Catalyst for preparing ethylene alpha-olefin copolymer, catalyst composition, and method for preparing ethylene alpha-olefin copolymer

Abstract

The present invention relates to a catalyst for preparing an ethylene-alpha olefin copolymer, a catalyst composition, and a method for preparing an ethylene-alpha olefin copolymer and, more specifically, to a catalyst for preparing an ethylene-alpha olefin copolymer represented by chemical formula 1, a catalyst composition, a method for preparing an ethylene-alpha olefin copolymer, an ethylene-alpha olefin resin composition prepared thereby, and an encapsulant for a solar cell comprising same. [Chemical formula 1] In chemical formula 1, R1, R2, R5, and R6 are each independently hydrogen; halogen; silyl; (C1-C20)alkyl; (C3-C20)cycloalkyl; (C2-C20)alkenyl; (C1-C20)alkoxy; (C6-C20)aryl unsubstituted or substituted with halogen, (C1-C12)alkyl, (C3-C12)cycloalkyl, (C1-C8)alkoxy, or (C6-C12)aryl; (C6-C20)aryl(C1-C20)alkyl unsubstituted or substituted with alkyl, halogen, (C1-C12)alkyl, (C3-C12)cycloalkyl, (C1-C8)alkoxy, or (C6-C12)aryl; or a metalloid radical of a Group 14 metal substituted with (C1-C20)hydrocarbyl; adjacent two or more of R1 to R4 may be connected to each other to form a ring, R3 and R4 are each independently selected from (C1-C20)alkyl, D is Si or C, M is a Group 4 transition metal, Q1 and Q2 are each independently hydrogen; halogen; (C1-C20)alkyl; (C3-C20)cycloalkyl; (C2-C20)alkenyl; (C6-C20)aryl; (C1-C20)alkyl(C6-C20)aryl; (C6-C20)aryl(C1-C20)alkyl; (C1-C20)alkylamino; (C6-C20)arylamino; or (C1-C20)alkylidene, E is -O-, -S-, -NR7-, or -PR7-, wherein R7 is hydrogen, halogen; (C1-C20)alkyl; (C3-C20)cycloalkyl; (C2-C20)alkenyl; (C1-C20)alkoxy; (C6-C20)aryl; (C6-C20)aryl(C1-C20)alkoxy; (C1-C20)alkyl(C6-C20)aryl; or (C6-C20)aryl(C1-C20)alkyl.

Description

Catalyst for producing ethylene-alpha olefin copolymer, catalyst composition and method for producing ethylene-alpha olefin copolymer

[0001] The present invention relates to a catalyst for producing an ethylene-alpha olefin copolymer, a catalyst composition, and a method for producing an ethylene-alpha olefin copolymer. More specifically, the catalyst of the present invention has excellent catalytic activity, and when a copolymer produced using the catalyst is used, a resin having excellent permeability, low yellowing, and high volume resistivity can be produced.

[0002] This application claims priority to and the benefit of Republic of Korea Patent Application No. 10-2023-0165600, filed November 24, 2023, which is incorporated herein by reference in its entirety.

[0003] Recently, there has been a growing global movement to shift away from traditional fossil fuel-based power generation to address climate change and embrace renewable energy sources that can reduce air pollution and carbon emissions. Consequently, demand for new materials needed for renewable energy generation is increasing, and research into various materials and technologies is actively underway. In line with this shift, even in the traditional field of polyolefins, significant interest and research are being focused on developing materials necessary for renewable energy generation.

[0004] In the field of renewable energy generation, solar power generation, which produces electricity from sunlight, solar encapsulation materials are used to attach and encapsulate photovoltaic cells or photovoltaic arrays to ferroelectrics, protecting the panels from moisture and external impact while also providing adhesion to glass and backsheets. EVA, a relatively inexpensive and highly effective material, is currently widely used as a solar encapsulation material. However, EVA suffers from problems such as reduced adhesive stability and discoloration due to oxidation by moisture and UV rays over long periods of use, leading to reduced module efficiency and corrosion due to moisture infiltration. Furthermore, encapsulation materials made of EVA generate greater stress during curing than other materials, which can damage the module.

[0005] To address these issues, recent attempts have been made to use polyolefin as a solar panel encapsulant. Unlike EVA, this polyolefin material does not contain polar functional groups, providing long-term stability in moisture and polar environments.

[0006] However, the polyolefin material above contains a crystal structure with ethylene as the main component of the chain, which results in optically unfavorable properties. To improve the optical properties of the polyolefin material above, it is necessary to reduce the proportion of crystals within the polymer resin. To this end, an ethylene-alpha olefin copolymer with a comonomer is used as an encapsulant.

[0007] Accordingly, if a technology is developed to manufacture ethylene-alpha-olefin copolymers with excellent optical properties and high volume resistivity, while also having improved productivity due to high catalytic activity, it is expected to be widely applied in related fields.

[0008] One aspect of the present invention is to provide a catalyst for producing an ethylene-alpha olefin copolymer having excellent catalytic activity and high volume resistivity.

[0009] Another aspect of the present invention is to provide a catalyst composition for producing an ethylene-alpha olefin copolymer comprising the same.

[0010] Another aspect of the present invention provides a method for producing an ethylene-alpha olefin copolymer using the catalyst for producing an ethylene-alpha olefin copolymer of the present invention.

[0011] Another aspect of the present invention is to provide an ethylene-alpha olefin resin composition having excellent physical properties manufactured using the catalyst composition of the present invention.

[0012] According to one aspect of the present invention, a catalyst for producing an ethylene-alpha olefin copolymer represented by chemical formula 1 is provided.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] R 1 , R 2 , R 5 , and R 6 are each independently hydrogen; halogen; silyl; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C1-C 20 )alkoxy; halogen, (C1-C 12 )alkyl, (C3-C 12 )cycloalkyl, (C1-C8)alkoxy, (C6-C 12 ) substituted or unsubstituted with aryl (C6-C 20 )aryl; halogen, (C1-C 12 )alkyl, (C3-C 12 )cycloalkyl, (C1-C8)alkoxy, (C6-C 12) substituted or unsubstituted with aryl (C6-C 20 )aryl(C1-C 20 )alkyl; or (C1-C 20 ) is a metalloid radical of a group 14 metal substituted with hydrocarbyl; R 1 Inland R 4 Two or more adjacent ones can be connected to each other to form a ring.

