Ethylene α-olefin copolymer, its production method, resin composition containing same, and molded article

Abstract

The present invention relates to an ethylene α-olefin copolymer and a resin composition containing the same. More specifically, the present invention provides an ethylene α-olefin copolymer containing ethylene structural units and α-olefin structural units, which has two or more distinct elution peaks in a temperature range of 250 K to 430 K when analyzed by TGIC (Thermal Gradient Interaction Chromatography), a method for producing the same, a resin composition containing the olefin copolymer, and a molded article.

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin copolymer, a method for producing the copolymer, a resin composition containing the copolymer, and a molded article. More specifically, the present invention relates to an ethylene-α-olefin copolymer having two types of chain distribution and thus having improved elongation and low-temperature impact strength, a method for producing the copolymer, a resin composition containing the copolymer, and a molded article. [Background technology]

[0002] Polyolefins are widely used polymeric materials, and in order to improve the low-temperature properties and mechanical properties of such polyolefins, they have mainly been mixed with ethylene α-olefin copolymers.

[0003] The Dow Chemical Company's [Me2Si(Me4C5)NtBu]TiCl2 (Constrained-Geometry Catalyst, "CGC") catalyst, which is used in conventional ethylene α-olefin copolymer reactions, is also excellent in copolymerization with sterically hindered α-olefins such as 1-hexene and 1-octene, and the polymerized olefin polymers are known to have not only narrow molecular weight distributions (MWD) but also a single chain structure with a consistent branched chain distribution.

[0004] On the other hand, since such conventional ethylene α-olefin copolymers basically have a single chain structure with uniform branch chain distribution, it is known that it is not easy to simultaneously achieve required physical properties such as compatibility with other resins, processability, strength, and impact strength.

[0005] For example, in order to improve low-temperature properties by blending ethylene α-olefin copolymers with polypropylene, a relatively low-density ethylene α-olefin copolymer should be used. However, if such a low-density ethylene α-olefin copolymer is mixed in an excessive amount, the tensile strength of the composite resin decreases.

[0006] Therefore, there is a need to research methods for improving the low-temperature properties and mechanical properties of composite resins without reducing properties such as tensile strength. Summary of the Invention [Problem to be solved by the invention]

[0007] An aspect of the present invention is to provide an ethylene α-olefin copolymer containing two chain structures with different branched chain contents, using a single metallocene catalyst in which R-type and S-type stereocompounds coexist, and a method for producing the same.

[0008] Another aspect of the present invention is to provide a resin composition and a molded article containing the copolymer of the present invention, which have improved elongation, impact strength, tensile strength, and shrinkage. [Means for solving the problem]

[0009] According to one aspect of the present invention, there is provided an ethylene α-olefin copolymer comprising ethylene structural units and α-olefin structural units, which has two or more distinct elution peaks in the temperature range of 250 K to 430 K when analyzed by TGIC (Thermal Gradient Interaction Chromatography).

[0010] The method for producing an ethylene α-olefin copolymer of the present invention includes a step of polymerizing ethylene and at least one olefin monomer in the presence of a main catalyst compound containing a transition metal compound represented by the following Chemical Formula 1, and one or more co-catalyst compounds selected from the compounds represented by the following Chemical Formulas 2 to 4: [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-C20 ) 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 13are 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] -[Al(Ra)-O] n - (In the above Chemical Formula 2, Each Ra is independently a halogen; or a halogen substituted or unsubstituted (C1-C 20 ) hydrocarbyl groups, n is an integer of 2 or greater), [Chemical formula 3] Q(Rb)3 (In the above Chemical Formula 3, Q is aluminum or boron; Each Rb is independently a halogen; or a halogen substituted or unsubstituted (C1-C 20 ) a hydrocarbyl group, [Chemical formula 4] [W] + [Z(Rc)4] - (In the above Chemical Formula 4, [W] + is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom attached, Z is a group 13 element, Rc is independently halogen, (C1-C 20 ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy, and phenoxy groups (C-C 20 ) aryl groups; halogens, (C1-C 20 ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy, and phenoxy groups (C1-C 20 ) alkyl).

[0011] The transition metal compound may be one in which R- and S-stereocompounds coexist.

[0012] The polypropylene resin composition of the present invention contains polypropylene and the ethylene α-olefin copolymer.

[0013] The molded article of the present invention can be produced from the polypropylene resin composition. [Effects of the Invention]

[0014] According to the present invention, an ethylene α-olefin copolymer having two chain structures with different comonomer contents obtained using a single metallocene catalyst has two chain structures with different short chain branch contents. According to the present invention, two polymer chains with different branch chain contents can be produced within the same density range, making it possible to synthesize a polymer containing low- to high-crystalline regions throughout. In this case, it is expected that polymer chains with a high branch chain content, which are amorphous or low-crystalline regions, can improve low-temperature impact strength and tensile elongation, while polymer chains with a low branch chain content can simultaneously improve tensile strength and shrinkage, which can be reduced by increasing the amorphous or low-crystalline regions. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a graph showing the results of low-temperature TGIC analysis of each polymer obtained in Examples 1 to 3 and Comparative Example 1. [Figure 2]1 is a graph showing the area ratio of TGIC depending on the proportion of catalyst composition for ethylene / 1-octene copolymers prepared in Examples 4 to 6. DETAILED DESCRIPTION OF THE INVENTION

[0016] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings, in which: FIG. 1 is a block diagram of a semiconductor device according to a first embodiment of the present invention;

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] Also, the term "halogen" according to the present invention means a fluorine, chlorine, bromine, or iodine atom.

[0030] In addition, the term "C" as used herein n " means that the number of carbon atoms is n.

[0031] The present invention aims to provide an ethylene α-olefin copolymer having two chain structures with different branched chain contents using one metallocene catalyst, using a catalyst isomer. That is, the present invention can provide an ethylene α-olefin copolymer having two chain structures with different branched chain contents using one metallocene catalyst, and a composition containing the same.

[0032] In particular, the copolymer of the present invention contains two polymer chains with different branch chain contents within the same density range, and includes a low-crystallinity region and a high-crystallinity region. The polymer chains with a high branch chain content, which are amorphous or low-crystallinity regions, can improve low-temperature impact strength and tensile elongation, while the polymer chains with a low branch chain content can simultaneously improve tensile strength and shrinkage, which can be reduced by increasing the amorphous or low-crystallinity region.

