Process for the preparation of organozinc compounds, chain transfer agents, block copolymers and resin compositions

Abstract

The present invention relates to a chain transfer agent comprising an organic zinc compound, a method for preparing the same, and a method for preparing a block copolymer using the same. The chain transfer agent is prepared by a preparation method comprising preparing a Grignard reagent containing a styrene residue and reacting the prepared Grignard reagent with an alkyl zinc alkoxide as a zinc compound, contains 96 wt% or more of the target compound without a catalyst poison and a by-product. A block copolymer polymerized using the chain transfer agent and a resin composition comprising the same have excellent mechanical properties.

Description

Technical Field

[0001] This application claims the rights of Korean Patent Application No. 10-2020-0096160 filed on July 31, 2020 and Korean Patent Application No. 10-2021-0100045 filed on July 29, 2021, the disclosures of which are incorporated herein by reference in their entirety.

[0002] This invention relates to a method for preparing organozinc compounds, chain transfer agents, block copolymers, and resin compositions. Specifically, it relates to a method for preparing organozinc compounds containing styrene residues that can be used in coordination chain transfer polymerization (CCTP) in the preparation of block copolymers; a method for preparing organozinc compounds that can be synthesized as a single compound without side reactions, thereby exhibiting excellent synthetic and polymerization reproducibility; a chain transfer agent comprising the organozinc compound thus prepared; a block copolymer obtained by polymerization using the compound; and a resin composition comprising the block copolymer. Background Technology

[0003] The synthesis and application of block copolymers is a major topic in polymer-related fields. In recent years, block copolymers based on polyolefins (PO) have attracted much attention. A representative block copolymer is PS-block-polybutadiene-block-PS (SBS, where PS is polystyrene), as shown in Reaction Formula 1 below, which is produced globally at a scale of 2 million tons per year via controlled anionic polymerization. Hydrogenation of the intermediate block segment of SBS (i.e., the polybutadiene block) provides a value-added product, PS-block-poly(ethylene-co-1-butene)-block-PS (SEBS), with a commercial scale of 300,000 tons per year globally.

[0004] [Reaction Formula 11]

[0005]

[0006] SBS excels in weather resistance, heat resistance, abrasion resistance, impact resistance, adhesion, transparency, and recyclability, leading to a continuously growing demand for SEBS. However, polymer hydrogenation requires a catalytic reaction in the molten state, inevitably involving complex processes such as catalyst removal. Consequently, SEBS is at least three times more expensive than SBS. This high resin price has become an obstacle to market expansion.

[0007] Furthermore, the inability to heat-trease SEBS is also an obstacle to market expansion. Commercial-grade SEBS is prepared through controlled anionic polymerization, resulting in a very narrow molecular weight distribution, thus preventing it from flowing in the molten state. Additionally, SEBS is typically used in combination with other polymers rather than alone. While most bulk polymers are granular and therefore readily available, SEBS is only available in block powder form, making it less convenient to supply.

[0008] Therefore, as a method to solve the aforementioned problems in the preparation of SEBS, Korean Patent Publication No. 1829382 (Patent Document 1) proposes a one-pot synthesis of triblock copolymers similar to SEBS. Specifically, Patent Document 1 discloses the growth of polyolefin (PO) chains from a diorganozinc compound having styrene residues via coordination chain transfer polymerization (CCTP), followed by the growth of polystyrene (PS) chains from Zn-C binding sites and styrene residues via one-pot anionic polymerization. Here, Patent Document 1 discloses a method for preparing a diorganozinc compound via the hydroboration of divinylbenzene as shown in Formula 2.

[0009] [Reaction 2]

[0010]

[0011] However, when preparing organozinc compounds via the hydroboration of divinylbenzene according to Formula 2 of Patent Document 1, an excess of triethylborane (Et3B) and diethylzinc (Et2Zn) should be used. However, triethylborane and diethylzinc are highly flammable, posing a significant hazard. Furthermore, triethylborane is continuously generated as a reaction intermediate; if it remains in the CCTP stage, it will act as a catalyst poison and must be continuously removed.

[0012] Furthermore, when preparing organozinc compounds via the hydroboration of divinylbenzene as described in Formula 2 above, there is a problem of low purity of the divinylbenzene used as a reactant. In particular, since divinylbenzene typically contains about 20 mol% ethylvinylbenzene, polystyrene cannot grow from the ethyl group via anionic polymerization when using organozinc compounds for CCTP, which leads to the formation of diblock copolymers.

[0013] Furthermore, since divinylbenzene has two vinyl groups, the simultaneous hydroboration of both vinyl groups inevitably produces dimers, trimers, etc., containing more than two zinc groups. Therefore, to reduce the formation of dimers, trimers, etc., divinylbenzene should be used in large quantities, approximately three times more than triethylborane.

[0014] Furthermore, considering all the aforementioned problems, when preparing organozinc compounds, it is difficult to ensure synthetic reproducibility because the hydroboration of divinylbenzene is an equilibrium reaction. Moreover, the prepared organozinc compounds are obtained in the form of a mixture comprising an average of approximately 82.4 mol% of compounds with vinyl-terminated ends, approximately 9.2 mol% of compounds with ethyl-terminated ends, and approximately 8.5 mol% of compounds as dimers. Even if only the compounds with vinyl-terminated ends are selectively purified, the terminal vinyl groups in the prepared organozinc compounds are present at the ortho, meta, and para positions because divinylbenzene is a mixture of ortho, meta, and para isomers. This makes it impossible to guarantee that the block copolymers prepared using the prepared organozinc compounds for CCTP will all have identical block linkage structures.

[0015] Furthermore, as shown in Patent Document 2, Korean Patent Publication No. 1732418 (Patent Document 2) also proposes a one-pot synthesis of triblock copolymers similar to SEBS. Specifically, Patent Document 2 discloses the growth of polyolefin (PO) chains from a diorganozinc compound having α-methylstyrene residues via coordination chain transfer polymerization (CCTP), followed by the growth of polystyrene (PS) chains from Zn-C binding sites and α-methylstyrene residues via one-pot anionic polymerization. Here, Patent Document 2 discloses a method for preparing a Grignard reagent by introducing magnesium powder into 1-chloromethyl-4-isopropenylbenzene, followed by a metathesis reaction with zinc chloride (ZnCl2) to prepare a diorganozinc compound having α-methylstyrene residues.

[0016] However, when preparing organozinc compounds via the reaction of Grignard reagents with zinc chloride, as in Patent Document 2, impurities containing magnesium and chlorine (Mg(α-methylstyrene residue)2, (α-methylstyrene residue)-Mg-Cl, and (α-methylstyrene residue)-Zn-Cl) may remain as catalyst poisons. Therefore, these impurities must be removed several times by recrystallization with an organic solvent such as hexane. Consequently, the reproducibility of the synthesis quality cannot be guaranteed for each attempt. Furthermore, for CCTP to proceed, the organozinc compound should be used in excess relative to the catalyst (e.g., a hafnium complex). However, as mentioned above, even trace amounts of impurities in the organozinc compound can deactivate the catalyst, sometimes preventing CCTP from being performed.

[0017] Furthermore, in the organozinc compounds containing α-methylstyrene residues disclosed in Patent Document 2, during anionic polymerization, the α-methylstyrene residues inevitably suffer from steric hindrance caused by the α-methyl group, resulting in lower anionic initiation efficiency compared to styrene residues. Therefore, when anionic polymerization is carried out in the same polymerization environment, PS chain growth is not promoted on the α-methylstyrene residue side, and PS homopolymers are generated at a ratio of 40% to 50% by weight. This becomes a factor inhibiting the formation of triblock copolymers.

[0018] Existing technical documents

[0019] [Patent Literature]

[0020] (Patent Document 1) KR10-1829382B1

[0021] (Patent Document 2) KR10-1732418B2 Summary of the Invention

[0022] Technical issues

[0023] One aspect of the present invention provides a method for preparing an organozinc compound containing styrene residues, which, when preparing a block copolymer, can be used in coordination chain transfer polymerization (CCCP) without the use of triethylborane, thereby ensuring operational safety. It is synthesized as a single compound and therefore does not contain by-reaction products such as dimers. In addition, it does not contain chlorine-containing impurities that may act as catalyst poisons, and it also helps to remove magnesium-containing impurities that may act as catalyst poisons.

[0024] Another aspect of the present invention provides a chain transfer agent for preparing block copolymers by coordination chain transfer polymerization, comprising an organozinc compound prepared according to the method for preparing the organozinc compound, thus exhibiting excellent synthetic reproducibility and polymerization reproducibility.

[0025] Another aspect of the present invention provides a polystyrene-polyolefin block copolymer prepared by coordination chain transfer polymerization and anionic polymerization using the chain transfer agent, thereby exhibiting a wide molecular weight distribution and excellent mechanical properties.

[0026] Another aspect of the present invention provides a resin composition comprising the block copolymer, thereby exhibiting excellent polypropylene dispersibility and therefore excellent mechanical properties.

[0027] Technical means

[0028] According to one aspect of the present invention, a method for preparing an organozinc compound is provided, the method comprising preparing a Grignard reagent containing styrene residues, reacting the prepared Grignard reagent with a zinc compound to prepare an organozinc compound represented by Formula 1, wherein the zinc compound is an alkyl zinc alkoxide.

[0029] [Formula 1]

[0030]

[0031] In Equation 1 above, R 1 and R 3 Each is independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 Alkylene or -SiR with 1 to 10 carbon atoms 4 R 5 - and R 4 and R 5 Each is an alkyl group with 1 to 10 carbon atoms.