[0017] R 3 and R 4 are each independently (C1-C 20 ) is selected from alkyl,

[0018] D is Si or C,

[0019] M is a group 4 transition metal,

[0020] Q 1 and Q 2 are each independently hydrogen; halogen; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C6-C 20 )aryl; (C1-C 20 )alkyl(C6-C 20 )aryl; (C6-C 20 )aryl(C1-C 20 )alkyl; (C1-C 20 )alkylamino; (C6-C 20 )arylamino; or (C1-C 20 ) is alkylidene,

[0021] E is -O-, -S-, -NR 7 - or -PR 7 - and here, R 7 Silver hydrogen, halogen; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C1-C 20 )alkoxy; (C6-C 20 )aryl; (C6-C 20 )aryl(C1-C 20 )alkoxy; (C1-C 20)alkyl(C6-C 20 )aryl; or (C6-C 20 )aryl(C1-C 20 ) is alkyl.

[0022] According to another aspect of the present invention, a catalyst composition for producing an ethylene-alpha olefin copolymer is provided, comprising the catalyst of the present invention; and at least one cocatalyst selected from the group consisting of a compound represented by chemical formula 2 and a compound represented by chemical formula 3.

[0023] [Chemical Formula 2]

[0024] [LH] + [Z(A)4] -

[0025] [Chemical Formula 3]

[0026] [L] + [Z(A)4] -

[0027] (In the above chemical formulas 2 and 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 ) is alkyl.)

[0028] According to another aspect of the present invention, a method for producing an ethylene-alpha olefin copolymer is provided, comprising a step of reacting ethylene and an alpha olefin in the presence of a catalyst composition comprising the catalyst for producing an ethylene-alpha olefin copolymer of the present invention.

[0029] According to another aspect of the present invention, a film manufactured using the catalyst composition of the present invention has a light transmittance of 91 to 99%, a YI (Yellow Index) of 1.0 to 3.0 and a volume resistivity of 1×10 when measured according to ASTM D257. 15 1 × 10 17 An ethylene-alpha olefin resin composition is provided.

[0030] The catalyst including the transition metal compound provided in the present invention can produce an ethylene-alpha olefin copolymer with improved optical properties and higher catalytic activity, and more specifically, can provide an ethylene-alpha olefin copolymer having high volume resistivity and excellent light transmittance.

[0031] Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0032] The term "alkyl" described in the present invention means a monovalent straight-chain or branched saturated hydrocarbon radical composed only 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.

[0033] In addition, the term "alkenyl" described in the present invention means a straight-chain or branched-chain hydrocarbon radical containing one or more carbon-carbon double bonds, including, but not limited to, ethenyl, propenyl, butenyl, pentenyl, etc.

[0034] In addition, the term "alkynyl" described in the present invention means a straight-chain 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.

[0035] In addition, the term "aryl" described in the present invention refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

[0036] In addition, the term “alkylaryl” described in the present invention means an organic group in which one or more hydrogens of an aryl group are replaced by an alkyl group, and includes, but is not limited to, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, t-butylphenyl, etc.

[0037] In addition, the term “arylalkyl” described in the present invention means an organic group in which one or more hydrogens of an alkyl group are replaced by an aryl group, and includes, but is not limited to, phenylpropyl, phenylhexyl, etc.

[0038] In addition, the term "amido" described in the present invention means an amino group (-NH2) bonded to a carbonyl group (C=O), "alkylamido" means an organic group in which at least one hydrogen in -NH2 of the amido group is replaced with an alkyl group, and "arylamido" means an organic group in which at least one hydrogen in -NH2 of the amido group is replaced with an aryl group, and the alkyl group in the alkylamido group and the aryl group in the arylamido group may be the same as the examples of the alkyl group and aryl group described above, but are not limited thereto.

[0039] In addition, the term "alkylidene" described in the present invention means a divalent aliphatic hydrocarbon group in which two hydrogen atoms are removed from the same carbon atom of an alkyl group, and includes, but is not limited to, ethylidene, propylidene, isopropylidene, butylidene, and pentylidene.

[0040] In addition, the term "acetal" described in the present invention means an organic group formed by a bond between an alcohol and an aldehyde, that is, 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.

[0041] In addition, the term "ether" described in the present invention is an organic group having at least one ether bond (-O-), and includes, but is 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, and the like.

[0042] In addition, the term "silyl" described in the present invention means a -SiH3 radical derived from silane, and at least one of the hydrogen atoms in the silyl group may be substituted with various organic groups such as alkyl and halogen, and specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimethoxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, triphenoxysilyl, etc.

[0043] In addition, the term "alkoxy" described in the present invention means an -O-alkyl radical, wherein "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.

[0044] Additionally, the term “halogen” described in the present invention means a fluorine, chlorine, bromine or iodine atom.

[0045] In addition, the term “C” described in the present invention n 」 means that the number of carbon atoms is n.

[0046] The present invention provides a catalyst composition for producing an ethylene-alpha olefin copolymer, comprising a specific transition metal compound. The present invention also provides a method for producing an ethylene-alpha olefin copolymer in the presence of the catalyst composition for producing an ethylene-alpha olefin copolymer.

[0047] The catalyst for producing an ethylene-alpha olefin copolymer of the present invention may be a transition metal compound represented by the following chemical formula 1.

[0048] [Chemical Formula 1]

[0049]

[0050] In the above chemical formula 1, R 1 , R 2 , R 5 , and R 6 are each independently hydrogen; halogen; silyl; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C1-C 20 )alkoxy; halogen, (C1-C 12 )alkyl, (C3-C 12 )cycloalkyl, (C1-C8)alkoxy, (C6-C 12 ) substituted or unsubstituted with aryl (C6-C 20 )aryl; halogen, (C1-C 12)alkyl, (C3-C 12 )cycloalkyl, (C1-C8)alkoxy, (C6-C 12 ) substituted or unsubstituted with aryl (C6-C 20 )aryl(C1-C 20 )alkyl; or (C1-C 20 ) is a metalloid radical of a group 14 metal substituted with hydrocarbyl; R 1 Inland R 4 Two or more adjacent ones can be connected to each other to form a ring.