[0033] That is, the ethylene α-olefin copolymer prepared in the present invention is an ethylene α-olefin copolymer containing ethylene structural units and α-olefin structural units, and when analyzed by TGIC, it is eluted at two different temperatures, thereby confirming that two chain structures with different branched chain contents are produced.

[0034] The present invention provides an olefin copolymer which, when analyzed by TGIC, contains two or more distinct elution peaks in the temperature range of 250K to 430K.

[0035] More specifically, the ethylene α-olefin copolymer according to the present invention has a multimodal TGIC distribution. During TGIC analysis, low-crystalline regions of the copolymer exhibit high polymer mobility and low elution temperatures, while high-crystalline regions exhibit low polymer mobility and high elution temperatures. Therefore, if low-crystalline and high-crystalline regions coexist, the copolymer will have two or more elution zones. Therefore, a resin composition formed by blending the ethylene α-olefin copolymer according to the present invention with a polyolefin may exhibit improved impact strength due to the low-crystalline regions of the ethylene α-olefin copolymer. Furthermore, the high-crystalline regions of the ethylene α-olefin copolymer prevent a decrease in tensile strength due to an increase in low-crystalline regions within the resin composition, resulting in a resin composition with sufficient tensile strength and impact strength.

[0036] According to one aspect of the present invention, there is provided an ethylene α-olefin copolymer comprising ethylene structural units and α-olefin structural units, which, when analyzed by TGIC, has two different elution peaks, and has a first elution temperature and a second elution temperature, the difference between the first and second elution temperatures being 10 to 60 K.

[0037] The α-olefin is C2-C 12 Or it may be a C2-C8 aliphatic α-olefin. More specifically, 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, 3,4-dimethyl-1-hexene, and the like may be mentioned, and any one or a mixture of two or more of these may be used.

[0038] The physical properties of the ethylene-α-olefin copolymer may vary depending on the ratio of ethylene structural units to α-olefin structural units present in the copolymer.

[0039] The ratio of the ethylene structural units and the α-olefin structural units in the ethylene α-olefin copolymer is not particularly limited, but the weight ratio of the ethylene structural units and the α-olefin structural units in the ethylene α-olefin copolymer may be 1:0.1 to 1:1, and preferably 1:0.15 to 1:0.75.

[0040] If the content of α-olefin structural units is lower than the above range, the improvement effect on tensile elongation, low-temperature impact strength and shrinkage rate will be slight, and if it exceeds the above range, stickiness may occur in the product, causing a decrease in workability.

[0041] In the present invention, the first elution temperature can be calculated by the following formula 1. -2.5 × (α-olefin monomer content) + 132.5...Equation 1

[0042] On the other hand, the eluted polymer at the first elution temperature satisfies the following formula: 1) SCB = 2.5429 × (α-olefin content) + 6.9429 2) Mw = [10.151 x (α-olefin content) + 198.09] * 1000

[0043] The higher the α-olefin content, the lower the first elution temperature and the better the mechanical properties.

[0044] Meanwhile, for example, the first elution temperature may be 310 to 345K, and the second elution temperature may be 350 to 380K, and in this case, the ratio of the elution amount at the first elution temperature to the elution amount at the second elution temperature may be 0.5 to 7.3, or 0.7 to 2, for example, 0.76 to 1.9.

[0045] For example, the ratio of the first elution temperature to the second elution temperature is 0.5 to 0.91, for example, 0.55 to 0.91.

[0046] In the present invention, the polymerization of ethylene and α-olefins can be carried out in the presence of a catalyst composition containing R-type and S-type transition metal compounds represented by the following Chemical Formula 1: [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 may be linked to each other to form a ring, and said R 12 and R 13 can be linked to each other to form a ring.

[0047] 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 an advantage in that it has higher copolymerization activity for ethylene and α-olefins than transition metal compounds that do not have a fused thiophene heterocycle.

[0048] 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 support the transition metal compound on the surface of the support.

[0049] In addition, in the transition metal compound represented by Chemical Formula 1, M may be titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0050] In addition, in the transition metal compound represented by the chemical formula 1, 1 and Q 2 are each independently a halogen or (C1-C 20 ) alkyl, more preferably chlorine or methyl.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] Meanwhile, the amine compound represented by Chemical Formula 1 can be obtained from a precursor compound represented by Chemical Formula 5: [ka] In the above formula 5, 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.

[0055] Here, the precursor compound represented by Chemical Formula 5 can be prepared by a method including the steps of: (i) reacting a tetrahydroquinoline derivative represented by Chemical Formula 6 below with an alkyllithium, followed by adding carbon dioxide to prepare a compound represented by Chemical Formula 7; and (ii) reacting a compound represented by Chemical Formula 7 below with an alkyllithium, followed by adding a compound represented by Chemical Formula 8 below, and treating with an acid. [ka] [ka] [ka] In the above formulas 6, 7, and 8, 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.

[0056] However, in the chemical formula 6, chemical formula 7, and chemical formula 8, 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 R 4 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 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.

[0057] In the preparation of the precursor compound represented by Chemical Formula 5, step i involves reacting the tetrahydroquinoline derivative represented by Chemical Formula 6 with an alkyllithium, followed by adding carbon dioxide to convert it into the compound represented by Chemical Formula 7. This can be carried out by methods described in known literature (Tetrahedron Lett. 1985, 26, 5935; Tetrahedron 1986, 42, 2571; J. Chem. SC. Perkin Trans. 1989, 16).

[0058] In addition, in step ii, the compound represented by chemical formula 7 is reacted with alkyllithium to induce a deprotonation reaction to generate an o-lithium compound, which is then reacted with a compound represented by chemical formula 8 and treated with an acid to obtain a precursor of the transition metal compound represented by chemical formula 5.

[0059] The reaction of reacting alkyllithium with the compound represented by Chemical Formula 7 to produce an o-lithium compound can be understood from known literature (Organometallics 2007,27,6685; Korean Antibody Patent No. 2008-0065868). In the present invention, the compound represented by Chemical Formula 8 is reacted with alkyllithium to produce an o-lithium compound, and the resulting compound is treated with an acid to obtain a precursor of the transition metal compound represented by Chemical Formula 5.

[0060] The compound represented by Formula 8 can be prepared by various known methods, one of which is shown in Reaction Scheme 1 below. This method not only allows 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]

[0061] 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 5 obtained by the above method. Approximately 2 equivalents of alkyllithium are added to the precursor compound represented by Chemical Formula 5 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.

[0062] In addition, the compound represented by the formula 5 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.