[0032] According to another aspect of the present invention, a chain transfer agent comprising an organozinc compound represented by Formula 1 above is provided, wherein the chain transfer agent comprises more than 96 mol% of the organozinc compound represented by Formula 1 above.

[0033] According to another aspect of the present invention, a block copolymer comprising aromatic vinyl polymer blocks and olefin polymer blocks is provided, wherein the block polymers have a molecular weight distribution (Mw / Mn) of 1.2 or higher.

[0034] According to another aspect of the present invention, a resin composition comprising the block copolymer and polypropylene is provided.

[0035] Beneficial effects

[0036] When preparing organozinc compounds according to the method of the present invention, triethylborane is not used, thereby ensuring work safety and having the following effects: synthesizing a single compound that is free from by-reaction products (such as dimers), free from chlorine-containing impurities that may become catalyst poisons, and promoting the removal of magnesium-containing impurities that may become catalyst poisons.

[0037] Furthermore, the chain transfer agent comprising the organozinc compound prepared by the method of preparing organozinc compounds according to the present invention exhibits excellent synthetic reproducibility and polymerization reproducibility.

[0038] Furthermore, the block copolymers prepared by coordination chain transfer polymerization and anionic polymerization using the chain transfer agent of the present invention have a wide molecular weight distribution and excellent mechanical properties.

[0039] Furthermore, the resin composition of the present invention contains the above-mentioned block copolymer, thereby exhibiting excellent polypropylene dispersibility and thus excellent mechanical properties. Attached Figure Description

[0040] Figure 1 GPC curves of polymers (i.e., poly(ethylene-co-1-hexene)) based on chain transfer coordination polymerization and block copolymers based on anionic polymerization according to Examples 1 to 5 of the present invention are shown.

[0041] Figure 2 These are TEM images of the block copolymers (SEHS) of Examples 1-5 and the block copolymers (SEBS) of Comparative Examples 1-4 of the present invention;

[0042] Figure 3 These are SEM images of the resin compositions of each block copolymer region of Examples 2-5 to 2-7 and Comparative Examples 2-4 to 2-6 after being etched with xylene. Detailed Implementation

[0043] The invention will be described in more detail below to facilitate understanding of it.

[0044] It should be understood that the words or terms used in the specification and claims of this invention should not be construed as having the meanings defined in commonly used dictionaries. It will be further understood that, based on the principle that the inventors may appropriately define the meanings of words or terms to best interpret the invention, the words or terms should be interpreted as having meanings consistent with their meanings in the context of the related art and in the technical concept of the invention.

[0045] In this invention, the term "monomer unit" can refer to the component, structure, or material itself derived from the monomer. A specific example can be a repeating unit formed in the polymer by a monomer introduced during polymer polymerization and participating in the polymerization reaction.

[0046] As used herein, the term "polymer" can refer to a homopolymer formed by the polymerization of a single monomer, and the term "copolymer" can refer to a copolymer formed by the polymerization of two or more comonomers. Furthermore, unless otherwise specified as "block copolymer," "copolymer" can refer to a "random copolymer" in which two or more comonomers are randomly copolymerized.

[0047] As used herein, the term "block" can refer to a group of repeating units consisting only of repeating units derived from the same monomer or repeating units derived from the same comonomer, since only the same monomer or the same comonomer participates in the polymerization reaction in the copolymer. As specific examples, aromatic vinyl polymer blocks can refer to blocks formed only of aromatic vinyl monomer units, and olefin polymer blocks can refer to blocks formed only of more than one type of olefin monomer unit.

[0048] As used herein, the term "anionic reactive polymer" refers to a polymer formed through anionic polymerization, and may also refer to a polymer that is capable of further polymerization or reaction due to the anionic state of one end of the polymer. Specific examples may include reactive anionic polymers.

[0049] As used herein, the term "composition" includes not only reaction products and decomposition products formed from the materials of the corresponding composition, but also mixtures of materials comprising the corresponding composition.

[0050] Preparation of organozinc compounds

[0051] This invention provides a method for preparing organozinc compounds.

[0052] According to one embodiment of the present invention, a method for preparing an organozinc compound includes: preparing a Grignard reagent containing styrene residues, reacting the prepared Grignard reagent with a zinc compound to prepare an organozinc compound represented by Formula 1, wherein the zinc compound may be an alkyl zinc alkoxide.

[0053] [Formula 1]

[0054]

[0055] In Equation 1 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 - and R 4 and R 5 Each can be an alkyl group having 1 to 10 carbon atoms.

[0056] According to one embodiment of the present invention, in formula 1 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 3 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 3 carbon atoms. 4 R 5 - and R 4 and R 5 Each can be an alkyl group having 1 to 3 carbon atoms.

[0057] According to one embodiment of the present invention, in formula 1 above, R 1 and R 3 Each can be an independent single bond or an alkylene group with one carbon atom, R 2 It can be an alkylene group with 1 carbon atom or -SiR 4R 5 - and R 4 and R 5 Each is an alkyl group with 1 carbon atom.

[0058] According to one embodiment of the present invention, the organozinc compound represented by Formula 1 above may be one or more selected from the group consisting of organozinc compounds represented by Formulas 1-1 to 1-4 below, and may preferably be any one of Formulas 1-3 and 1-4.

[0059] [Equation 1-1]

[0060]

[0061] [Equation 1-2]

[0062]

[0063] [Equation 1-3]

[0064]

[0065] [Equations 1-4]

[0066]

[0067] According to one embodiment of the present invention, the organozinc compound represented by Formula 1 prepared according to the method for preparing organozinc compounds is synthesized as a single compound, thus excluding by-reaction products (such as dimers) and, moreover, excluding chlorine-containing impurities that may act as catalyst poisons, such as organozinc chloride (R-Zn-Cl). Furthermore, when the organozinc compound represented by Formula 1 is prepared according to the method for preparing organozinc compounds, the organozinc compound is synthesized as a single compound, thus exhibiting excellent synthetic reproducibility. Meanwhile, in the preparation of the organozinc compound, in order to avoid including by-reaction products and impurities in the present invention, it may be important to select Grignard reagents and zinc compounds containing styrene residues.

[0068] According to one embodiment of the present invention, a Grignard reagent containing styrene residues can be represented by the following formula 2.

[0069] [Equation 2]

[0070]

[0071] In equation 2 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 -, R4 and R 5 Each can be an alkyl group with 1 to 10 carbon atoms, and X can be a halogen group.

[0072] According to one embodiment of the present invention, in formula 2 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 3 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 3 carbon atoms. 4 R 5 -, R 4 and R 5 Each can be an alkyl group with 1 to 3 carbon atoms, and X can be a halogen group.

[0073] According to one embodiment of the present invention, in formula 2 above, R 1 and R 3 Each can be an independent single bond or an alkylene group with one carbon atom, R 2 It can be an alkylene group with 1 carbon atom or -SiR 4 R 5 -, R 4 and R 5 Each can be an alkyl group with 1 carbon atom, and X can be a halogen group selected from the group consisting of Cl, Br and I.

[0074] According to one embodiment of the present invention, the Grignard reagent containing styrene residues represented by Formula 2 above can be one of the Grignard reagents containing styrene residues represented by Formulas 2-1 to 2-4 below.

[0075] [Equation 2-1]

[0076]

[0077] [Equation 2-2]

[0078]

[0079] [Equation 2-3]

[0080]

[0081] [Equation 2-4]

[0082]

[0083] According to one embodiment of the present invention, the Grignard reagent containing styrene residues represented by Formula 2 above can be replaced by a halogen (-X) with R. 1 It is prepared by reacting halides with magnesium (specifically magnesium powder or magnesium metal).

[0084] According to one embodiment of the present invention, the Grignard reagent containing styrene residues represented by Formula 2 above can be prepared by reacting the compound represented by Formula 3 below with magnesium (specifically magnesium powder or metallic magnesium).

[0085] [Formula 3]

[0086]

[0087] In equation 3 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 -, R 4 and R 5 Each can be an alkyl group with 1 to 10 carbon atoms, and X can be a halogen group.

[0088] According to one embodiment of the present invention, in formula 3 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 3 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 3 carbon atoms. 4 R 5 -, R 4 and R 5 Each can be an alkyl group with 1 to 3 carbon atoms, and X can be a halogen group.

[0089] According to one embodiment of the present invention, in formula 3 above, R 1 and R 3 Each can be an independent single bond or an alkylene group with one carbon atom, R 2 It can be an alkylene group with 1 carbon atom or -SiR 4 R 5 -, R 4 and R 5 Each can be an alkyl group with 1 carbon atom, and X can be a halogen group selected from the group consisting of Cl, Br and I.

[0090] According to one embodiment of the present invention, the compound represented by Formula 3 above may be one of the compounds selected from the group consisting of compounds represented by Formulas 3-1 to 3-4 below.

[0091] [Equation 3-1]

[0092]

[0093] [Equation 3-2]

[0094]

[0095] [Equation 3-3]

[0096]

[0097] [Equation 3-4]

[0098]

[0099] According to one embodiment of the present invention, in preparing the Grignard reagent containing styrene residues represented by Formula 2 above, the reaction of the compound represented by Formula 3 with magnesium powder or magnesium metal can be carried out at a molar ratio in which magnesium powder or magnesium metal is in excess to 1 mole of the compound represented by Formula 3, i.e., a molar ratio greater than 1 mole. In this case, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of the compound represented by Formula 3 above can be converted into the Grignard reagent containing styrene residues represented by Formula 2 above.