[0051] R 3 and R 4 are each independently (C1-C 20 ) is selected from alkyl,

[0052] D is Si or C,

[0053] M is a group 4 transition metal,

[0054] Q 1 and Q 2 are each independently hydrogen; halogen; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C6-C 20 )aryl; (C1-C 20 )alkyl(C6-C 20 )aryl; (C6-C 20 )aryl(C1-C 20 )alkyl; (C1-C 20 )alkylamino; (C6-C 20 )arylamino; or (C1-C 20 ) is alkylidene,

[0055] E is -O-, -S-, -NR 7 - or -PR 7 - and here, R 7 Silver hydrogen, halogen; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C1-C 20 )alkoxy; (C6-C 20)aryl; (C6-C 20 )aryl(C1-C 20 )alkoxy; (C1-C 20 )alkyl(C6-C 20 )aryl; or (C6-C 20 )aryl(C1-C 20 ) is alkyl.

[0056] More preferably, the R 3 and R 4 are each independently a straight chain (C1-C2) alkyl, and a straight chain or branched chain (C3-C 20 ) may be selected from alkyl, for example, may be selected from the group consisting of methyl, ethyl, and propyl, and most preferably R 3 and R 4 are all methyl.

[0057] When the transition metal compound represented by the above chemical formula 1 contains substituents as described above, it is preferable because the electronic and steric environment around the metal can be controlled.

[0058] In the above chemical formula 1, R 1 , R 2 , R 5 , and R 6 Each of the above may be independently substituted with a substituent including an acetal, ketal or ether group. When substituted with a substituent such as the above, it may be more advantageous for supporting on the surface of the carrier.

[0059] More preferably, the R 1 , R 2 , R 5 , and R 6 are each independently hydrogen or (C1-C 20 ) may be alkyl, and preferably each independently may be hydrogen or methyl.

[0060] In the transition metal compound represented by the above chemical formula 1, D may be Si or C, and more preferably may be Si.

[0061] In the transition metal compound represented by the above chemical formula 1, M is a Group 4 transition metal, and more specifically, may be titanium (Ti), zirconium (Zr), or hafnium (Hf), and more preferably, may be Ti.

[0062] In the transition metal compound represented by the above chemical formula 1, Q 1 and Q 2 are each independently hydrogen; halogen; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C6-C 20 )aryl; (C1-C 20 )alkyl(C6-C 20 )aryl; (C6-C 20 )aryl(C1-C 20 )alkyl; (C1-C 20 )alkylamino; (C6-C 20 )arylamino; or (C1-C 20 ) may be alkylidene, and more specifically, the above Q 1 and Q 2 are each independently halogen or (C1-C 20 ) may be alkyl, more specifically chlorine or methyl.

[0063] In the transition metal compound represented by the above chemical formula 1, E is -O-, -S-, -NR 7 - or -PR 7 - and R 7 Silver hydrogen, halogen; (C1-C 20 )alkyl; (C3-C 20 )cycloalkyl; (C2-C 20 )alkenyl; (C1-C 20 )alkoxy; (C6-C 20 )aryl; (C6-C 20 )aryl(C1-C 20 )alkoxy; (C1-C 20 )alkyl(C6-C 20 )aryl; or (C6-C 20 )aryl(C1-C 20 ) is alkyl.

[0064] The transition metal compound represented by the above chemical formula 1 provided in the present invention includes a ligand having a novel structure in which an amido ligand and an ortho-phenylene form a condensed ring, and a five-membered ring pi-ligand bonded to the ortho-phenylene is fused by a thiophene heterocycle. Accordingly, the transition metal compound can exhibit improved copolymerization activity of ethylene-alpha olefins compared to a transition metal compound in which a thiophene heterocycle is not fused.

[0065] As a catalyst provided in the present invention, the transition metal compound represented by the chemical formula 1 may be, for example, a transition metal compound represented by the following chemical formula 1-1.

[0066] [Chemical Formula 1-1]

[0067]

[0068] A method for producing a transition metal compound represented by the chemical formula 1-1 provided in the present invention is described.

[0069] The method for preparing the above transition metal compound may include a ligand synthesis step, a metal reaction step, and an alkylation step. In particular, the transition metal compound provided in the present invention may have a structure in which Ti is substituted with dimethyl, as shown in the above chemical formula 1-1, and the above alkylation step may be included for such substitution with dialkyl.

[0070] For the substitution with the above alkyl, an alkylation step can be performed using alkyllithium, for example, methyllithium. In this way, by alkylating using alkyllithium as a reagent, a transition metal compound such as the above chemical formula 1-1 can be obtained. Furthermore, the above transition metal compound has a low content of Mg, which can act as an impurity in the transition metal compound provided in the present invention, so that the catalytic performance can be further improved, and further, the optical properties of the ethylene-alpha olefin copolymer obtained by the use of the above transition metal compound can be further improved.

[0071] In the present invention, the transition metal compound represented by the chemical formula 1-1 may not contain Mg, and even if it contains Mg, it is preferable to contain it in an amount of 1000 ppm or less in the transition metal compound.

[0072] By producing the transition metal compound of the present invention by the above method, the content of impurities (Mg) in the catalyst including the obtained transition metal compound can be reduced, and thus the light transmittance of an ethylene-alpha olefin copolymer produced using the transition metal compound can be increased, and also, it can have a high volume resistivity.

[0073] The present invention provides a catalyst composition comprising the above transition metal compound. The catalyst composition may comprise a cocatalyst compound of Chemical Formula 2 and / or Chemical Formula 3.

[0074] [Chemical Formula 2]

[0075] [LH] + [Z(A)4] -

[0076] [Chemical Formula 3]

[0077] [L] + [Z(A)4] -

[0078] In the above chemical formulas 2 and 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 above (C1-C 20 )aryl or (C1-C 20 )alkyl is halogen, (C1-C 20 )hydrocarbyl, (C1-C 20 )alkoxy, or (C6-C 20 ) may be substituted or unsubstituted with aryloxy.

[0079] The cocatalyst compound represented by the above chemical formula 2 or chemical formula 3 can activate the transition metal compound, which is the main catalyst component represented by the above chemical formula 1.