[0063] The transition metal compound represented by Formula 1 prepared by the above process includes both R-type and S-type structures. Therefore, when a polymerization reaction is carried out under a catalyst composition containing both of these structures, two types of polymers having different structures and physical properties may be formed.

[0064] This is believed to be due to the difference in ethylene conversion between the R-type and S-type. Although the comonomer conversion rates of the R-type and S-type are similar, they may have different ethylene conversion rates due to differences in their steric structures. Specifically, the S-type has a larger space into which ethylene can be inserted than the R-type, requiring additional energy to form a specific sequence for the polymerization reaction. Therefore, the S-type exhibits a low ethylene conversion rate, which can result in the formation of polymer chains with a relatively high comonomer content and a thin lamellar thickness. In contrast, the R-type exhibits a high ethylene conversion rate and can form polymer chains with a relatively low comonomer content and a thick lamellar thickness.

[0065] Thus, the transition metal compound of the present invention has two stereocompounds, and thus can produce polymers with different structures even though a single catalyst is used. As shown in the structural formula below, the transition metal compound of the present invention has two compounds, an S-type stereocompound (a) and an R-type stereocompound (b), and therefore acts as two catalysts. [ka]

[0066] The R-type steric compound (b) forms polymer chains containing a low amount of comonomer, while the S-type steric compound (a) forms polymer chains containing a high amount of comonomer. The reason for this is that the R-type steric compound (b) and the S-type steric compound (a) have similar comonomer conversion rates, but the S-type steric compound (a) has a lower ethylene conversion rate, which is why it is believed that the S-type steric compound (a) forms polymer chains with a relatively higher amount of comonomer.

[0067] When the catalyst transforms into an active species, the methyl group of Ti is positioned on the opposite side due to steric hindrance caused by the sulfur (S) element of thiophene. Then, in the case of R-type steric compound (b), the space for ethylene insertion is too narrow to allow rotation, and ethylene is placed on the same plane as the methyl group (Me), as shown in the following structural formula showing the insertion structure of meso-active ethylene, allowing for easy polymerization by migration. [ka]

[0068] On the other hand, in the S-type steric compound (a), as shown in the following structural formula showing the insertion structure of the racemic active species ethylene, the insertion space of ethylene is large, so ethylene rotates and coordinates with Ti, and for polymerization, energy is required for rotation to be placed on the same plane as the methyl group (Me). Therefore, the ethylene conversion rate of the R-type steric compound (b) is lower than that of the S-type steric compound (a). [ka]

[0069] When a comonomer is inserted, its molecular size is larger than that of ethylene, so the S-type stereocompound is also placed on the same plane as the methyl group (Me) due to steric hindrance of the ligand, and the comonomer conversion rate is considered to be similar to that of the R-type stereocompound (b).

[0070] To produce an ethylene α-olefin copolymer containing two types of polymer chains with different comonomer contents in the presence of the catalyst composition, it is preferable that the S type and the R type are present in a molar ratio of 1.5:0.1 to 1:1, for example, 1.1:0.1 to 1:1. If the molar ratio is less than 1.5:0.1, the S type predominates, and a large amount of low-density polymer chains is formed, which can cause the product to become sticky. If the molar ratio exceeds 1:1, a large amount of high-density polymer chains is formed, which results in insufficient improvement in tensile elongation and low-temperature impact strength.

[0071] In the present invention, the catalyst composition may further include a promoter compound. The promoter compound activates the transition metal compound and may be an aluminoxane compound, an organoaluminum compound, or a bulky compound that activates the catalyst composition. Specifically, the promoter compound may be selected from the group consisting of compounds represented by the following chemical formulas 2 to 4:

[0072] [Chemical formula 2] -[Al(Ra)-O] n - In the above Chemical Formula 2, Each Ra is independently a halogen; or a halogen substituted or unsubstituted (C1-C 20 ) hydrocarbyl groups, n is an integer of 2 or greater.

[0073] [Chemical formula 3] Q(Rb)3 In the above Chemical Formula 3, Q is aluminum or boron; Each Rb is independently a halogen; or a halogen substituted or unsubstituted (C1-C 20 ) hydrocarbyl groups.

[0074] [Chemical formula 4] [W] + [Z(Rc)4] - In the above Chemical Formula 4, [W] + is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom attached, Z is a group 13 element, Rc is independently halogen, (C1-C 20 ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy, and phenoxy groups (C-C 20 ) aryl groups; halogens, (C1-C 20 ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy, and phenoxy groups (C1-C 20 ) alkyl.

[0075] The co-catalyst compound is included in the catalyst together with the transition metal compound represented by Formula 1 and serves to activate the transition metal compound. Specifically, in order for the transition metal compound to become an active catalyst component used in olefin polymerization, the co-catalyst compound extracts the ligands in the transition metal compound and converts them into the central metal (M 1 or M 2 ) is positively ionized, and the compound having a unit represented by Chemical Formula 2, the compound represented by Chemical Formula 3, and the compound represented by Chemical Formula 4, which can act as a counter ion having a weak bonding force, i.e., an anion, act together as co-catalysts.

[0076] The "unit" represented by Chemical Formula 2 is a structure in which n units of the structure in [ ] are linked within a compound. As long as the compound contains a unit represented by Chemical Formula 2, other structures within the compound are not particularly limited, and the compound may be a cluster-like, for example, spherical, compound in which repeating units of Chemical Formula 2 are linked to each other.

[0077] In order to enable the co-catalyst compound to exhibit a more excellent activation effect, the compound represented by Chemical Formula 2 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and a particularly preferred compound is methylaluminoxane.

[0078] The compound represented by Chemical Formula 3 is an alkyl metal compound and is not particularly limited, and non-limiting examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc. In consideration of the activity of the transition metal compound, one or more selected from the group consisting of trimethylaluminum, triethylaluminum, and triisobutylaluminum may be preferably used.

[0079] When considering the activity of the transition metal compound, the compound represented by Chemical Formula 4 is + is a cationic Lewis acid with hydrogen atoms bonded to it, then it is a dimethylanilinium cation, [W] + is a positive ionic Lewis acid, then [(C6H5)3C] + and the [Z(Rc)4] - is [B(C6F5)4] - can be preferably used.

[0080] The compound represented by chemical formula 4 is not particularly limited, but may be [W]+is a cationic Lewis acid having a hydrogen atom bonded thereto, non-limiting examples thereof include triphenylcarbenium borate, trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentafluorophenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium 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(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,It is preferably one or more selected from the group consisting of N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate, methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, and dialkylammonium.