[0100] According to one embodiment of the present invention, the reaction between the compound represented by Formula 3 and magnesium powder or magnesium metal can be carried out in a molar ratio greater than 1:1 to 1:10, greater than 1:1 to 1:5, greater than 1:1 to 1:2, or 1:1.01 to 1:1.60. Within this range, the Grignard reagent containing styrene residues, represented by Formula 2, exhibits high conversion rate, and the residual magnesium content after the reaction can be minimized, thereby facilitating the removal of residual magnesium powder or metallic magnesium.

[0101] According to one embodiment of the invention, the zinc compound needs to be a zinc compound that, during the preparation of the organozinc compound, is based on zinc and capable of inducing the substitution of zinc with two organic groups of the same type. Therefore, as described above, zinc chloride (ZnCl2) can be readily considered. However, when zinc chloride is used as the zinc compound, there is a problem of residual chlorine-containing impurities (e.g., alkyl zinc chloride) that could potentially become catalyst poisons. Therefore, the present invention uses alkyl zinc alkoxides as the zinc compound.

[0102] According to one embodiment of the present invention, the alkyl group of the alkyl zinc alkoxide can be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or an ethyl group, and the alkoxide group can be an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a methoxy group. As a specific example, the zinc compound can be ethylmethoxide zinc.

[0103] According to one embodiment of the present invention, alkyl zinc alkoxides can be prepared from dialkyl zinc. As a specific example, alkyl zinc alkoxides can be prepared by in-situ reaction of dialkyl zinc with an alcohol. In this case, the alkyl group of the dialkyl zinc can be the same as the alkyl group of the aforementioned alkyl zinc alkoxide, and the alcohol can be an alcohol with a hydrogen atom bonded to the alkoxide group of the aforementioned alkyl zinc alkoxide.

[0104] According to one embodiment of the present invention, when an alkyl zinc alkoxide is used as the zinc compound, a magnesium halide alkoxide is generated during the reaction of the Grignard reagent with the zinc compound. This halide is an insoluble salt, which facilitates filtration to prevent impurity residue.

[0105] According to one embodiment of the present invention, the reaction between the Grignard reagent and the zinc compound can be carried out in molar ratios of 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1.5:1 to 1:1.5, or 1:1. Within this range, the following effects are achieved: the synthesis of a single compound is free from by-reaction products such as dimers, free from chlorine-containing impurities that may act as catalyst poisons, and facilitates the removal of magnesium-containing impurities that may act as catalyst poisons.

[0106] According to one embodiment of the present invention, all steps and all reactions of the method for preparing zinc compounds can be carried out in an organic solvent, and the reaction temperature and reaction pressure can be adjusted according to the purpose of improving yield and purity.

[0107] In the method for preparing zinc compounds according to embodiments of the present invention, typical borane compounds containing styrene residues are replaced by Grignard reagents containing styrene residues, and alkyl zinc or zinc chloride is replaced by alkyl zinc alkoxides, thereby completely removing catalyst poisons.

[0108] Furthermore, by improving the above method, unlike the prior art which yields a mixture of dimers, trimers and terminal saturated zinc compounds, a single compound with fully retained terminal vinyl groups can be obtained as a monomer. This not only improves the storage stability of the zinc compound but also enhances the physical properties of the final copolymer, thereby significantly reducing the amount of non-triblock diblock copolymers produced.

[0109] Chain transfer agent

[0110] This invention provides a chain transfer agent comprising an organozinc compound prepared by the method for preparing organozinc compounds. As a specific example, the chain transfer agent can be a chain transfer agent used for preparing block copolymers via coordination chain transfer polymerization.

[0111] According to one embodiment of the present invention, the chain transfer agent comprises an organozinc compound represented by Formula 1, wherein the chain transfer agent comprises more than 96 mol% of the organozinc compound represented by Formula 1, and preferably, may exclude by-products other than the organozinc compound represented by Formula 1.

[0112] [Formula 1]

[0113]

[0114] In Equation 1 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 - and R 4 and R 5 Each can be an alkyl group having 1 to 10 carbon atoms.

[0115] According to one embodiment of the present invention, the chain transfer agent is prepared by the method for preparing organozinc compounds. Therefore, the organozinc compound represented by Formula 1 above can be the same as the organozinc compound represented by Formula 1 described in the above method for preparing organozinc compounds.

[0116] According to one embodiment of the present invention, the chain transfer agent preferably comprises 97 mol% or more, more preferably 98 mol% or more, or 99 mol% or more of the organozinc compound of Formula 1 above, and most preferably does not include by-products other than the organozinc compound. This means that, apart from the organozinc compound represented by Formula 1, it does not include by-products such as dimers or impurities containing chlorine or magnesium.

[0117] That is, the chain transfer agent may consist only of the organozinc compound represented by Formula 1 above. As a specific example, the chain transfer agent is prepared according to the method for preparing the organozinc compound, thus synthesizing a single compound as the organozinc compound represented by Formula 1 above, and excluding by-reaction products (such as dimers), further excluding chlorine-containing impurities that could act as catalyst poisons, and also excluding magnesium-containing impurities that could act as catalyst poisons, because all impurities are removed therefrom. Therefore, the chain transfer agent exhibits excellent polymerization reproducibility during coordination chain transfer polymerization for the preparation of block copolymers, and processability can be improved by inducing a high molecular weight distribution during the preparation of block copolymers.

[0118] Block copolymers and their preparation methods

[0119] This invention provides a block copolymer obtained by polymerization using the above-mentioned chain transfer agent and a method for preparing the same.

[0120] According to one embodiment of the present invention, the block copolymer comprises aromatic vinyl polymer blocks and olefin polymer blocks, wherein the molecular weight distribution (Mw / Mn) of the block polymer can be 1.2 or higher.

[0121] According to one embodiment of the present invention, the block copolymer may be a triblock copolymer comprising aromatic vinyl polymer blocks, olefin polymer blocks, and aromatic vinyl polymer blocks. A specific example may be polystyrene-block-poly(ethylene-co-olefin)-block-polystyrene.

[0122] According to one embodiment of the invention, the block copolymer may contain repeating units represented by Formula 6 below.

[0123] [Formula 6]

[0124]

[0125] In equation 6 above, R 1 and R 3 Each can be an independent single bond or an alkylene group with 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 -, R 4 and R 5 Each can be an alkyl group having 1 to 10 carbon atoms, PO is an olefin polymer block, PS is an aromatic vinyl polymer block, and * is a portion connected in the repeating unit or the end of the repeating unit, wherein, when * is the end of the repeating unit, * can be a functional group derived from hydrogen or an anionic polymerization initiator.

[0126] According to one embodiment of the present invention, the aromatic vinyl polymer block can be a block formed by polymerization of aromatic vinyl monomers. The aromatic vinyl monomers used to form the aromatic vinyl polymer block can be selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene. A specific example is styrene.

[0127] According to one embodiment of the present invention, the content of aromatic vinyl polymer blocks, based on the total content of the block copolymer, can be 10% to 60% by weight, 15% to 40% by weight, or 20% to 35% by weight. Within this range, the block copolymer exhibits excellent mechanical properties and processability.

[0128] According to one embodiment of the present invention, the olefin polymer block (i.e., poly(ethylene-co-olefin)) may include ethylene monomer units and α-olefin monomer units having 3 to 20 carbon atoms. Specific examples may include ethylene monomer units and α-olefin monomer units having 6 to 8 carbon atoms. As described above, when the olefin polymer block comprises ethylene monomer units and α-olefin monomer units having 3 to 20 carbon atoms or 6 to 8 carbon atoms, the block copolymer exhibits excellent weather resistance, heat resistance, abrasion resistance, impact resistance, adhesion, transparency, and recyclability, thus improving the mechanical properties of resin compositions containing the block copolymer.

[0129] According to one embodiment of the present invention, the α-olefin monomer used to form an α-olefin monomer unit having 3 to 20 carbon atoms may be one or more 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-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene.

[0130] According to one embodiment of the present invention, the α-olefin monomer used to form an α-olefin monomer unit having 6 to 8 carbon atoms may be one or more selected from the group consisting of 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 4,4-dimethyl-1-pentene, and 3,4-dimethyl-1-hexene. A specific example may be 1-hexene.

[0131] According to one embodiment of the present invention, the content of olefin polymer blocks, based on the total content of the block copolymer, can be 40% to 90% by weight, 60% to 85% by weight, or 65% to 80% by weight. Within this range, the block copolymer exhibits excellent mechanical properties and processability.

[0132] According to one embodiment of the present invention, when the olefin polymer block contains ethylene monomer units, the content of ethylene monomer units can be 20% to 70% by weight, 30% to 60% by weight, or 35% to 50% by weight, based on the total content of the block copolymer. Within this range, the block copolymer exhibits excellent mechanical properties and processability.

[0133] According to one embodiment of the present invention, when the olefin polymer block includes α-olefin monomer units, the content of α-olefin monomer units can be 10% to 50% by weight, 15% to 45% by weight, or 20% to 40% by weight, depending on the total content of the block copolymer. Within this range, the block copolymer exhibits excellent mechanical properties and processability.

[0134] According to one embodiment of the present invention, the molecular weight distribution (Mw / Mn) of the block copolymer can be 1.2 or more, 1.2 to 5.0, 1.5 to 4.0, 1.5 to 3.0, 1.5 to 2.5, or 1.6 to 2.2. Within this range, the block copolymer exhibits excellent mechanical properties and processability. Here, the molecular weight distribution (Mw / Mn) may refer to the polydispersity index (PDI).