[0080] Specifically, the cocatalyst compound represented by the above chemical formula 2 or chemical formula 3 has strong electrophilicity and is bonded to the central metal M of the transition metal compound represented by the above chemical formula 1. 1 and / or Q 2 can be quickly dissociated. The above Q 1 and / or Q 2 By rapidly dissociating, the polymerization activity of ethylene and alpha olefin can be increased. In addition, the central metal M can remain stable for a longer period of time, so that the number of double bonds contained in ethylene and alpha olefin can increase, that is, the number of double bonds that can be coordinated, that is, reacted, can be increased, thereby forming longer chains, and thus, an ethylene-alpha olefin copolymer having a higher molecular weight can be obtained.

[0081] According to the present invention, in the cocatalyst compound represented by the above chemical formula 2, the [LH] + is a dimethylanilinium cation, and the above [Z(A)4] - is [B(C6F5)4] - It is desirable that.

[0082] In addition, in the cocatalyst compound represented by the above chemical formula 3, the above [L] + is [(C 18 H 37 )2N(H)(C6H5)] + and the above [Z(A)4] - is [B(C6F5)4] - It is desirable that.

[0083] Here, the co-catalyst compound represented by the above chemical formula 2 includes, but is not limited to, 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 N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium Tetrakis(4-(t-triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate (N,N-dimethylanilinium tetrakis(4-(t-triisopropylsilyl)-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-dimethylammonium tetrakis(2,3,5,6-tetrafluorophenyl)borate tetrakis(2,3,5,6-tetrafluorophenyl)borate), N,N-diethylammonium 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 (2,3,4,6-tetrafluorophenyl)borate), N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate (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), N,N-dioctadecylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate N,N-(Dioctadecylanilinium tetrakis(tetrafluorophenyl)borate), N,N-dihexadecylanilinium Tetrakis(2,3,4,6-tetrafluorophenyl)borate N,N-(Dihexadecylanilinium tetrakis(tetrafluorophenyl)borate), N,N-ditetradecylanilinium tetrakis(tetrafluorophenyl)borate N,N-(Ditetradecylanilinium tetrakis(tetrafluorophenyl)borate), N,N-dioctadecylammonium tetrakis(tetrafluorophenyl)borate N,N-(Dioctadecylammonium tetrakis(tetrafluorophenyl)borate), N,N-dihexadecylammonium tetrakis(tetrafluorophenyl)borate N,N-(Dihexadecylammonium tetrakis(tetrafluorophenyl)borate), N,N-ditetradecylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate N,N-(Ditetradecylammonium tetrakis(tetrafluorophenyl)borate),It may be at least one selected from the group consisting of bis(hydrogenated-tallowalkyl)methylammonium tetrakis(pentafluorophenyl)borate and dialkylammonium.

[0084] The above dialkylammonium may include, but is not limited to, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, etc.

[0085] In addition, the cocatalyst compound represented by the above chemical formula 3 may be, but is not limited to, at least one selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salts.

[0086] The above trialkylphosphonium may include, but is not limited to, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(o-tolylphosphonium tetrakis(pentafluorophenyl)borate, or tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

[0087] The above dialkyloxonium may include, but is not limited to, diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluororphenyl)borate, or di(2,6-dimethylphenyl oxonium tetrakis(pentafluorophenyl)borate.

[0088] The above dialkylsulfonium may include, but is not limited to, diphenylsulfonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, or bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate.

[0089] Non-limiting examples of the carbonium salt include tropylium tetrakis(pentafluorophenyl)borate, triphenylmethylcarbenium tetrakis(pentafluorophenyl)borate, or benzene(diazonium)tetrakis(pentafluorophenyl)borate.

[0090] These co-catalyst compounds may further include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum.

[0091] Meanwhile, the amount of the cocatalyst compound to be added can be determined by considering the amount of the main catalyst compound to be added and the amount required to sufficiently activate the cocatalyst compound. According to the present invention, the cocatalyst compound can be included in an amount of 1 to 100,000 moles per mole of the transition metal compound, preferably 1 to 10,000 moles, and more preferably 1 to 5,000 moles.

[0092] More specifically, the cocatalyst compound represented by the above chemical formula 2 or chemical formula 3 may be included in a ratio of 1 to 100 moles, preferably 1 to 10 moles, and more preferably 1 to 4 moles, per 1 mole of the transition metal compound represented by the above chemical formula 1.

[0093] Meanwhile, the catalyst of the present invention comprising the above transition metal compound and the above cocatalyst compound may further comprise a carrier.

[0094] Here, the carrier may be a carrier commonly used in the production of a catalyst in the technical field to which the present invention belongs, and a carrier made of an inorganic or organic material may be used.

[0095] In one embodiment of the present invention, the carrier may be, but is not limited to, 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, for example.

[0096] Preferably, the carrier may be at least one selected from the group consisting of silica (SiO2), silica-alumina (SiO2-Al2O3), and silica-magnesia (SiO2-MgO), which contains a hydroxyl group on the surface.

[0097] As a method for supporting a catalyst including the transition metal compound and the cocatalyst compound on the carrier, a method of directly supporting the transition metal compound on a dehydrated carrier; a method of pretreating the carrier with the cocatalyst compound and then supporting the transition metal compound; a method of supporting the transition metal compound on the carrier and then post-treating it with the cocatalyst compound; a method of reacting the transition metal compound and the cocatalyst compound and then adding the carrier to cause a reaction, etc. may be used.

[0098] The solvent usable in the above-mentioned method may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, or a mixture thereof.

[0099] Non-limiting examples of the above aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, decane, undecane, or dodecane.

[0100] Non-limiting examples of the above aromatic hydrocarbon solvents include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, or toluene.

[0101] Non-limiting examples of the above halogenated aliphatic hydrocarbon solvent include dichloromethane, trichloromethane, dichloroethane, or trichloroethane.

[0102] In addition, the above-mentioned loading method can be performed at a temperature of -70 to 200°C, preferably -50 to 150°C, more preferably 0 to 100°C, to improve the efficiency of the loading process.

[0103] In the present invention, an ethylene-alpha olefin copolymer can be obtained by copolymerizing ethylene and alpha olefin in the presence of a catalyst composition as described above.