[0081] Non-limiting examples of the dialkylammonium include di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetrakis(pentafluorophenyl)borate.

[0082] In addition, as a compound represented by chemical formula 4, [W] + When is a cationic Lewis acid, non-limiting examples thereof are preferably one or more selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salts.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] Non-limiting examples of the carbonium salt include tropylium tetrakis(pentafluorophenyl)borate, triphenylmethylcarbenium tetrakis(pentafluorophenyl)borate, and benzene(diazonium)tetrakis(pentafluorophenyl)borate.

[0087] The compounds of Formulas 1 to 4 may be used to prepare catalysts, and the following methods may be used to prepare the catalysts.

[0088] First, Q of a transition metal compound represented by chemical formula 1 1 and Q 2 When Q is a halogen, there is a method of contacting a compound represented by Chemical Formula 2. 1 and Q 2 When is an alkyl radical, the catalyst can be prepared by contacting a mixture of a transition metal compound and the compounds represented by Chemical Formulas 3 and 4, or by directly adding the compounds represented by Chemical Formulas 3 and 4 to a polymerization vessel.

[0089] The amount of the co-catalyst compound to be added may be determined taking into consideration the amount of the transition metal compound represented by Chemical Formula 1 to be added and the amount necessary to sufficiently activate the transition metal compound. The content of the co-catalyst compound may be 1:1 to 100,000, preferably 1:1 to 10,000, and more preferably 1:1 to 5,000, based on the molar ratio of the metal contained in the co-catalyst compound to 1 mole of the transition metal compound contained in the transition metal compound represented by Chemical Formula 1.

[0090] More preferably, in the first method, the compound represented by Chemical Formula 2 is contained in a molar ratio of 1:10 to 5,000, more preferably 1:50 to 1,000, and most preferably 1:100 to 1,000 relative to the transition metal compound represented by Chemical Formula 1. If the molar ratio of the compound represented by Chemical Formula 2 to the transition metal compound of Chemical Formula 1 is less than 1:10, the amount of aluminoxane may be too small, resulting in incomplete activation of the transition metal compound. If the molar ratio exceeds 1:5,000, the excess aluminoxane may act as a catalyst poison, preventing successful growth of polymer chains.

[0091] In the second method, when Q of the co-catalyst compound represented by Chemical Formula 3 is boron, it may be contained in a molar ratio of 1:1 to 100, preferably 1:1 to 10, more preferably 1:1 to 3, relative to the transition metal compound of Chemical Formula 1. When A of the co-catalyst compound represented by Chemical Formula 3 is aluminum, it may be contained in a molar ratio of 1:1 to 1000, preferably 1:1 to 500, more preferably 1:1 to 100, relative to the transition metal compound of Chemical Formula 1, although this may vary depending on the amount of water in the polymerization system.

[0092] In addition, the co-catalyst compound represented by Chemical Formula 4 may be included in a molar ratio of 1:0.5-30, preferably 1:0.7-20, and more preferably 1:1-10, relative to the transition metal compound of Chemical Formula 1. If the ratio of the co-catalyst compound represented by Chemical Formula 4 is less than 1:0.5, the amount of activator is relatively small, which may prevent complete activation of the transition metal compound and result in reduced activity of the resulting catalyst composition. If the ratio exceeds 1:30, the metal compound may be fully activated, but the remaining excess activator may result in uneconomical unit cost of the catalyst composition or reduced purity of the resulting polymer.

[0093] Meanwhile, the catalyst composition of the present invention, which includes the transition metal compound and the cocatalyst compound, may further include a support, which may be any inorganic or organic support used in the preparation of catalysts in the technical field to which the present invention pertains, without limitation.

[0094] According to the present invention, the support 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.

[0095] 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).

[0096] The transition metal compound (main catalyst compound) and the co-catalyst compound may be supported on the support by, for example, directly supporting the transition metal compound on a dehydrated support; pretreating the support with the co-catalyst compound and then supporting the transition metal compound; supporting the transition metal compound on the support and then post-treating the co-catalyst compound; or reacting the transition metal compound with the co-catalyst compound and then adding the support to the reaction.

[0097] 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.

[0098] Non-limiting examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane.

[0099] Non-limiting examples of the aromatic hydrocarbon solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene.

[0100] Non-limiting examples of the halogenated aliphatic hydrocarbon solvent include dichloromethane, trichloromethane, dichloroethane, and trichloroethane.

[0101] Furthermore, the above-mentioned supporting method is advantageous in terms of the 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.

[0102] Meanwhile, in the present invention, the ethylene α-olefin polymers produced by the polymerization process in which ethylene and an α-olefin comonomer compound are directly contacted can be produced by polymerizing the monomers under conditions in which the catalyst site is relatively insoluble and / or immobilized, so that the polymer chains are rapidly immobilized by these sites. Such immobilization can be achieved, for example, by using a solid insoluble catalyst, carrying out polymerization in a medium in which the produced polymer is generally insoluble, and by heating the polymerization reactants and product to the crystallization temperature (T c ) can be achieved by maintaining

[0103] The above-mentioned catalyst can be preferably applied to copolymerization of ethylene and α-olefin. Hereinafter, a method for producing an ethylene α-olefin copolymer, which includes a step of copolymerizing ethylene and α-olefin in the presence of the above catalyst, will be described.

[0104] Polymerization processes for ethylene and α-olefins are well known in the art and include bulk polymerization, solution polymerization, slurry polymerization, and low-pressure gas phase polymerization. Metallocene catalysts are particularly useful in known operating configurations using fixed-bed, moving-bed, or slurry processes conducted in single, series, or parallel reactors.

[0105] When the polymerization reaction is carried out in a liquid or slurry phase, a solvent or the propylene or ethylene monomer itself may be used as the medium.

[0106] Because the catalysts disclosed in the present invention exist in a homogeneous form within the polymerization reactor, they are preferably used in solution polymerization processes carried out at temperatures above the melting point of the corresponding polymer. However, as disclosed in U.S. Pat. No. 4,752,597, they may also be used in slurry or gas-phase polymerization processes in the form of a heterogeneous catalyst composition obtained by supporting the transition metal compound and cocatalyst on a porous metal oxide support. Therefore, when the catalysts of the present invention are used with an inorganic support or an organic polymer, they can also be used in slurry or gas-phase processes. In other words, the transition metal compound and cocatalyst compound may be used in a form supported on an inorganic support or an organic polymer support.