[0135] According to one embodiment of the present invention, the weight-average molecular weight (Mw) of the block copolymer can be 20,000 g / mol to 1,000,000 g / mol, 30,000 g / mol to 800,000 g / mol, 40,000 g / mol to 500,000 g / mol, 50,000 g / mol to 400,000 g / mol, or 53,000 g / mol to 357,000 g / mol. Here, the weight-average molecular weight can be measured using polystyrene (PS) standard gel permeation chromatography (GPC).

[0136] According to one embodiment of the present invention, the tensile strength of the block copolymer can be 5 MPa to 50 MPa, 6 MPa to 40 MPa, or 7 MPa to 35 MPa. Within this range, it has the effect of ensuring the mechanical properties of the resin composition containing the block copolymer.

[0137] According to one embodiment of the invention, the elongation at break of the block copolymer is 1000%–3000%, 1200%–2800%, or 1300%–2500%. Within this range, it has the effect of ensuring the mechanical properties of the resin composition containing the block copolymer.

[0138] According to one embodiment of the present invention, a method for preparing a block copolymer includes: (S10) polymerizing one or more olefin monomers in the presence of a chain transfer agent using a transition metal catalyst to prepare an olefin polymer block intermediate represented by Formula 4; (S20) introducing an anionic polymerization initiator and an aromatic vinyl monomer and polymerizing them in the presence of the olefin polymer block intermediate represented by Formula 4 prepared in step (S10) to prepare a block copolymer intermediate represented by Formula 5; and (S30) obtaining a block copolymer containing repeating units represented by Formula 6 from the block copolymer intermediate represented by Formula 5 prepared in step (S20), wherein the chain transfer agent contains an organozinc compound represented by Formula 1, and the chain transfer agent may not contain by-reaction products other than the organozinc compound represented by Formula 1.

[0139] [Formula 1]

[0140]

[0141] In Equation 1 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 - and R 4 and R 5 Each can be an alkyl group having 1 to 10 carbon atoms.

[0142] [Formula 4]

[0143]

[0144] In equation 4 above, R 1 and R 3 Each can be an independent single bond or an alkylene group having 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 - and R 4 and R 5 Each can be an alkyl group with 1 to 10 carbon atoms, and PO can be an olefin polymer block.

[0145] [Formula 5]

[0146]

[0147] In equation 5 above, R 1 and R 3 Each can be an independent single bond or an alkylene group with 1 to 10 carbon atoms, R2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 -, R 4 and R 5 Each can be an alkyl group having 1 to 10 carbon atoms, PO is an olefin polymer block, PS is an aromatic vinyl polymer block, and * is a portion connected in the repeating unit or the end of the repeating unit, wherein, when * is the end of the repeating unit, * can be a functional group derived from hydrogen or an anionic polymerization initiator.

[0148] [Formula 6]

[0149]

[0150] In equation 6 above, R 1 and R 3 Each can be an independent single bond or an alkylene group with 1 to 10 carbon atoms, R 2 It can be an alkylene group or -SiR with 1 to 10 carbon atoms. 4 R 5 -, R 4 and R 5 Each can be an alkyl group having 1 to 10 carbon atoms, PO is an olefin polymer block, PS is an aromatic vinyl polymer block, and * is a portion connected in the repeating unit or the end of the repeating unit, wherein, when * is the end of the repeating unit, * can be a functional group derived from hydrogen or an anionic polymerization initiator.

[0151] According to one embodiment of the present invention, the above step (S10) may be a step of using a transition metal catalyst to grow an olefin polymer chain from a chain transfer agent containing an organozinc compound represented by Formula 1 above via coordination chain transfer polymerization (CCTP) to prepare an olefin polymer block intermediate.

[0152] According to one embodiment of the present invention, the transition metal catalyst is a catalyst for growing olefin polymers via coordination chain transfer polymerization, and may be a catalyst composition comprising a transition metal catalyst as a main catalyst and a co-catalyst, wherein the co-catalyst may be an organoaluminum or boron compound. As a specific example, the catalyst composition comprising the transition metal catalyst may be a homogeneous (metallocene) catalyst or a heterogeneous (Ziegler) catalyst, more specifically, it may be a homogeneous (metallocene) catalyst.

[0153] According to one embodiment of the present invention, the transition metal catalyst can be [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] -The activated pyridylaminohafnium complex, in this case, has the effect of preventing polyolefin chains that are not bonded to zinc by the chain transfer agent.

[0154] According to one embodiment of the present invention, the one or more olefin monomers may be the same as the olefin monomers used to form the olefin polymer blocks described above. Specific examples may include one or more α-olefin monomers selected from the group consisting of ethylene monomers and α-olefin monomers having 3 to 20 carbon atoms. Furthermore, the olefin monomer may be introduced to satisfy the content requirements of the aforementioned olefin polymer blocks.

[0155] According to one embodiment of the present invention, when one or more olefin monomers selected from ethylene monomers and α-olefin monomers having 3 to 20 carbon atoms are introduced as olefin monomers, the ethylene monomers can be introduced in gas phase form, and the α-olefin monomers having 3 to 20 carbon atoms can be introduced in gas phase or liquid phase form.

[0156] According to one embodiment of the present invention, step (S20) may be a step in which an anionic polymerization initiator and an aromatic vinyl monomer are introduced and polymerized in the presence of the olefin polymer block intermediate represented by Formula 4 prepared in step (S10), and the anionic polymerization is initiated by the Zn-C bonding sites and styrene residues of the olefin polymer block intermediate represented by Formula 4 to grow the aromatic vinyl monomer, thereby preparing the block copolymer intermediate represented by Formula 5. Here, step (S20) may be performed in one pot with step (S10).

[0157] According to one embodiment of the present invention, the anionic polymerization initiator may be an initiator composition comprising an organolithium compound, a specific example of which may be an initiator composition comprising an organolithium compound and a triamine compound.

[0158] According to one embodiment of the present invention, the organolithium compound may be one or more selected from the group consisting of n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyllithium, vinyllithium, phenyllithium, benzyllithium, pentylallyllithium, and (trimethylsilyl)methyllithium. In this case, it has the effect of initiating anionic polymerization from the Zn-C bond site of the olefin polymer block intermediate and styrene residues and can effectively grow aromatic vinyl monomers. Furthermore, based on the molar ratio of the chain transfer agent to the organolithium compound, the organolithium compound may be introduced at a molar ratio of 1:0.1–2.0, 1:0.5–1.5, or 1:0.8–1.2.

[0159] According to one embodiment of the present invention, the triamine compound is an additive for initiating anionic polymerization from the Zn-C bonding sites and styrene residues of olefinic polymer block intermediates and efficiently growing aromatic vinyl monomers. It has the effect of efficiently growing aromatic vinyl monomers when included in the initiator composition together with an organolithium compound. As a specific example, the triamine compound may be N,N,N',N”,N”-pentamethyldiethylenetriamine (PMDTA). Furthermore, based on the molar ratio of the organolithium compound and the triamine compound, the triamine compound may be introduced in a molar ratio of 0.5:1 to 1:1.

[0160] According to one embodiment of the present invention, the block copolymer intermediate represented by Formula 5 prepared in step (S20) above can be an intermediate of a triblock copolymer in which aromatic vinyl polymer blocks-olefin polymer blocks-aromatic vinyl polymer blocks are symmetrically formed around zinc.

[0161] According to one embodiment of the present invention, the aromatic vinyl monomer may be the same as the aromatic vinyl monomer used to form the aromatic vinyl polymer block described above. Furthermore, the aromatic vinyl monomer may be introduced in an amount sufficient to satisfy the content of the aromatic vinyl polymer block described above.

[0162] According to one embodiment of the present invention, step (S30) can be a step of obtaining a block copolymer containing repeating units represented by formula 6 from the block copolymer intermediate prepared in step (S20) represented by formula 5, which can be carried out by reaction with water, oxygen or an organic acid. In this case, in the block copolymer symmetrically formed around zinc, the bonds between zinc and the block copolymer bonded to zinc may break, thereby obtaining two block copolymers. As a specific example, the organic acid can be ethylhexanoic acid.

[0163] According to one embodiment of the present invention, all steps and all reactions of the method for preparing block copolymers can be carried out in an organic solvent, and the reaction temperature and reaction pressure can be adjusted as needed.

[0164] Resin Composition

[0165] The present invention provides a resin composition comprising the block copolymer.

[0166] According to one embodiment of the present invention, the resin composition may comprise the block copolymer and polypropylene, and as a specific example, may comprise the block copolymer as well as polypropylene and / or rubber polymer.

[0167] According to one embodiment of the present invention, the resin composition may comprise 5% to 90% by weight of block copolymer, 0% to 95% by weight of polypropylene, and 0% to 80% by weight of rubber polymer. As a specific example, it may comprise 5% to 90% by weight, 5% to 70% by weight, 5% to 50% by weight, or 10% to 30% by weight of block copolymer, 0% to 95% by weight, 20% to 90% by weight, 40% to 90% by weight, or 70% to 90% by weight of polypropylene, and 0% to 80% by weight, 0% to 60% by weight, 0% to 40% by weight, or 0% to 20% by weight of rubber polymer.

[0168] According to one embodiment of the invention, the rubber polymer may be one or more selected from the group consisting of solution-polymerized styrene-butadiene rubber and ethylene-propylene rubber. Furthermore, the resin composition may include processing oil.

[0169] According to one embodiment of the present invention, the tensile strength of the resin composition can be 15 MPa to 40 MPa, 20 MPa to 30 MPa, or 24 MPa to 28 MPa. Within this range, the resin composition exhibits excellent mechanical properties.

