one section where the tangent gradient changes is present (more specifically, only the first section where the tangent gradient decreases), an incomplete phenomenon occurred at a strain rate of less than 1000%, indicating an elongation of less than 1000%.

[0114] Considering this, the ethylene α-olefin copolymers of Examples 1 and 2, which exhibit two or more sections where the tangent slope changes in the graph of the stress versus strain rate curve during stress-strain curve analysis, are judged to have relatively excellent tensile elongation, flexural strength, processability, etc. [Industrial Applicability]

[0115] As noted above, the features of the present invention may be applied in whole or in part to ethylene α-olefin copolymers and methods for making same.

Claims

1. An ethylene α-olefin copolymer containing ethylene structural units and α-olefin structural units, The stress-strain curve measured according to ASTM D638 has two or more sections where the tangent slope changes, The section in which the gradient of the tangent line changes includes a first section in which the gradient of the tangent line decreases and a second section in which the gradient of the tangent line increases. Ethylene α-olefin copolymer.

2. The first section occurs at a strain rate of 0 to 200%, The second section occurs at a strain rate of 500 to 1000%. The ethylene α-olefin copolymer according to claim 1.

3. There is a yield point in the first section. The ethylene α-olefin copolymer according to claim 1.

4. The elongation rate is 900% or more. The ethylene α-olefin copolymer according to claim 1.

5. Spreading gradient values ​​range from 1 to 5 (x10 ６ Pa / m), The ethylene α-olefin copolymer according to claim 1.

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