[0104] The above alpha olefin is C2-C 12 , or an aliphatic alpha olefin of C2-C8. More specifically, the alpha 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-itocene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, or 3,4-dimethyl-1-hexene, and any one of these or a mixture of two or more thereof may be used.

[0105] The ratio of ethylene and alpha olefin fed into the reactor during the polymerization reaction is not particularly limited, but ethylene and alpha olefin can be fed in a weight ratio of 0.5 to 1.3 for 1 ethylene. When ethylene and alpha olefin are fed in the above weight ratio, an olefin copolymer having a high molecular weight and a high comonomer content can be obtained.

[0106] Meanwhile, the polymerization reaction of ethylene and alpha olefin of the present invention can be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase.

[0107] When the above polymerization reaction is carried out in a liquid or slurry phase, a solvent or ethylene or alpha olefin monomer itself can be used as a medium.

[0108] 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.

[0109] Non-limiting examples of the above aliphatic hydrocarbon solvent include butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, or cyclohexane.

[0110] Non-limiting examples of the above aromatic hydrocarbon solvents include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, or chlorobenzene.

[0111] Non-limiting examples of the above halogenated aliphatic hydrocarbon solvent include dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, or 1,2-dichloroethane.

[0112] Meanwhile, in the polymerization reaction of the present invention, the amount of the catalyst added can be determined within a range in which the polymerization reaction of the monomer can sufficiently occur in a slurry phase, liquid phase, gas phase or bulk phase process, and is therefore not particularly limited.

[0113] However, in the present invention, the amount of the catalyst added is 10 based on the concentration of the central metal (M) in the main catalyst compound per unit volume (L) of monomer. -11 It may be 1 mol / L, preferably 10 -10 10 inland -1 mol / L, more preferably 10 -10 10 inland -2 It can be mol / L.

[0114] In addition, the polymerization reaction of the present invention may be carried out as a batch type, semi-continuous type or continuous type reaction, and preferably may be a continuous type reaction.

[0115] The temperature and pressure conditions of 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 are not particularly limited, but can be performed under conditions of a temperature of 100 to 200°C, preferably a temperature of 120 to 160°C, and a pressure of 1 to 3000 atm, preferably 1 to 1000 atm.

[0116] According to the present invention, the ethylene-alpha olefin copolymer of the present invention can be produced by copolymerizing ethylene and alpha olefin in the presence of the catalyst composition and under polymerization conditions as described above.

[0117] An ethylene-alpha olefin copolymer prepared in the presence of a catalyst composition comprising a transition metal compound of the present invention can increase the polymerization activity of ethylene and alpha olefin monomers, thereby obtaining an ethylene-alpha olefin copolymer having a high molecular weight.

[0118] The transition metal compound represented by the above chemical formula 1 has excellent catalytic activity, preferably 100 to 1000 kg / g-cat, for example 130 to 250 kg / g-cat.

[0119] In addition, the transition metal compound represented by Chemical Formula 1 provided in the present invention has a low content of Mg as an impurity, as described above. Specifically, the transition metal compound provided in the present invention may contain Mg at 1000 ppm or less. By including a small amount of Mg as an impurity, an ethylene-alpha olefin copolymer having high light transmittance and volume resistivity can be produced.

[0120] Furthermore, the ethylene-alpha olefin copolymer obtained in the present invention may have a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 30,000 to 800,000, and more preferably 40,000 to 300,000. Although not particularly limited, the weight average molecular weight can be measured by using gel permeation chromatography (GPC) to measure the number average molecular weight (Mn) and the weight average molecular weight (Mw), and the molecular weight distribution can be calculated by Mw / Mn from the weight average molecular weight and the number average molecular weight.

[0121] Additionally, the ethylene-alpha olefin copolymer may have a molecular weight distribution (Mw / Mn) of 1 to 10, preferably 1.5 to 8, and more preferably 1.5 to 3.

[0122] Additionally, the ethylene-alpha olefin copolymer may have a density of 0.860 to 0.885 g / mL, more specifically, 0.870 to 0.880 g / mL.

[0123] Additionally, the ethylene-alpha olefin copolymer provided in the present invention may have a melt index (MI) of 0.1 to 50 g / 10 min.

[0124] In the ethylene-alpha olefin copolymer provided in the present invention, the content of the ethylene monomer and the alpha olefin monomer is not particularly limited, but for example, the comonomer may be included in an amount of 19 to 40 wt%, specifically 20 to 35 wt%, more specifically 20 to 32 wt%, and even more specifically 20 to 30 wt%.

[0125] According to another aspect of the present invention, a resin composition comprising the ethylene-alpha olefin copolymer described above is provided. The resin composition comprises the ethylene-alpha olefin copolymer and a crosslinking agent, and may further comprise a crosslinking aid as needed.

[0126] As the crosslinking agent, any agent commonly used for crosslinking ethylene-alpha olefin copolymers can be suitably used in the present invention, and for example, at least one selected from the group consisting of dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethyl cyclohexane, and TBEC (tert-butylperoxy 2-ethylhexyl carbonate) can be used.

[0127] Furthermore, the crosslinking auxiliary agent is not particularly limited, but may include at least one selected from the group consisting of trivinylbenzene, divinylbenzene, trivinylpropane, trivinylcyclohexane, and TAIC (Triallyl isocyanurate).

[0128] More specifically, the resin composition may include 85 to 95 wt% of an ethylene-alpha olefin copolymer, 0.5 to 10 wt% of a crosslinking agent, and 0.5 to 10 wt% of a crosslinking assistant, based on the total weight of the resin composition, and the resin composition may be provided as a resin composition for a solar cell encapsulating material.

[0129] In the manufacture of the resin composition for a solar cell encapsulating material according to the present invention, in order to apply the resin composition for a solar cell encapsulating material of the present invention to various solar cell module encapsulating materials, in addition to the above components, at least one additive such as a colorant, a coupling agent, an antioxidant, a discoloration inhibitor, a UV stabilizer, a UV absorber, etc. may be additionally used within a range that does not depart from the technical spirit of the present invention, and for example, may be used in an amount of 0.1 to 5 wt%, for example, 0.2 to 1 wt%, based on the total weight of the encapsulating material composition.