[0170] According to one embodiment of the present invention, the elongation at break of the resin composition is 100%–1500%, 300%–1000%, or 390%–980%. Within this range, the resin composition exhibits excellent mechanical properties.

[0171] According to one embodiment of the present invention, the impact strength of the resin composition can be 5 kgf·m / m or more, 7 kgf·m / m or more, or 10 kgf·m / m or more. Within this range, the resin composition exhibits excellent mechanical properties.

[0172] According to one embodiment of the present invention, the low-temperature (-40°C) impact strength of the resin composition can be 4 kgf·m / m or more, 4.5 kgf·m / m or more, or 4.5 kgf·m / m to 15.0 kgf·m / m. Within this range, the resin composition exhibits excellent mechanical properties.

[0173] According to one embodiment of the present invention, the melt flow index (230°C, 2.16 kg) of the resin composition can be 10 g / 10 min or more, 11.8 g / 10 min or more, or 11.8 g / 10 min to 40.0 g / 10 min. Within this range, the resin composition exhibits excellent processability.

[0174] According to one embodiment of the present invention, the melt flow index (230°C, 5kg) of the resin composition may be 0.5g / 10min to 2.0g / 10min, 0.7 to 1.5g / 10min, or 0.95 to 1.00g / 10min.

[0175] According to one embodiment of the present invention, the melt flow index (230°C, 10kg) of the resin composition can be 5g / 10min or more, 6g / 10min or more, or 6g / 10min to 8g / 10min.

[0176] According to one embodiment of the present invention, the Shore A hardness of the resin composition may be 10-60, 30-50 or 45-50.

[0177] The embodiments of the present invention will be described in detail below to enable those skilled in the art to readily implement the invention. However, the present invention can be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein.

[0178] Preparation examples, examples, comparative examples and experimental examples

[0179] In the preparation examples, examples, comparative examples, and experimental examples, all operations were performed under an inert atmosphere using a standard glove box and the Schlenk technique. Toluene, hexane, and diethyl ether were derived from benzophenone. Ketone The ethylene / propylene gas mixture was obtained by distillation. The mixture was purified in a 2.0 L bomb reactor over 0.6 M trioctyl aluminum in mineral oil. Recording was performed using a JEOL ECZ 600 apparatus. 1 H NMR (600MHz) and 13 C10 NMR (150 MHz) spectra. Gel permeation chromatography (GPC) was performed on 1,2,4-trichlorobenzene at 160 °C using an HLC-8321GPC / HT system equipped with an RI detector and two columns (PLgelmixed-B 7.5 x 300 mm, Varian Polymer Lab.). All chlorinated compounds containing styrene residues were filtered immediately before use through short alumina pads to remove free radical scavengers.

[0180] 1: Preparation and Evaluation of Organozinc Compounds

[0181] Preparation Example 1

[0182] At room temperature, 10.0 g (60.0 mmol) of 4-(2-chloroethyl)styrene dissolved in a mixed solvent of 20 ml toluene and 8.65 g (120 mmol) tetrahydrofuran (THF) was added dropwise to a suspension obtained by stirring 2.19 g (90.0 mmol) of magnesium powder in 40 ml toluene. After stirring for 3.5 hours to generate a slight heat, the reaction mixture was filtered through diatomaceous earth to remove excess magnesium. The filtrate was added to ethylmethoxide zinc (EtZn(OMe)) prepared by reacting 4.05 g (32.8 mmol) diethylzinc (Et2Zn) and 1.05 g (32.8 mmol) methanol in 30 ml toluene at room temperature for 1.0 hour. After stirring for 1.0 hour at room temperature, 21.5 g of mineral oil (boiling point 179–210 °C) was added, and magnesium methoxide chloride (MgCl(OMe)) was removed as an insoluble salt on diatomaceous earth. Subsequently, toluene and tetrahydrofuran were removed using a high-vacuum line to obtain an organozinc compound represented by formula 1-1 as a mineral oil solution. Aliquots were taken and the mineral oil was completely removed by vacuum distillation at 70°C under full vacuum. The yield was 80% by weight (7.95 g) according to gravimetric analysis, and the determination of... 1 H NMR and 13 C NMR spectrum.

[0183] Meanwhile, methylcyclohexane was added to the resulting organozinc compound represented by formula 1-1 to prepare a 10% by weight solution, which was subsequently used for polymerization in the examples.

[0184] [Equation 1-1]

[0185]

[0186] 1 H NMR (C6D6): δ7.28(d,J=8.4Hz,2H), 6.99(d,J=8.4Hz,2H), 6.65(dd,J=17,11Hz 1H, =CH), 5.65 (d, J = 17Hz, 1H, = CH2), 5.08 (d, J = 11Hz, 1H, = CH2), 2.62 (t, J = 7.2Hz, 2H, CH2), 0.42 (t, J = 7.2Hz, 2H, ZnCH2) ppm.

[0187] 13 C NMR (C6D6): δ18.88, 32.76, 112.73, 127.06, 127.99, 135.40, 137.30, 148.60ppm.

[0188] Preparation Example 2

[0189] At 0 °C, 5.00 g (32.8 mmol) of 4-vinylbenzyl chloride dissolved in 10 mL of diethyl ether was added dropwise to a suspension obtained by stirring 0.876 g (36.0 mmol) of metallic magnesium in 20 mL of diethyl ether. After stirring for 1 hour in an ice bath, the reaction mixture was filtered through diatomaceous earth to remove excess magnesium. The resulting Grignard reagent was added to ethylmethoxide zinc (EtZn(OMe)) prepared by reacting 4.05 g (32.8 mmol) of diethylzinc (Et2Zn) and 1.05 g (32.8 mmol) of methanol in 30 mL of toluene at room temperature for 1 hour. After stirring for 1 hour at room temperature, magnesium methoxide chloride (MgCl(OMe)) was removed as an insoluble salt on diatomaceous earth. The filtered cake was washed with 20 mL of diethyl ether. The solvent was then removed using a high-vacuum line to give an oily compound. Toluene 14 g was added to the obtained oily compound, and the temporarily generated volatiles, including toluene and diethylzinc, were completely removed using a high-vacuum line to give 4.35 g of a pale yellow solid. The solid was dissolved in 44 g of hot methylcyclohexane, and the insoluble fraction was removed by filtration under hot conditions. The filtrate was stored at -35 °C, and a pale yellow solid, represented by formula 1-2, precipitated. The yield was 81% by weight (3.79 g) according to gravimetric analysis, and the determination of... 1 H NMR and 13 C NMR spectrum.

[0190] [Equation 1-2]

[0191]

[0192] 1 H NMR (C6D6): δ7.24(d,J=8.4Hz,2H), 6.81(d,J=8.4Hz,2H), 6.66(dd,J=18,10Hz,1H, =CH), 5.64 (d, J = 18Hz, 1H, = CH2), 5.06 (d, J = 10Hz, 1H, = CH2), 1.50 (s, 2H, CH2Zn) ppm.

[0193] 13 C NMR (C6D6): δ23.92, 111.30, 127.04, 127.51, 132.46, 137.48, 144.90ppm.

[0194] Preparation Example 3

[0195] At 0 °C, 10.00 g (65.5 mmol) of 4-vinylbenzyl chloride dissolved in 20 mL of diethyl ether was added dropwise to a suspension obtained by stirring 1.752 g (72.0 mmol) of metallic magnesium in 40 mL of diethyl ether. After cooling in an ice bath with stirring for 1.0 hour, the reaction mixture was filtered through diatomaceous earth to remove excess magnesium. 9.38 g (65.5 mmol) of chloro(chloromethyl)dimethylsilane was added dropwise to the generated 4-vinylbenzyl-magnesium chloride (4-vinylbenzyl-MgCl) Grignard reagent at room temperature. After stirring for 2.5 hours, 30 mL of water was added to give the organic phase. The product was further extracted three times from the aqueous phase with 20 mL of hexane. The resulting organic phase and the product extracted from the aqueous phase were added together and dried over anhydrous magnesium sulfate (MgSO4). The solution was then filtered through a short silica gel pad, and the solvent was removed using a rotary evaporator to give a yellow oily compound represented by formula 3-3-1. Based on the gravimetric analysis, the yield was 79% by weight (11.6 g), and the yield was determined to be... 1 HNMR and 13 C NMR spectrum.

[0196] Equation (3-3-1):

[0197]

[0198] 1 H NMR (C6D6): δ7.19(d,J=8.4Hz,2H), 6.83(d,J=8.4Hz,2H), 6.61(dd,J=17,12Hz,1H,=CH), 5.63(d,J=17Hz ,1H,=CH2), 5.08(d,J=12Hz,1H,=CH2), 2.43(s,2H,CH2Cl), 1.97(s,2H,CH2Si), -0.086(s,3H,CH3Si)ppm.

[0199] 13 C NMR (C6D6): δ-5.02, 23.45, 29.34, 112.42, 126.79, 128.51, 134.45, 137.20, 138.96ppm.