[0107] Solvents usable in the polymerization reaction may be aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents, or mixtures thereof. Non-limiting examples of the aliphatic hydrocarbon solvents include butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, and cyclohexane. Non-limiting examples of the aromatic hydrocarbon solvents include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, and chlorobenzene. In addition, examples of the halogenated aliphatic hydrocarbon solvent include, but are not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, and 1,2-dichloroethane.

[0108] As described above, the ethylene α-olefin copolymer according to the present invention can be prepared by polymerizing ethylene and an α-olefin comonomer in the presence of the catalyst composition. In this case, the transition metal compound and the cocatalyst component can be separately charged into a reactor, or the components can be premixed and charged into the reactor, and there are no particular limitations on the mixing conditions, such as the charging order, temperature, or concentration.

[0109] Meanwhile, in the polymerization reaction according to the present invention, the amount of the catalyst added is not particularly limited, as it can be determined within a range in which the polymerization reaction of the monomer can be sufficiently carried out in a slurry phase, liquid phase, gas phase, or solution process. However, the amount of the catalyst added is 10 times the concentration of the central metal M in the transition metal compound per unit volume L of the monomer. -8 It is preferably 10 to 1 mol / L, -7 〜10 -1 mol / L, more preferably 10 -7 〜10 -2 It is more preferable that the concentration is mol / L.

[0110] The polymerization reaction of the present invention may be carried out in a batch, semi-continuous, or continuous manner, preferably in a continuous manner.

[0111] The temperature conditions for the polymerization reaction of the present invention can be determined by considering the efficiency of the polymerization reaction depending on the type of reaction and reactor to be applied. However, since the temperature of the polymerization reaction affects the amount of ethylene α-olefin copolymer eluted during TGIC analysis, it is preferable to carry out the polymerization reaction at 130 to 160°C. Temperatures below 130°C or above 160°C are not preferable because the polymerization conversion decreases.

[0112] Meanwhile, the pressure conditions for the polymerization reaction 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 pressure may be 1 to 3,000 atmospheres, or 1 to 1,000 atmospheres, or 1 to 100 atmospheres, preferably 5 to 50 atmospheres.

[0113] The ethylene α-olefin copolymer of the present invention is produced by the above-mentioned method for producing an ethylene α-olefin copolymer.

[0114] The ethylene α-olefin copolymer produced by the above method uses one metallocene catalyst, but produces an ethylene α-olefin copolymer having two chains with different branched chain contents depending on the catalyst isomer. As mentioned above, the transition metal compound used as the main catalyst in the present invention is a transition metal compound in which two different stereocompounds, an R-type stereocompound and an S-type stereocompound, coexist within one transition metal, and it is believed that the S-type stereocompound transition metal compound forms a polymer chain with a high branched chain content, while the R-type stereocompound transition metal compound forms a polymer chain with a low branched chain content.

[0115] Therefore, the ethylene α-olefin copolymer of the present invention has two chain structures with different branched chain contents, which indicate the number of carbon atoms attached to side branches, and the amorphous or low-crystalline regions include polymer chains with a high branched chain content and polymer chains with a low branched chain content. The amorphous or low-crystalline polymer chains with a high branched chain content can improve low-temperature impact strength and tensile elongation. Meanwhile, while an increase in the amorphous or low-crystalline regions can decrease physical properties such as tensile strength and shrinkage, the presence of polymer chains with a low branched chain content contributes to improving physical properties such as tensile strength and shrinkage. Therefore, the ethylene α-olefin copolymer of the present invention has improved low-temperature impact strength while also exhibiting improved tensile elongation, tensile strength, and shrinkage.

[0116] When the ethylene α-olefin copolymer of the present invention is analyzed by TGIC, the elution temperatures of the amorphous or low-crystalline polymer chains with a high content of branched chains and the highly branched chains with a low content of branched chains are different, and thus the copolymer has two peaks eluted at two different temperatures.

[0117] The ethylene α-olefin copolymer of the present invention has two or more clearly separated elution peaks in the temperature range of 250K to 430K when analyzed by TGIC.

[0118] For example, the ethylene α-olefin copolymer of the present invention may exhibit a bimodal elution pattern when subjected to TGIC analysis, which means that there are two types of chains with different structures.

[0119] Specifically, the ethylene α-olefin copolymer of the present invention contains both chains with a high comonomer content and chains with a low comonomer content, and therefore exhibits a bimodal elution pattern when analyzed by TGIC.

[0120] In addition, the ethylene α-olefin copolymer may have properties in a range similar to that of conventional ethylene α-olefin copolymers, specifically, a density of 0.850 to 0.920 g / mL and a melt index (MI) of 0.1 to 50 g / 10 min.

[0121] The ethylene α-olefin copolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000 g / mol, preferably 50,000 to 950,000 g / mol, or 50,000 to 800,000, more preferably 10,000 to 300,000.

[0122] The ethylene α-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.

[0123] The ethylene α-olefin copolymer may have a density of 0.857 to 0.903 g / ml.

[0124] A resin composition containing an ethylene α-olefin copolymer and a polyolefin according to the present invention can have high impact strength, particularly high low-temperature impact strength, and low shrinkage without reducing tensile strength and tensile elongation.

[0125] More specifically, the resin composition of the present invention contains 10 to 30 wt % of the above-mentioned ethylene α-olefin copolymer of the present invention, 40 to 80 wt % of a polyolefin, and 10 to 30 wt % of an inorganic filler, based on the total weight of the resin composition.

[0126] The inorganic filler can improve the rigidity and dimensional stability of molded articles using the resin composition. The inorganic filler can be, for example, in the form of fine particles or flakes. Non-limiting examples include mica, quartz powder, titanium dioxide, silicate, and aluminosilicate. Other examples include chalk, wollastonite, montmorillonite (particularly ion-exchange-modified parent organo-form montmorillonite), talc, kaolin, zeolite, vermiculite, aluminum oxide, silica, magnesium hydroxide, aluminum hydroxide, and glass flakes. Mixtures of different inorganic fillers can also be used. Preferred examples include talc, mica, and combinations thereof. In one embodiment, the inorganic filler can be talc.

[0127] The polyolefin resin may be at least one selected from the group consisting of a random copolymer resin obtained by polymerizing one monomer selected from the group consisting of propylene, ethylene, butylene, and octane, a block copolymer resin obtained by blending polypropylene with ethylene-propylene rubber, a copolymer resin of polyethylene, ethylene vinyl acetate, and α-olefin, and a homopolypropylene resin. However, examples of usable polyolefin resins are not limited thereto.