[0130] In addition, the ethylene-alpha olefin copolymer of the present invention can significantly shorten the time required for crosslinking, and thus, compared to the polymer resins used as existing solar encapsulating materials, it can reach the same degree of crosslinking at a faster rate, thereby reducing the work time when manufacturing solar panels. Specifically, when crosslinking a resin composition comprising the ethylene-alpha olefin copolymer of the present invention and a crosslinking agent, the time required for crosslinking may be 20 minutes or less, specifically 15 minutes or less, or 12 minutes or less.

[0131] Specifically, the resin composition including the ethylene-alpha olefin copolymer provided in the present invention may have a time (T90) until the torque value reaches 90% saturation of 600 seconds to 700 seconds, or may also have a time of 650 seconds to 700 seconds.

[0132] According to another aspect of the present invention, a solar cell encapsulating material manufactured from the resin composition of the present invention is provided.

[0133] When the resin composition of the present invention is used, the encapsulating material for solar cells can obtain a crosslinking rate of 90% to 99%.

[0134] When a solar encapsulating agent is manufactured using the ethylene-alpha olefin copolymer provided in the present invention, the light transmittance measured by ASTM D1003 based on a film having a thickness of 3 mm may be 90% or more, more specifically 90% to 99%, 91% to 95%, and more specifically 91% to 93%, and thus, the solar encapsulating agent may be suitably used.

[0135] Furthermore, when manufacturing a solar bag using the ethylene-alpha olefin copolymer according to the present invention, it can have a yellow index of 2 or less, more specifically 1.9 or less, and even more specifically 1.0 to 3.0 based on a film having a thickness of 3 mm.

[0136] In addition, when manufacturing a solar bag using the ethylene-alpha olefin copolymer according to the present invention, the volume resistivity measured according to ASTM D257 is 1× 10 15 It can be Ω·cm or more, and specifically 0.5×10 16 Ω·cm or more, more specifically 1.0×10 16 Ω·cm or more to 1 × 10 17It may be Ω·cm. Therefore, the ethylene-alpha olefin copolymer of the present invention may be suitable for use as a solar encapsulating material because it has a high volume resistivity.

[0137] Thus, according to the present invention, a resin composition for a sealing material is provided that exhibits a high crosslinking rate, high light transmittance and fast crosslinking speed, and has low yellowing, and can be used as a sealing material for solar cells.

[0138] Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely illustrative examples to aid understanding of the present invention and are not intended to limit the scope of the present invention.

[0139]

[0140] Example

[0141] 1. Preparation of transition metal compounds: Preparation of dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(3a,4,5,6,6a-η)-2,3,4,5-tetramethyl-6H-cyclopenta[b]thien-6-yl]silanaminato(2-)-κN]titanium

[0142] (1) Preparation of 2,3,4,5-tetramethyl-4,5-dihydro-6H-cyclopenta[b]thiophene-6-one

[0143] 37.4 g of polyphosphoric acid was added to a 500 mL round flask and the temperature was raised to 50°C. 2,3-methylthiophene (5.1 g) and tiglic acid (4.6 g) were dissolved in 10 mL of dichloromethane and slowly injected into the round flask above over 1 hour. After the injection was completed, the mixture was allowed to react for 4 hours.

[0144] Ice was added to the flask to terminate the reaction, and the reaction solution was extracted into the organic layer using diethyl ether. The extract was washed with a saturated aqueous solution of NaHCO3, and the organic layers were collected and dried over MgSO4. After removing MgSO4 and concentrating, the mixture was distilled at 110°C to obtain 6.7 g of 2,3,4,5-tetramethyl-4,5-dihydro-6H-cyclopenta[b]thiophen-6-one.

[0145] 1 H NMR (C6D6): 2.71-2.67 (q, 0.9H), 2.31-2.26 (q, 0.6H), 2.20-2.15 (q, 0.6H), 1.79 (s, 3H), 1.60 (s, 3H), 1.16-1.15 (d, 1.7H), 1.11-1.09 (d, 1.3H), 0.89-0.88 (d, 1.7H), 0.76-0.74 (d, 1.3H).

[0146] (2) Preparation of 2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophene

[0147] The above-obtained 2,3,4,5-tetramethyl-4,5-dihydro-6H-cyclopenta[b]thiophene-6-one was placed in a 500 mL round flask containing 75 mL of a mixed solvent of THF (tetrahydrofuran) and methanol (2:1, v / v).

[0148] While maintaining the temperature of the flask below 5°C, 10.5 g of NaBH4 was added, the temperature was raised to room temperature, and the reaction was allowed to proceed overnight.

[0149] The reaction solution was extracted with diethyl ether, washed three times with water, and dried over MgSO4. After removing MgSO4 and concentrating, 100 mL of THF / water (1:1, v / v) was added.

[0150] Next, 78 mL of 12% concentration hydrochloric acid aqueous solution was added to the obtained solution and reacted at 70°C for 4 hours.

[0151] Subsequently, after the reaction was completed, the temperature was lowered to room temperature, the mixture was extracted with diethyl ether, and neutralized with NaHCO3. The organic layer was collected, dried with MgSO4, filtered, and concentrated to obtain 5.9 g of 2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophene.

[0152] 1 H NMR (C6D6): 6.15 (s, 0.85H), 2.86 (s, 0.30H), 2.74-2.71 (q, 0.85H), 2.14 (s, 0.4H), 2.11 (s, 2.6H), 2.03 (s, 0.4H), 1.98 (s, 3H), 1.76 (s, 2.6H), 1.73 (s, 0.4H), 1.05-1.04 (d, 2.6H).

[0153] (3) Preparation of N-tert-butyl-1,1-dimethyl-1-(2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophen-6-yl)silanamine

[0154] 5.9 g of the above-obtained 2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophene and 500 mL of hexane were placed in a 1 L Schlenk flask under inert conditions and the temperature was lowered to -78°C.

[0155] 14.5 mL of n-butyllithium (2.5 M in hexane) was slowly added to the flask above, and the temperature was raised to room temperature and reacted overnight.

[0156] The reaction solution was filtered to obtain 6.1 g of lithiated 2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophene.

[0157] A 500 mL Schlenk flask containing a solution of 11.9 mL of dichlorodimethylsilane diluted with 120 mL of THF in an argon atmosphere was prepared. 60 mL of a THF solution containing 6.1 g of the above-obtained lithiated 2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophene was slowly injected into the flask at -78°C, and the temperature was raised to room temperature, followed by reaction overnight.