[0200] Then, 5.00 g (22.2 mmol) of the compound represented by Formula 3-3-1 prepared above was dissolved in 10 mL of diethyl ether and added dropwise at 0 °C to a suspension obtained by stirring 0.59 g (24.5 mmol) of metallic magnesium in 20 mL of diethyl ether. After cooling in an ice bath with stirring for 1.0 hour, the reaction mixture was filtered through diatomaceous earth to remove excess magnesium. The generated Grignard reagent was added to ethylmethoxide zinc (EtZn(OMe)) prepared by reacting 2.75 g (22.2 mmol) of diethylzinc (Et2Zn) and 0.71 g (22.2 mmol) of methanol in 30 mL of toluene at room temperature for 1.0 hour. After stirring at room temperature for 1.0 hour, magnesium methoxide chloride (MgCl(OMe)) was removed as an insoluble salt on diatomaceous earth. The filtered cake was washed with 20 mL of diethyl ether. Then, the solvent was removed using a high vacuum line to obtain an oily compound. 14 g of toluene was added to the obtained oily compound, and the temporarily generated volatiles, including toluene and diethylzinc, were completely removed using a high-vacuum line to obtain a solid. The obtained solid was dissolved in 100 g of hexane and stored at -30 °C, precipitating out the solid compound represented by formula 1-3. The yield was 58 wt% (2.86 g) according to gravimetric analysis, and the determination of... 1 H NMR and 13 C NMR spectrum.

[0201] [Equation 1-3]

[0202]

[0203] 1 H NMR (C6D6): δ7.21(d,J=7.8Hz,2H), 6.81(d,J=7.8Hz,2H), 6.63(dd,J=18,11Hz,1H,=CH), 5.63(d,J=18Hz ,1H,=CH2), 5.09(d,J=11Hz,1H,=CH2), 1.93(s,2H,CH2Cl), 0.03(s,6H,CH3Si), -1.04(s,2H,CH2Zn)ppm.

[0204] 13 C NMR (C6D6): δ-1.30, 1.27, 28.94, 112.26, 127.23, 128.31, 134.13, 137.24, 141.81ppm.

[0205] Preparation Example 4

[0206] 15.0 g (98.3 mmol) of 4-vinylbenzyl chloride and 2.628 g (108.1 mmol) of metallic magnesium were added to 78 mL of diethyl ether, and the mixture was stirred at 0 °C for 1.0 h. The mixture was then filtered through diatomaceous earth to remove excess magnesium. 19.2 g (81.9 mmol) of p-tolyl-OCH2CH2Cl dissolved in 27 mL of diethyl ether was added dropwise to the generated 4-vinylbenzyl-magnesium chloride (4-vinylbenzyl-MgCl) Grignard reagent. The mixture was stirred overnight and filtered through diatomaceous earth to remove magnesium chloride toluenesulfonic acid (MgCl(OTs)) as an insoluble salt. The filter cake was washed three times with 70 mL of hexane, and the solvent was removed using a rotary evaporator to give 14.2 g of crude product. 43 mg (3000 ppm) of tert-butylcatechol was added as a free radical scavenger, and the mixture was vacuum distilled at 85 °C under full vacuum to give the compound shown in formula 3-4-1. Based on the gravimetric analysis of the obtained compound, the yield was 81% by weight (12.0 g), and the determination of... 1 H NMR and 13 C NMR spectrum.

[0207] [Equation 3-4-1]

[0208]

[0209] 1 H NMR (C6D6): δ7.20(d,J=8.4Hz,2H), 6.88(d,J=8.4Hz,2H), 6.61(dd,J=16,9.6Hz,1H,=CH), 5.63(d,J=16Hz,1H,=CH2), 5. 09(d,J=9.6Hz,1H,=CH2), 3.04(t,J=6.6Hz,2H,CH2), 2.42(t,J=6.6Hz,2H,CH2), 1.64(quintet,J=6.6Hz,2H,CH2Cl)ppm.

[0210] 13 C NMR (C6D6): δ32.61, 34.12, 44.07, 113.13, 126.74, 128.97, 135.99, 137.11, 140.63ppm.

[0211] Then, 10.0 g (55.3 mmol) of the compound represented by Formula 3-4-1 (4-(3-chloropropyl)styrene) prepared as above was dissolved in a mixed solvent of 20 mL toluene and 7.98 g (111 mmol) tetrahydrofuran (THF), and then added dropwise at room temperature to a suspension obtained by stirring 2.02 g (83.0 mmol) of magnesium powder in 40 mL toluene. After stirring for 5.0 h to generate a slight heat, the reaction mixture was filtered through diatomaceous earth to remove excess magnesium. Ethylmethoxide zinc, obtained by reacting 6.94 g (55.3 mmol, based on 1 equivalent of Grignard reagent) with 6.83 g (55.3 mmol) diethylzinc (Et2Zn) and 1.78 g (55.3 mmol) methanol in 30 mL toluene at room temperature for 1.0 h, was added to the filtrate. Subsequently, 60 mL of toluene was added, and the mixture was stirred at room temperature for 1.0 h, then the solvent was removed using a high-vacuum line. Subsequently, 96 g of hexane was added, and magnesium methoxide (MgCl(OMe)) was removed as an insoluble salt on diatomaceous earth. The filtrate was stored at -30°C to precipitate a white crystalline solid containing compounds represented by formulas 1-4. The yield was 56 wt% (7.28 g) according to gravimetric analysis, and the determination of... 1 H NMR and 13 CNMR spectrum.

[0212] [Equations 1-4]

[0213]

[0214] 1 H NMR (C6D6): δ7.24(d,J=7.8Hz,2H), 6.90(d,J=7.8Hz,2H), 6.64(dd,J=17,11Hz,1H,=CH), 5.66(d,J=17Hz,1H,=CH2), 5.11(d,J=11Hz,1H,=CH2), 2.43(t,J=7.2Hz,2H,CH2), 1.80(t,J=7.2Hz,2H,CH2), -0.19(t,J=7.2Hz,2H,CH2Zn)ppm.

[0215] 13 C NMR (C6D6): δ12.66, 28.82, 40.09, 113.15, 127.31, 129.23, 136.05, 137.10, 142.91ppm.

[0216] Comparative Preparation Example 1

[0217] Borane dimethyl sulfide (1.6 mL, 3.2 mmol) was slowly introduced into triethylborane (0.6 g) with stirring, and the reaction was allowed to proceed for 90 minutes. The mixture was then slowly introduced into divinylbenzene (3.8 g) dissolved in anhydrous diethyl ether (10 mL) cooled to -20 °C, and the mixture was stirred overnight. The solvent was removed using a vacuum pump, and then diethylzinc (0.8 g) was added. The reaction was carried out at 0 °C for 5 hours, while the generated triethylborane was removed by vacuum distillation. Excess divinylbenzene and diethylzinc were removed by vacuum distillation at 40 °C. Methylcyclohexane (150 mL) was added to redissolve the product, and the mixture was then filtered through diatomaceous earth to remove the solid compound that formed as a byproduct, thus preparing the organozinc compound represented by Formula 1-1 above.

[0218] Comparative Preparation Example 2

[0219] Except that zinc chloride (ZnCl2) was used instead of ethyl zinc methoxide (EtZn(OMe)) in Preparation Example 1, the organozinc compound represented by Formula 1-1 above was prepared in the same manner as in Preparation Example 1.

[0220] Experimental Example 1: Evaluation of Organozinc Compounds

[0221] For the organozinc compounds prepared in Preparation Examples 1-4 and Comparative Preparation Examples 1 and 2, the content (purity) of the target organozinc compound and the content of alkyl zinc chloride (R-Zn-Cl) and borane compounds (triethylborane or hydrogenated diethylborane) that act as catalyst poisons were measured.

[0222] * Measurement of various component contents: 1H (500MHz) NMR spectra were measured and analyzed using a Varian 500MHz spectrometer. The residual solvent peak was used as a reference, and the shift was displayed in ppm by TMS in the low field, with the ratio calculated.

[0223] 1) Target compound:

[0224] 2) Terminally saturated compounds:

[0225] 3) By-reaction products:

[0226] * Chlorine content measurement: The chlorine content was measured by combustion IC (ICS-2000 / AQF-2100H) under the following conditions and methods.

[0227] 1) Combustion temperature: Inlet temperature 900℃, outlet temperature 1000℃

[0228] 2) Gas flow rate: Ar gas 200 mL / min, O2 gas 400 mL / min

[0229] 3) Humidification rate: 0.23 mL / min, internal standard (PO4) 3- ): 20mg / kg

[0230] 4) Absorbent (H2O2): 900 mg / kg, absorption liquid volume: 5 mL, final dilution volume: 17 mL

[0231] 5) Column: IonPac AS18 (4×250mm)

[0232] 6) Elution buffer type: KOH (30.5mM), elution buffer flow rate: 1mL / min

[0233] 7) Detector: Suppressed conductivity detector, SRS current: 76mA

[0234] 8) Injection volume: 100 μL, isocratic / gradient condition: isocratic

[0235] 9) Accurately measure approximately 0.005 g of sample in the sample boat, add combustion accelerant (WO3), and measure the sample using a combustion IC.

[0236] [Table 1]

[0237]

[0238] As can be confirmed from Table 1 above, most of the compounds in Preparation Examples 1-4 were the target compounds, and no terminally saturated zinc compounds or by-reaction products were present. However, Comparative Preparation Example 1 contained approximately 20 mol% of terminally saturated zinc compounds and by-reaction products. Terminally saturated compounds cannot induce anionic polymerization, thus increasing the content of diblock copolymers in the final polymer. By-reaction products are intermediates that convert to oligomers or higher forms. When such oligomers of organozinc compounds are present, they cannot induce chain transfer reactions due to increased viscosity, thus inhibiting the polymer synthesis reaction. In other words, it can be seen that the organozinc compounds in Comparative Preparation Example 1 have the aforementioned problems.

[0239] Furthermore, although the proportion of the target compound in Comparative Preparation Example 2 was high, it contained up to 1000 ppm of chlorine, which could potentially act as a catalyst poison, and the proportion of the target compound in Comparative Preparation Example 2 was lower compared to that in Preparation Examples 1-4. Therefore, it can be reasonably inferred that the organozinc compounds in Preparation Examples 1-4 were improved.