[0128] The ethylene α-olefin copolymer may have a tensile elongation of 100 to 1000% and a tensile strength of 0.1 to 100 MPa.

[0129] A polypropylene resin composition can be produced by mixing and blending the ethylene α-olefin copolymer of the present invention with a polypropylene resin. When a molded article is produced using the polypropylene resin composition, the molded article has excellent low-temperature impact strength as well as excellent tensile elongation, tensile strength, and shrinkage properties.

[0130] The present invention will be described in more detail below with reference to specific examples. The following examples are merely illustrative examples to aid in understanding the present invention, and the scope of the present invention is not limited thereto. [Example]

[0131] 1. Synthesis example - Synthesis of transition metal compounds Synthesis Example 1 The transition metal compound 2 used as the main catalyst was synthesized from compound 1 according to the following reaction scheme 2. The specific synthesis process is as follows. [ka]

[0132] 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).

[0133] The solution obtained in step i was stirred at room temperature overnight, and then cooled to -30°C, and Ti(NMe2)2Cl2 (0.37 g, 1.79 mmol) was added to the solution in one portion (step ii).

[0134] After stirring the solution obtained in step ii for 3 hours, the solvent was completely removed using a vacuum pump to obtain a solid product, resulting in red solid compound 2 (0.59 g, 75% yield) (step iii).

[0135] 11 H NMR spectroscopy confirmed that compound 2 has S- and R-isomers, and that these two stereocompounds exist.

[0136] 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. 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%.

[0137] Synthesis Example 2 The synthesis was carried out in the same manner as in Synthesis Example 1, except that the solid product obtained in step iii above was dissolved in 8 mL of toluene, and then 1.16 g (8.96 mmol) of Me2SiCl2 was added (step iii-1).

[0138] The solution obtained in step iii-1 was stirred at 80° C. for 3 days, and then the solvent was removed using a vacuum pump, yielding 0.59 g of red solid compound 2 (yield 75%).

[0139] The resulting red solid compound 1 The 1 H NMR spectrum confirmed the presence of two stereocompounds in a 2:1 ratio.

[0140] 1 H NMR(C6D6):δ7.10(t,J=4.4Hz,1H),6.90(d,J=4.4Hz,2H),5.27 and 5.22(m,1H,NCH),2.54-2.38(m,1H,CH2),2.20-2.08(m,1H,CH2),2.36 and 2.35(s,3H),2.05 and 2.03(s,3H),1.94 and 1.93(s,3H),1.89 and 1.84(s,3H),1.72-1.58(m,2H,CH2),1.36-1.28(m,2H,CH2),1.17 and 1.14(d,J=6.4,3H,CH3)ppm. 13 C{1H} NMR(C6D6):162.78,147.91,142.45,142.03,136.91,131.12,130.70,130.10,128.90,127 .17,123.39,121.33,119.87,54.18,26.48,21.74,17.28,14.46,14.28,13.80,13.27ppm.

[0141] The S- and R-isomers of compound 2 obtained in Synthesis Examples 1 and 2 have the following structures: When a transition metal compound of compound 2 is used as the main catalyst, the ethylene conversion rate differs depending on the stereostructure of compound 2, and therefore two types of polymer chains with different comonomer contents may be formed. [ka]

[0142] 2. Production of ethylene α-olefin copolymer (1) Production of ethylene α-olefin copolymer using compound 2 obtained in Synthesis Example 1 Example 1 The inside of a high-pressure reactor (internal volume: 2.8 L, stainless steel) was purged with nitrogen at room temperature, and 1 L of normal hexane and 2.9 mmol of triisobutylaluminum were added. Then, 121.5 g of purified 1-butene was added to the alumina. Next, 135.0 g of ethylene gas (1-butene / ethylene input ratio: 0.9 by weight) was injected, and the reactor temperature was preheated to 158°C.

[0143] A mixed solution containing the solid transition metal compound (7.5 μmol) synthesized in the synthesis example and triisobutylaluminum (187.5 μmol) was mixed with a solution of dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (45.0 μmol), and the mixture was poured into a reactor, followed by carrying out a polymerization reaction for 5 minutes.

[0144] After the polymerization reaction was completed, the temperature was lowered to room temperature, the excess solvent was discharged, and the copolymer dispersed in the solvent was dried at 80° C. in a vacuum oven.

[0145] Example 2 A copolymer was produced by carrying out a polymerization reaction in the same manner as in Example 1, except that 135 g of 1-butene and 135.0 g of ethylene gas (1-butene / ethylene input ratio 1.0 by weight) were injected and the reactor temperature was preheated to 152°C.

[0146] Example 3 A copolymer was produced by carrying out a polymerization reaction in the same manner as in Example 1, except that 162 g of 1-butene and 135.0 g of ethylene gas (1-butene / ethylene input ratio 1.2 by weight) were injected and the reactor temperature was preheated to 135°C.

[0147] Comparative Example 1 A commercially available ethylene-1-butene copolymer (LG Chem, LC565) was used.

[0148] The physical properties of Examples 1 to 3 and Comparative Example 1 were measured, and the results are shown in Table 1.

[0149] The resin composition was prepared by blending 60 wt% polypropylene (Lotte Chemical Co., Ltd., JM-380), 20 wt% ethylene α-olefin copolymer of Examples 1 to 3 or Comparative Example 1, and 20 wt% talc using a tumbler mixer, and extruding the blend in a single-screw extruder with an L / D of 35 and a diameter of 40 mm at a temperature of 190 to 230°C to prepare a pelletized resin composition. The pelletized resin composition was then molded in an injection molding machine at a temperature of 190 to 240°C to prepare a physical property test specimen.

[0150] [Table 1]

[0151] Examples 1, 2, and 3 are polyolefin copolymers having the same density but different 1-butene contents, and exhibiting two elution amounts.

[0152] In Example 3, it was confirmed that the first elution temperature decreased as the 1-butene content increased, and the polymer detected at that temperature had a thick molecular weight (SCB). Based on this, a higher 1-butene content resulted in a polymer with low density and high molecular weight. This reinforced the strength properties that can be reduced at low density with high molecular weight, improving tensile strength and impact strength while maintaining tensile elongation. Under the conditions of Example 3, it is believed that the [S-type] catalyst, which has a relatively high comonomer conversion rate, was stabilized to produce low-density, high-molecular-weight polymer chains with a long lifetime.