[0158] After the reaction was completed, the solvent and unreacted silane compound were removed and extracted with hexane.

[0159] The above extract was diluted with 120 mL of THF, the temperature was lowered to -78°C, 6.5 mL of tert-butylamine was slowly added, and the mixture was reacted overnight at room temperature.

[0160] After the reaction was completed, the solvent and unreacted amine compound were removed and extracted with hexane to obtain 5.6 g of N-tert-butyl-1,1-dimethyl-1-(2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophen-6-yl)silanamine.

[0161] 1 H NMR (C6D6): 3.18 (s, 1H), 2.11 (s, 3H), 2.02 (s, 3H), 1.97 (s, 3H), 1.95 (s, 3H), 0.24 (s, 3H), 0.01 (s, 3H).

[0162] (4) Preparation of dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(3a,4,5,6,6a-η)-2,3,4,5-tetramethyl-6H-cyclopenta[b]thien-6-yl]silanaminato(2-)-κN]titanium

[0163] Under inert conditions, 5.6 g of the above-obtained N-tert-butyl-1,1-dimethyl-1-(2,3,4,5-tetramethyl-6H-cyclopenta[b]thiophen-6-yl)silanamine was placed in a 500 mL Schlenk flask and diluted with 60 mL of THF.

[0164] After lowering the temperature inside the Schlenk flask to -78°C, 24.0 mL of methyllithium solution (3.1 M in diethyl ether) was slowly injected into the Schlenk flask. After the injection was completed, the temperature was raised to room temperature and the reaction was allowed to proceed for 2 hours.

[0165] The reaction flask temperature was then lowered to -78°C, and 2.0 mL of titanium tetrachloride was slowly injected. After the injection was completed, the temperature was raised to room temperature and the reaction was allowed to proceed overnight.

[0166] After the reaction was completed, the solvent was removed, extracted with hexane, and filtered through celite to obtain 5.9 g of the transition metal compound dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(3a,4,5,6,6a-η)-2,3,4,5-tetramethyl-6H-cyclopenta[b]thien-6-yl]silanaminato(2-)-κN]titanium (chemical formula A).

[0167] 1 H NMR (C6D6): 2.24 (s, 3H), 2.00 (s, 3H), 1.99 (s, 3H) 1.88 (s, 3H), 1.52 (s, 9H), 0.69 (s, 3H), 0.58 (s, 3H), 0.44 (s, 3H), 0.23 (s, 3H).

[0168] [Chemical Formula A]

[0169]

[0170]

[0171] 2. Preparation of ethylene-alpha olefin copolymer

[0172] Manufacturing Example 1

[0173] n-Hexane and 1-butene were continuously fed into a high-pressure reactor (internal capacity: 2 L, stainless steel) at room temperature at rates of 5.2 kg / hr and 0.6 kg / hr, respectively. Subsequently, 0.82 kg / hr of ethylene gas (1-butene / ethylene input ratio: 0.73 by weight) was continuously injected, and the reactor pressure was adjusted to 60 bar and the reactor temperature to 130°C.

[0174] Thereafter, as a main catalyst, 13.2 μmol / hr of the transition metal compound of the above chemical formula A, 0.9 mmol / hr of a triisobutyl aluminum cocatalyst, and 63.4 μmol / hr of a dioctadecylanilinium tetrakis(pentablueorophenyl)borate cocatalyst were continuously injected into the reactor, and a polymerization reaction was performed for 10 minutes.

[0175] Polymerization was stopped by continuously adding ethanol at a rate of 1.5 mmol / hr to the rear end of the reactor, and the polymerization solution was dried in a vacuum oven at 80°C to obtain an ethylene-alpha olefin copolymer.

[0176] Comparative Manufacturing Example 1

[0177] An ethylene-alpha olefin copolymer was prepared by carrying out a polymerization reaction in the same manner as in Manufacturing Example 1, except that a transition metal compound represented by chemical formula B was used as a main catalyst.

[0178] [Chemical Formula B]

[0179]

[0180] Comparative Manufacturing Example 2

[0181] An ethylene-alpha olefin copolymer was prepared by carrying out a polymerization reaction in the same manner as in Manufacturing Example 1, except that a transition metal compound represented by chemical formula C was used as the main catalyst.

[0182] [Chemical Formula C]

[0183]

[0184]

[0185] 3. Analysis of catalyst and copolymer properties

[0186] The following physical properties were measured for the ethylene-alpha olefin copolymers manufactured in Manufacturing Example 1 and Comparative Manufacturing Examples 1 and 2, respectively, and the results are shown in Table 1.

[0187] (1) Catalytic activity

[0188] The weight of copolymer produced per hour was measured and divided by the amount of catalyst added per hour to calculate the amount.

[0189] Catalytic activity (kg / g-cat.) = copolymer production / catalyst input

[0190] (2) Density

[0191] Sheets with a thickness of 3 mm and a radius of 2 cm were produced using a compression mold at 180°C using a copolymer, cooled to room temperature, and measured according to ASTM D-792 (Manufacturer: Toyoseiki, Model: T-001).

[0192] (3) Melt index (MI)

[0193] Measured according to ASTM D-1238 (Condition E, 190℃, 2.16 kg load) (Manufacturer: Mirage, Model: SD-120L).

[0194] Classification MwMWD Density (g / mL) Activity (kg / g-cat) MI (g / 10 min) Manufacturing Example 183,9473.240.878137.15.0 Comparative Manufacturing Example 1104,7072.870.87936.12.2 Comparative Manufacturing Example 233,2184.970.89830.914.1

[0195] As can be seen from Table 1 above, when using a catalyst utilizing the transition metal compound used in Manufacturing Example 1, it can be confirmed that the catalytic activity significantly increases during the production of an ethylene-alpha olefin copolymer. Therefore, since the catalyst of the present invention exhibits sufficiently excellent catalytic activity even without purification to a high purity, the purification cost and time for improving the catalytic activity can be reduced. In addition, since the catalyst of the present invention has a low freezing point, even when the temperature is low in winter, the catalyst can be stored in a solution state without being precipitated as a solid.