[0240] 2. Preparation and Evaluation of Polyolefin-Polystyrene Block Copolymers

[0241] Examples 1-1 to 1-4

[0242] 1200 g of methylcyclohexane containing 1.0 mmol-Al of modified methylaluminoxane-3A (MMAO-3A) was added to a 3.7 L Parr reactor, and the mixture was stirred at 90 °C for 30 minutes using a heating mantle. The solution was removed using a mantle, and 1200 g of methylcyclohexane, 560 g of 1-hexene, and a solution containing 3.50 mmol of the compound prepared in Preparation Example 1 dissolved in 1.00 mmol-Al (a free radical scavenger) in methylaluminoxane-3A (MMAO-3A) and methylcyclohexane were added to the reactor under an inert atmosphere. The temperature was set to 90 °C. Subsequently, methylcyclohexane containing 10.0 μmol of [(C 18 H 37 )2N(H)Me] + [B(C6F5)4] - A catalyst solution containing 10.0 μmol of activated pyridine aminohafnium complex was injected into the reactor. Immediately after catalyst injection, ethylene gas was introduced at a pressure of 25 bar and maintained at a constant pressure of 25 bar throughout the supply. Although cooling was achieved through internal coils, the temperature rose to 115 °C within 5 minutes due to the exothermic reaction. After the initial temperature increase, the temperature began to decrease slowly and remained at 90 °C due to catalyst deactivation. The ethylene gas was depleted after 40 minutes of polymerization. Then, a solution of 3.10 mmol N,N,N',N”,N”-pentamethyldiethylenetriamine (PMDTA) dissolved in methylcyclohexane was added. After stirring the mixture for 30 minutes while maintaining the temperature at 90 °C, 100 g of styrene was added. The reactor was allowed to stand overnight to allow complete styrene conversion while maintaining the solution temperature at 100 °C. 2-Ethylhexanoic acid was added as a quencher, and after opening the reactor, excess ethanol was added to the solution. The precipitated polymer block was then dried overnight in a vacuum oven at 80°C to obtain 350g of polymer block.

[0243] Examples 1-5

[0244] 1200 g of methylcyclohexane containing 1.0 mmol-Al of modified methylaluminoxane-3A (MMAO-3A) was added to a 3.7 L Parr reactor, and the mixture was stirred at 90 °C for 30 minutes using a heating mantle. The solution was removed using a mantle, and 1200 g of methylcyclohexane, 560 g of 1-hexene, and a solution containing 3.50 mmol of the compound prepared in Preparation Example 4 dissolved in 1.00 mmol-Al (a free radical scavenger) of methylaluminoxane-3A (MMAO-3A) and methylcyclohexane were added to the reactor under an inert atmosphere. The temperature was set to 90 °C. Then, using a syringe, methylcyclohexane containing 10.0 μmol of [(C 18 H 37 )2N(H)Me] +[B(C6F5)4] - A catalyst solution containing 10.0 μmol of activated pyridine aminohafnium complex was injected into the reactor. Immediately after catalyst injection, ethylene gas was introduced at a pressure of 25 bar and maintained at a constant pressure of 25 bar throughout the supply. Although cooling was provided through an internal coil, the temperature rose to 115 °C within 5 minutes due to the exothermic reaction. After the initial temperature increase, the temperature began to decrease slowly and remained at 90 °C due to catalyst deactivation. The ethylene gas was depleted after 40 minutes of polymerization. Then, a solution of 3.10 mmol N,N,N',N”,N”-pentamethyldiethylenetriamine (PMDTA) dissolved in methylcyclohexane was added, and after stirring for 30 minutes while maintaining the temperature at 90 °C, 100 g of styrene was added. The reactor was allowed to stand overnight to allow complete styrene conversion while maintaining the solution temperature at 100 °C. 2-Ethylhexanoic acid was added as a quencher, and after opening the reactor, excess ethanol was added to the solution. The precipitated polymer block was then dried overnight in a vacuum oven at 80°C to obtain 350g of polymer block.

[0245] Comparative Example 1-1

[0246] The polymers were prepared in the same manner as in Examples 1-1, except that the organozinc compound of Comparative Preparation Example 1 was used instead of the organozinc compound of Preparation Example 1 in Examples 1-1.

[0247] Comparative Examples 1-2

[0248] The polymers were prepared in the same manner as in Examples 1-1, except that the organozinc compound of Comparative Preparation Example 2 was used instead of the organozinc compound of Preparation Example 1 in Examples 1-1.

[0249] Comparative Examples 1-3

[0250] The polymer was prepared in the same manner as in Examples 1-1, except that dihexylzinc was used instead of the organozinc compound in Example 1-1.

[0251] Comparative Examples 1-4

[0252] SEBS (Kraton G1651) is ready for commercial sale.

[0253] Experimental Example 2: Evaluation of Block Copolymers 1

[0254] For the block copolymers prepared by coordination chain transfer polymerization (CCTP) and anionic polymerization according to Examples 1-1 to 1-5 and Comparative Examples 1-2 to 1-4, and the block copolymer of Comparative Example 1-1, the content of ethylene units, the content of hexene units, the content of styrene units, the weight-average molecular weight, the tensile strength and the elongation at break were determined by the following methods, and the results are shown in Table 2 below.

[0255] *Content of ethylene, hexene (or butene), and styrene units (wt%): using 1 1H NMR spectroscopy was used to measure the content of various monomer units.

[0256] *Number-average molecular weight (Mn, g / mol), weight-average molecular weight (Mw g / mol), and molecular weight distribution (Mw / Mn): Number-average and weight-average molecular weights were measured using polystyrene (PS) standard gel permeation chromatography (GPC). GPC was performed on 1,2,4-trichlorobenzene at 160 °C using an HLC-8321GPC / HT system equipped with an RI detector and two columns (PLgel mixed-B 7.5 x 300 mm, Varian Polymer Lab.). The measured number-average and weight-average molecular weights were converted to SEBS equivalents using a universal calibration.

[0257] *Tensile strength (MPa) and elongation at break (%): According to ASTM D638, the block copolymers of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 prepared above were compressed at 25 bar for 10 minutes and then at 75 bar for 30 minutes between hot plates at 140°C (240°C for Comparative Examples 1-4). Subsequently, the resulting polymer films, approximately 1 mm thick, were cut into dog-bone shapes, and their tensile strength and elongation at break were determined using UTM according to ISO-37 standard method.

[0258] [Table 2]

[0259]

[0260]

[0261] As shown in Table 2, the block copolymers prepared in Examples 1-1 to 1-5 exhibited a wider molecular weight distribution than the block copolymers in Comparative Examples 1-4, and were proven to have excellent processability.

[0262] In addition, Examples 1-1 to 1-3 confirmed that tensile strength and elongation at break vary with the content of each monomer unit.

[0263] Furthermore, it was confirmed that although the block copolymers of Examples 1-5 could be synthesized on a large scale, they still exhibited physical properties comparable to those of the block copolymers of Comparative Examples 1-4. In particular, the viscosity of the block copolymers of Examples 1-5, measured using a rotational rheometer at 160°C and 500 rad / s, was 955 Pa·s, but the viscosity of the block copolymers of Comparative Examples 1-4 could not be measured.

[0264] Meanwhile, the GPC curves of the polymers polymerized according to chain transfer coordination polymerization (i.e., poly(ethylene-co-1-hexene)) and the block copolymers polymerized according to anionic polymerization are shown in Examples 1-5. Figure 1 ,according to Figure 1 The formation of block copolymers was clearly confirmed by the shift of the GPC curve after styrene polymerization via anionic polymerization.

[0265] Experimental Example 3: Evaluation of Block Copolymers 2

[0266] The block copolymers (SEHS) prepared according to Examples 1-5 and the block copolymers (SEBS) of Comparative Examples 1-4 were each photographed using TEM. The TEM images are shown below. Figure 2 .

[0267] Specifically, the block copolymers of Examples 1-5 and Comparative Examples 1-4 were dissolved in toluene at 100°C to a concentration of 10% by weight, and the solution was poured into a frame. The solvent was slowly evaporated at room temperature for 5 days, followed by overnight vacuum treatment at 80°C. Before staining with RuO4, the prepared samples were quenched in an oven at 150°C for 6 hours and then photographed using TEM.

[0268] from Figure 2 It can be confirmed that the block copolymers (SEBS) of Comparative Examples 1-4 exhibit a well-organized layered structure, while the block copolymers (SEHS) prepared according to Examples 1-5 form a disordered spherical structure, thus confirming the difference in polydispersity.

[0269] 3. Preparation and Evaluation of Resin Compositions 1

[0270] Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3

[0271] Resin compositions were prepared by mixing the block copolymers prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3 with polypropylene (product name CB5230) in the proportions listed in Table 3 below on xylene at 180°C.

[0272] *Tensile strength (MPa) and elongation at break (%): According to ASTM D638, the resin compositions prepared in the above examples and comparative examples were compressed between hot plates at 140°C (240°C for Comparative Examples 1-4) and 25 bar for 10 minutes, and then compressed at 75 bar for 30 minutes. Subsequently, the resulting resin composition film with a thickness of approximately 1 mm was cut into dog-bone shapes, and its tensile strength and elongation at break were determined using UTM according to the ISO-37 standard method.