[0153] These results are due to the copolymer being produced in the presence of a catalyst containing Compound 2. Compound 2 has R-type and S-type isomers as described below. Therefore, depending on the catalyst isomer, an ethylene α-olefin copolymer having two chains with different branched chain contents is produced. Therefore, when the ethylene α-olefin copolymer produced in the present invention is analyzed by low-temperature TGIC, it is eluted at two different temperatures, thereby confirming that two chain structures with different branched chain contents are produced.

[0154] (2) Production of ethylene α-olefin copolymer using Compound 2 obtained in Synthesis Example 2 Examples 4 to 6 The inside of a high-pressure reactor (internal volume: 2 L, stainless steel) was purged with nitrogen at room temperature, and 1 L of normal hexane and 2 mL of triisobutylaluminum were added. Next, 210 mL of 1-octene and ethylene gas were added at adjusted rates. The reactor was preheated to 140°C, and a mixed solution of 1.5 μmol of the synthesized transition metal compound 2 and triisobutylaluminum (187.5 μmol) was mixed with a solution of dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (45.0 μmol). The mixture was then injected into the reactor and polymerization reaction was carried out for 5 minutes.

[0155] After the polymerization reaction was completed, the reaction was terminated using ethanol diluted with 10% HCl, the temperature was lowered to room temperature, and excess gas was released. Next, the copolymer solution dispersed in the solvent was transferred to a container and dried in a vacuum oven at 80°C for 15 hours or more. Ethylene / 1-octene copolymers with different ratios of S-type and R-type were produced by catalyst recrystallization, and the results are shown in Table 2.

[0156] [Table 2]

[0157] As can be seen from Table 2, it can be seen that as the proportion of S-type stereocompounds in the transition metal compounds used as the main catalysts in Examples 4 to 6 increases, the area proportion of the first fraction (polymer chains with a high branched chain content) is higher than the area proportion of the second fraction (polymer chains with a low branched chain content) to produce ethylene α-olefin copolymers.

[0158] Meanwhile, in Table 2, the ratio obtained as the result of area ratio Te-1 / area ratio Te-2 corresponds to the ratio of the elution amount at the first elution temperature / the elution amount at the second elution temperature.

[0159] Although this is a single catalyst, it is believed that the properties of the polymer can be controlled by adjusting the ratio of S-type and R-type in the presence of isomers, thereby controlling the polymer structure produced.

[0160] Examples 7 and 8 The inside of a high-pressure reactor (internal volume: 2 L, stainless steel) was purged with nitrogen at room temperature, and 1 L of normal hexane and 2 mL of triisobutylaluminum were added. Next, the input amounts of 1-butene and ethylene gas were adjusted and injected, and the reactor temperature was preheated to 140°C. A mixed solution of 1.5 μmol of the synthesized transition metal compound 2 and triisobutylaluminum (187.5 μmol) was mixed with a solution of dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (45.0 μmol), and the mixture was injected into the reactor, and a polymerization reaction was carried out for 5 minutes.

[0161] After the polymerization reaction was completed, the reaction was terminated using ethanol diluted with 10% HCl, and the temperature was lowered to room temperature to release excess gas. Next, the copolymer solution dispersed in the solvent was transferred to a container and dried in a vacuum oven at 80°C for 15 hours or more to produce ethylene / 1-butene copolymers.

[0162] The physical properties of each of the prepared ethylene / 1-butene copolymers were measured, and the results are shown in Table 3.

[0163] Comparative Example 2 An ethylene-1-butene copolymer (LC175) commercially produced by LG Chem was purchased and its physical properties were measured. The results are shown in Table 3.

[0164] [Table 3]

[0165] As can be seen from Table 3, the ethylene α-olefin copolymers of Examples 7 and 8 were confirmed to contain both a first fraction (polymer chains with a high branched chain content) and a second fraction (polymer chains with a low branched chain content), which are defined by first and second peaks that are clearly distinguishable from each other in the TGIC analysis results.

[0166] In addition, the fraction ratio of the first peak region is larger than that of the second peak region, and the average SCB content is higher, indicating that more comonomer is introduced in the first peak region than in the second peak region.

[0167] This is thought to be because the transition metal compound, the main catalyst used in Examples 7 and 8, acts as two catalysts with different structures, having an R-type stereocompound and an S-type stereocompound, thereby forming polymer chains with a low elution temperature, a high branched chain content, and a high molecular weight, as well as polymer chains with a low branched chain content.

[0168] Such differences in branched chain content also lead to differences in crystallinity. Polymer chains with a high branched chain content are amorphous or have low crystallinity, while chains with a low branched chain content have high crystallinity. This means that the comonomer in the above example contains two types of chains with large differences in crystallinity due to the difference in branched chain content between them.

[0169] 3. Analysis of physical properties of copolymers and resin compositions (1) Density (g / mL) The antioxidant-treated copolymer was used to produce a sheet with a thickness of 3 mm and a radius of 2 cm in a compression mold at 180°C, which was then cooled to room temperature and measured according to ASTM D-792 (manufacturer: Toyoseiki, model name: T-001). (2) Melt index (MI) Measurement was performed in accordance with ASTM D-1238 (condition E, 190°C, 2.16g load) (manufacturer: Mirage, model name: SD-120L). (3) Low-temperature TGIC analysis The copolymer was dissolved in 1,2,4-trichlorobenzene and injected into the instrument (manufacturer: PolymerChar, model name: CFC), after which it was eluted through a GPC column at a flow rate of 1 mL / min while the temperature was increased in 5°C increments from 250 K to 430 K. The amount of polymer, SCB degree, and Mw at each temperature were measured using an infrared detector. (4) Tensile elongation Measurement was carried out using a universal material testing machine (INSTRON 4466) in accordance with the method of ASTM D638. (5) Tensile strength Measurement was carried out using a universal material testing machine (INSTRON 4466) in accordance with the method of ASTM D638. (6) IZOD impact strength (23°C) Notched impact strength was measured on 1 / 8" specimens at 23°C according to ASTM D256 method. (7) IZOD impact strength (-10°C) Notched impact strength was measured on 1 / 8" specimens at -10°C according to ASTM D256 method. (8) IZOD impact strength (-30°C) Notched impact strength was measured on 1 / 8" specimens at -30°C according to ASTM D256 method. (9) Molecular weight distribution (Mwd) Measurement was carried out at 180°C using GPC (Gel Permeation Chromatography, device name: PL-GPC220, manufacturer: Agilent) analysis using 1,2,4-trichlorobenzene solvent. (10) Melting point (Tm) A differential scanning calorimeter (DSC, device name: DSC2920, manufacturer: TA) was used. DSC was measured by equilibrating at 0°C, increasing the temperature by 10°C per minute to 200°C, decreasing the temperature by 10°C per minute to -90°C, and then increasing the temperature by 10°C per minute to 200°C. The melting point was obtained by measuring the peak region of the endothermic curve during the second temperature increase. (11) Comonomer content (wt%) 1 Analysis was performed by 1 H NMR (apparatus name: Avance DRX400, manufacturer: Bruker). (12)TGIC analysis The Polymer Char CFC (Cross-Fraction Chromatography) equipment was used. The sample to be analyzed was dissolved in 1,2,4-trichlorobenzene (2.5 mg / mL) by stirring at 150°C for 60 minutes. The dissolved sample was then loaded onto a TGIC (Temperature Gradient Interaction Chromatography) column at 1 mL / min and stabilized at 150°C for 20 minutes. The TGIC column was then cooled to 35°C at a cooling rate of 20°C / min. The temperature was increased from 35°C to 130°C in 5°C increments, and the sample was eluted on a GPC column at a flow rate of 1 mL / min. The elution time was 5 minutes, and the analysis time per fraction was 20 minutes. After passing through the GPC column, an infrared detector (IR5) was used to determine the elution volume by temperature fraction, the molecular weight of the polymer in each fraction, and the branching distribution. The peak area of ​​each fraction was confirmed using the analysis software "CFC calc," with n-heptane used as an internal standard.