[0196]

[0197] 4. Analysis of resin composition properties

[0198] The following physical properties were analyzed for the resin compositions manufactured using the ethylene-alpha olefin copolymers manufactured in Manufacturing Example 1 and Comparative Manufacturing Examples 1 and 2, and the results are shown in Table 2. The physical properties of the resin compositions in Table 2 are indicated by the type of copolymer used.

[0199] (1) Light transmittance

[0200] A sheet with a thickness of 3 mm and a radius of 2 cm was produced using a compression mold at 180°C using a copolymer, and after cooling to room temperature, the total light transmittance for light with a wavelength of 550 nm was measured using a color & haze meter (Hazemeter, CHN Spec., Model CS-700).

[0201] The transmittance was measured three times by placing a 3 mm thick specimen in a specimen holder and calculating the average value of these measurements, and the measurement was performed under the standard conditions of JIS K 7105.

[0202] (2) Yellow Index

[0203] Using a copolymer, a sheet with a thickness of 3 mm and a radius of 2 cm was produced using a compression mold at 180°C, and after cooling to room temperature, a color & haze meter (Hazemeter, CHN Spec., Model CS-700) was used to place a 3 mm thick specimen in a specimen holder and measure it three times, and the average value was calculated. The measurement was performed under the ASTM E313-73 standard conditions.

[0204] (3) Volume resistance

[0205] A sheet with a thickness of 3 mm and a radius of 2 cm was produced using a compression mold at 180°C using a copolymer, and after cooling to room temperature, the volume resistivity was measured using an SM7120 electrometer combined with an SME8310 (test fixture) from HIOKI using a volume resistivity measurement method based on ASTM D257.

[0206] Distinctive Light Transmittance (%)Yellow IndexVolume Resistivity (Ω·cm)Manufacturing Example 191.181.21.2E+15Comparative Manufacturing Example 191.011.22.2E+15Comparative Manufacturing Example 290.123.36.8E+14

[0207] As can be seen from Table 2 above, it was found that the resin composition including the ethylene-alpha olefin copolymer manufactured using the catalyst utilizing the transition metal compound used in Manufacturing Example 1 had excellent transmittance, low yellowing, and high volume resistivity. Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and it will be apparent to those skilled in the art that various modifications and variations are possible within a range that does not depart from the technical spirit of the present invention described in the claims.

Claims

1. Catalyst for producing ethylene-alpha olefin copolymer represented by chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 , R 2 , R 5 , and R 6 are each independently hydrogen; halogen; silyl; (C 1 -C 20 )alkyl; (C 3 -C 20 )cycloalkyl; (C 2 -C 20 )alkenyl; (C 1 -C 20 )alkoxy; halogen, (C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 1 -C 8 )alkoxy, (C 6 -C 12 ) substituted or unsubstituted with aryl (C 6 -C 20 )aryl; halogen, (C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 1 -C 8 )alkoxy, (C 6 -C 12 ) substituted or unsubstituted with aryl (C 6 -C 20 )Aryl(C 1 -C 20 ) alkyl; or (C 1 -C 20 ) is a metalloid radical of a group 14 metal substituted with hydrocarbyl; R 1 Inland R 4 Two or more adjacent ones can be connected to each other to form a ring. R 3 and R 4 are each independently (C 1 -C 20 ) is selected from alkyl, D is Si or C, M is a group 4 transition metal, Q 1 and Q 2 are each independently hydrogen; halogen; (C 1 -C 20 )alkyl; (C 3 -C 20 )cycloalkyl; (C 2 -C 20 )alkenyl; (C 6 -C 20 )Aryl; (C 1 -C 20 )alkyl(C 6 -C 20 )Aryl; (C 6 -C 20 )Aryl(C 1 -C 20 )alkyl; (C 1 -C 20 )alkylamino; (C 6 -C 20 )arylamino; or (C 1 -C 20 ) is alkylidene, E is -O-, -S-, -NR 7 - or -PR 7 - and, here, R 7 Silver hydrogen, halogen; (C 1 -C 20 )alkyl; (C 3 -C 20 )cycloalkyl; (C 2 -C 20 )alkenyl; (C 1 -C 20 )alkoxy; (C 6 -C 20 )Aryl; (C 6 -C 20 )Aryl(C 1 -C 20 )alkoxy; (C 1 -C 20 )alkyl(C 6 -C 20 )aryl; or (C 6 -C 20 )Aryl(C 1 -C 20 ) is alkyl.

2. A catalyst for producing an ethylene-alpha olefin copolymer, wherein the catalyst in paragraph 1 is represented by chemical formula 1-1. [Chemical Formula 1-1] 3. A catalyst for producing an ethylene-alpha olefin copolymer, wherein the catalyst has a catalytic activity of 100 to 1000 kg / g-cat in the first paragraph.

4. A catalyst according to any one of clauses 1 to 3; and At least one cocatalyst selected from the group consisting of a compound represented by chemical formula 2 and a compound represented by chemical formula 3 A catalyst composition for producing an ethylene-alpha olefin copolymer, comprising: [Chemical formula 2] [L-H] + [Z(A) 4 ] - [Chemical Formula 3] [L] + [Z(A) 4 ] - In the above chemical formulas 2 and 3, L is a neutral or cationic Lewis acid, Z is a group 13 element, A is (C 6 -C 20 )aryl or (C 1 -C 20 ) is alkyl.

5. A method for producing an ethylene-alpha olefin copolymer, comprising the step of reacting ethylene and an alpha olefin in the presence of a catalyst composition comprising a catalyst for producing an ethylene-alpha olefin copolymer according to any one of claims 1 to 3.

6. A method for producing an ethylene-alpha olefin copolymer in the fifth paragraph, wherein the alpha olefin comprises at least one selected from the group consisting of 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-itocene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene.

7. A catalyst composition manufactured using the catalyst composition of clause 4, wherein the light transmittance for light of a wavelength of 550 nm for a film having a thickness of 3 mm is 91 to 99%, the YI (Yellow Index) of the film having a thickness of 3 mm is 1.0 to 3.0, and the volume resistivity measured according to ASTM D257 is 1× 10 15 Inside 1 × 10 17 A composition comprising an ethylene-alpha olefin resin.

8. A sealing material for a solar cell comprising the resin composition of clause 7.

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