[0273] *Impact strength at room temperature (23±2℃) and low temperature (-40℃) (cantilever impact strength, kgf·m / m): The block copolymers of the examples and comparative examples were mixed with polypropylene (trade name CB5230) in xylene at 180℃ according to the proportions shown in Table 3, and then precipitated in ethanol to recover the resin composition from the solution. The recovered resin composition was dried in a vacuum oven and then injected into a mold at 210℃ for 10 seconds under a pressure of 6 bar to form a notched shape with dimensions of 63.5 mm × 10.16 mm × 3.2 mm according to ASTM D256. The impact strength at room temperature (23±2℃) and low temperature (-40℃) was measured using a Tinius olsen Corporation Model 104 cantilever impact tester with a weight of 0.944 kg from the prepared specimen according to ASTM D256. The low-temperature (-40℃) impact strength is determined as follows: the prepared sample is placed in a low-temperature chamber set at -40℃ and exposed at -40℃ for more than 12 hours. Then the sample is removed from the low-temperature chamber and the impact strength is measured within 3 seconds.

[0274] *Mel flow index (g / 10min): According to ASTM D1238, using a GOTTFERT Corporation MI-4 model, the resin compositions prepared in the above examples and comparative examples were filled into the feed section, melted at 230°C for 5 minutes, and then measured at 230°C under a load of 2.16 kg.

[0275] [Table 3]

[0276]

[0277] *NB: Not broken

[0278] Referring to Table 3 above, it was confirmed that the tensile strength and room temperature and low temperature impact strength of Examples 2-1 to 2-4 were significantly superior compared to Comparative Examples 2-1 to 2-3, and it was also confirmed that the elongation at break and melt flow index remained at the same level or higher. It can be seen from the above that the properties of the resin composition (compound) can be greatly improved when using the block copolymer prepared by the organozinc compound of the present invention.

[0279] 4. Preparation and Evaluation of Resin Compositions 2

[0280] Examples 2-5 to 2-7 and Comparative Examples 2-5 to 2-6

[0281] In xylene at 180°C, the block copolymers prepared in Examples 1-5 and the block copolymers in Comparative Examples 1-4 were mixed with polypropylene (product name CB5230) in the proportions listed in Tables 4 to 6 to prepare resin compositions.

[0282] Experimental Example 4: Performance Evaluation of Resin Compositions 1

[0283] The physical properties of the resin compositions prepared according to Examples 2-5 to 2-7 and the resin compositions prepared according to Comparative Examples 2-4 to 2-6 were measured in the following manner, and the results are shown in Tables 4 to 6 below.

[0284] *Tensile strength (MPa) and elongation at break (%): According to ASTM D638, the resin compositions prepared in Examples 2-5 to 2-7 and Comparative Examples 2-4 to 2-6 were each compressed at 25 bar for 10 minutes and then at 75 bar for 30 minutes between hot plates at 140°C and 240°C. Subsequently, the resulting resin composition film with a thickness of approximately 1 mm was cut into dog-bone shapes, and its tensile strength and elongation at break were determined using UTM according to the ISO-37 standard method.

[0285] *Room temperature impact strength, low temperature impact strength, and melt flow index: measured in the same manner as in Experimental Example 3 above.

[0286] [Table 4]

[0287]

[0288] [Table 5]

[0289]

[0290]

[0291] [Table 6]

[0292]

[0293] *NB: Not broken

[0294] As shown in Tables 4-6, when comparing Examples 2-5 and Comparative Examples 2-4, 2-6 and Comparative Examples 2-5, and 2-7 and Comparative Examples 2-6 with the same amount of block copolymers, it was confirmed that the examples prepared using the organozinc compound of the present invention were superior in all mechanical properties compared to the comparative examples. The differences in these mechanical properties are due to the differences in the comonomers of the olefin polymer blocks that form the intermediate blocks of the block copolymers and the high molecular weight distribution of the block copolymers.

[0295] Experimental Example 5: Performance Evaluation of Resin Compositions 2

[0296] After etching the block copolymer regions of Examples 2-5 to 2-7 and Comparative Examples 2-4 to 2-6 with xylene, the resin compositions were photographed using SEM. The SEM images are shown below. Figure 3 .

[0297] Specifically, the block copolymers prepared in Examples 2-5 to 2-7 and Comparative Examples 2-4 to 2-6 were mixed with polypropylene (product name CB5230) in the proportions described in Tables 4 to 6 above on xylene at 180°C. The mixture was then precipitated in ethanol to recover the resin composition from the solution. After drying the recovered resin composition in a vacuum oven, it was injected into a mold at 210°C for 10 seconds under a pressure of 6 bar to form a dog-bone shape. The impact strength of the dog-bone-shaped specimens was measured at -40°C, and then the fractured surfaces were treated with xylene at room temperature for 4 hours to etch SEHS or SEBS, followed by SEM imaging.

[0298] from Figure 3 It can be confirmed that in the resin compositions (PP+SEHS) of Examples 2-5 to 2-7 of the present invention, the block copolymer (SEHS) forms small and uniform regions in the polypropylene (PP) matrix, while in the resin compositions (PP+SEBS) of Comparative Examples 2-4 to 2-6, the block copolymer (SEBS) forms large and irregular regions in the polypropylene (PP) matrix. From the above, it can be seen that the block copolymer exhibits excellent dispersibility in the resin compositions of the present invention.

[0299] The results of Experiments 1 to 5 above confirm that when preparing organozinc compounds according to the method of the present invention, triethylborane is not used, ensuring operational safety, and a single compound is synthesized, which does not include by-reaction products such as dimers, does not include chlorine-containing impurities that may become catalyst poisons, and facilitates the removal of magnesium-containing impurities that may become catalyst poisons.

[0300] Furthermore, it has been confirmed that chain transfer agents comprising organozinc compounds prepared by the method for preparing organozinc compounds according to the present invention exhibit excellent synthetic reproducibility and polymerization reproducibility.

[0301] Furthermore, it has been confirmed that block copolymers prepared by coordination chain transfer polymerization and anionic polymerization using the chain transfer agent of the present invention have a wide molecular weight distribution and excellent mechanical properties.

[0302] Furthermore, it has been confirmed that the resin composition of the present invention contains the above-mentioned block copolymer, thereby exhibiting excellent polypropylene dispersibility and thus excellent mechanical properties.

Claims

1. A chain transfer agent comprising at least 96 mol% of an organozinc compound represented by Formula 1 below, and free of borane compounds: [Formula 1] ， in, In Equation 1 above, R 1 and R 3 Each is independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 -SiR 4 R 5 - and R 4 and R 5 Each is independently an alkyl group having 1 to 10 carbon atoms. In the chain transfer agent, the content of Cl, by weight, is less than 10 ppm.

2. The chain transfer agent as described in claim 1, wherein, In the chain transfer agent, the content of Mg is less than 10 ppm by weight.

3. The chain transfer agent as described in claim 1, wherein, The chain transfer agent comprises more than 99 mol% of an organozinc compound represented by Formula 1 above.

4. The chain transfer agent as described in claim 1, wherein, R 1 and R 3 Each is independently a single bond or an alkylene group having 1 to 3 carbon atoms, and R 4 and R 5 Each is an alkyl group having 1 to 3 carbon atoms.

5. The chain transfer agent as described in claim 1, wherein, The organozinc compounds represented by Formula 1 above are the organozinc compounds represented by Formulas 1-3 below: [Equation 1-3] 。 6. A method for preparing a chain transfer agent comprising 96 mol% or more of an organozinc compound represented by Formula 1, the method comprising: Preparation of Grignard reagents containing styrene residues; and The prepared Grignard reagent is reacted with a zinc compound to prepare the organozinc compound represented by Formula 1 below. The zinc compound is an alkyl zinc alkoxide: [Formula 1] ， In Equation 1 above, R 1 and R 3 Each is independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 Alkylene or -SiR with 1 to 10 carbon atoms 4 R 5 - and R 4 and R 5 Each is an alkyl group with 1 to 10 carbon atoms.

7. The method of claim 6, wherein, The Grignard reagent containing styrene residues is represented by the following formula 2: [Equation 2] ， In Equation 2 above, R 1 and R 3 Each is independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 Alkylene or -SiR with 1 to 10 carbon atoms 4 R 5 -, R 4 and R 5 Each is an alkyl group having 1 to 10 carbon atoms, and X is a halogen group.

8. The method of claim 7, wherein, The Grignard reagent containing styrene residues, represented by Formula 2 above, is prepared by reacting a compound represented by Formula 3 below with magnesium: [Formula 3] ， In Equation 3 above, R 1 and R 3 Each is independently a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 Alkylene or -SiR with 1 to 10 carbon atoms 4 R 5 -, R 4 and R 5 Each is an alkyl group having 1 to 10 carbon atoms, and X is a halogen group.

9. The method of claim 6, wherein, The zinc compound is ethyl methoxide zinc.

10. Use of the chain transfer agent according to any one of claims 1 to 5 in the preparation of block copolymers by coordination chain transfer polymerization, wherein, The block copolymer is a triblock copolymer in which one or more aromatic vinyl polymer blocks are alternately bonded to one or more olefin polymer blocks, wherein the molecular weight distribution Mw / Mn of the block copolymer is 1.5 or more.

11. The use as described in claim 10, wherein, The block copolymer is a triblock copolymer comprising aromatic vinyl polymer blocks, olefin polymer blocks, and aromatic vinyl polymer blocks.

12. The use as described in claim 10, wherein, The olefin polymer block comprises ethylene monomer units and α-olefin monomer units with 3 to 20 carbon atoms.

13. The use as described in claim 10, wherein, The olefin polymer block comprises ethylene monomer units and α-olefin monomer units with 6 to 8 carbon atoms.

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