[0170] The S-type / S-type+R-type ratio, S-type:R-type molar ratio, Te-1 area ratio (%), and Te-2 area ratio (%) of the copolymers obtained in Examples 1 to 8 of the present invention are summarized in Table 4 below.

[0171] [Table 4]

[0172] Although the embodiments of the present invention have been described in detail above, it should be obvious to those skilled in the art that the scope of the present invention is not limited thereto, and that various modifications and variations are possible within the scope that does not deviate from the technical idea of ​​the present invention as set forth in the claims.

Claims

1. An ethylene α-olefin copolymer containing ethylene structural units and α-olefin structural units, It has two or more distinct elution peaks in the temperature range of 250 K to 430 K when analyzed by TGIC (Thermal Gradient Interaction Chromatography); Ethylene α-olefin copolymer.

2. The ethylene α-olefin copolymer according to claim 1, wherein the copolymer has two different elution peaks, and has a first elution temperature and a second elution temperature when analyzed by TGIC, and the difference between the first elution temperature and the second elution temperature is 10 to 60 K.

3. 3. The ethylene α-olefin copolymer according to claim 2, wherein the first elution temperature is 310 to 345K and the second elution temperature is 350 to 380K.

4. 3. The ethylene α-olefin copolymer according to claim 2, wherein the ratio of the first elution temperature to the second elution temperature is 0.5 to 0.

91.

5. 3. The ethylene α-olefin copolymer according to claim 2, wherein the ratio of the amount eluted at the first elution temperature to the amount eluted at the second elution temperature is 0.5 to 7.

3.

6. 2. The ethylene α-olefin copolymer according to claim 1, which has a density of 0.857 to 0.903 g / ml.

7. The method includes polymerizing ethylene and at least one olefinic monomer in the presence of a main catalyst compound including a transition metal compound represented by the following Chemical Formula 1 and one or more co-catalyst compounds selected from compounds represented by the following Chemical Formulas 2 to 4: A method for producing an ethylene α-olefin copolymer, which comprises producing the ethylene α-olefin copolymer according to any one of claims 1 to 6: 【Chemistry 1】 (In the above Chemical Formula 1, M is a Group 4 transition metal; Q １ and Q ２ are each independently a halogen, (C １ -C ２０ ) alkyl, (C ２ -C ２０ ) alkenyl, (C ２ -C ２０ ) alkynyl, (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 ) alkylamide, (C ６ -C ２０ ) arylamide, or (C １ -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 １ -C ２０ ) alkyl; with or without acetal, ketal, or ether groups (C ２ -C ２０ ) alkenyl; with or without acetal, ketal, or ether groups (C １ -C ２０ ) alkyl(C ６ -C ２０ ) aryl; with or without acetal, ketal, or ether groups (C ６ -C ２０ ) aryl (C １ -C ２０ ) alkyl; or with or without acetal, ketal, or ether groups (C １ -C 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 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 １ -C ２０ ) alkyl; with or without acetal, ketal, or ether groups (C ２ -C ２０ ) alkenyl; with or without acetal, ketal, or ether groups (C １ -C ２０ ) alkyl(C ６ -C ２０ ) aryl; with or without acetal, ketal, or ether groups (C ６ -C ２０ ) aryl (C １ -C ２０ ) alkyl; with or without acetal, ketal, or ether groups (C １ -C ２０ ) alkylsilyl; (C １ -C ２０ ) alkoxy; or (C ６ -C ２０ ) aryloxy; １１ and R １２ or R １２ and R １３ may be linked to each other to form a ring.) [Chemical formula 2] - [Al (Ra) - O] ｎ - (In the above Chemical Formula 2, Each Ra is independently a halogen; or a halogen substituted or unsubstituted (C １ -C ２０ ) hydrocarbyl groups, n is an integer of 2 or greater), [Chemical formula 3] Q(Rb) ３ (In the above Chemical Formula 3, Q is aluminum or boron; Each Rb is independently a halogen; or a halogen substituted or unsubstituted (C １ -C ２０ ) a hydrocarbyl group, [Chemical formula 4] [W] ＋ [Z(Rc) ４ ] － (In the above Chemical Formula 4, [W] ＋ is a cationic Lewis acid; or a cationic Lewis acid having a hydrogen atom bonded thereto, Z is a group 13 element, Each Rc is independently a halogen, (C １ -C ２０ ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy, and phenoxy groups (C ６ -C ２０ ) aryl group; halogen, (C １ -C ２０ ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy, and phenoxy groups (C １ -C ２０ ) alkyl).

8. 8. The method for producing an ethylene α-olefin copolymer according to claim 7, wherein the transition metal compound is a compound in which R-type and S-type stereocompounds coexist.

9. Polypropylene and The ethylene α-olefin copolymer according to any one of claims 1 to 6, A polypropylene resin composition comprising:

10. A molded article produced from the polypropylene resin composition according to claim 9.

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