TW202225199A - Method for preparing polyolefin-polystyrene-based multiblock copolymer - Google Patents

Abstract

The present invention relates to a method for preparing a polyolefin-polystyrene-based multiblock copolymer having a uniform structure and showing excellent physical properties through continuous type coordination polymerization and batch type anionic polymerization.

Description

Process for preparing polyolefin-polystyrene-based multiblock copolymers

The present invention relates to a method for preparing a polyolefin-polystyrene-based multi-block copolymer having a uniform structure and exhibiting excellent physical properties through continuous coordination polymerization and batch anionic polymerization.

Block copolymers are widely used materials even in high-tech devices as well as typical plastics, and their related research and development is being actively carried out. In particular, a styrene-olefin copolymer resin comprising both a polyolefin-based (PO) block and a polystyrene-based (PS) block has excellent properties such as heat resistance, light resistance, elasticity, and the like, and can be used in a wide range of technical fields .

Currently, there is a global market of polyolefin-polystyrene block copolymers with a scale of hundreds of thousands of tons, such as styrene-ethylene-butylene-styrene (SEBS) or styrene-ethylene-propylene-styrene (SEPS). Typically, a polystyrene-block-poly(ethylene-co-1-butene)-block polystyrene (SEBS) triblock copolymer can be an example of one of the styrene-olefin copolymer resins. The hard polystyrene domains in the structure of the SEBS triblock copolymer are separated from the soft poly(ethylene-co-1-butene) matrix and serve as physical crosslinking sites, as well as exhibit thermoplastic elastomeric properties. Based on these properties, SEBS is more widely used in product groups that require rubber and plastics, and as the scope of use expands, the demand increases significantly.

Conventional SEBS is prepared by a two-step reaction comprising anionic polymerization of styrene and butadiene and hydrogenation of the SBS obtained thereby. Conventional SEPS is also prepared by a two-step reaction comprising anionic polymerization of styrene and isoprene and hydrogenation of the SIS obtained therefrom. As mentioned above, the process cost of saturating all double bonds contained in the polymer main chain by hydrogenation reaction is high, and the unit cost of SEBS and SEPS is significantly increased compared with SBS and SIS before hydrogenation reaction. Therefore, these points will limit market expansion. Furthermore, it is virtually impossible to saturate all double bonds in the polymer chain through hydrogenation, and commercial SEBS and SEPS contain some residual double bonds, the presence of which often causes problems.

Therefore, in order to prepare a multi-block structure with triblock or more blocks to achieve thermoplastic elastomer properties and to be industrially usable block copolymers, a one-pot process from olefin-based monoliths has been developed. A technology for preparing polyolefin-polystyrene diblock copolymers with styrene monomers, which is to form polyolefin blocks by performing coordination polymerization of olefin-based monomers, and then performing anionization with styrene monomers. Polymerization to form polyolefin-polystyrenic multiblocks.

However, if the coordination polymerization and the anionic polymerization are carried out in batch mode, the heat removal of the batch reactor is difficult, and the recycling of reactants such as unreacted monomer is difficult, and the operating cost is uneconomically increased . In addition, the limited control over the uniformity of the concentration of reactants in the reactor, and the problems that the physical properties of the polyolefin-polystyrene-based multi-block copolymer deteriorate and become non-uniform, and these are additional concerns. the subject.

[PRIOR ART DOCUMENT]

[patent document]

Korean Registered Patent No. 10-1657925

technical problem

The object of the present invention is to provide a polyolefin-polystyrene system having a uniform structure and exhibiting excellent physical properties by sequentially performing continuous coordination polymerization of olefin-based monomers and batch anionic polymerization of styrene-based monomers Methods of Multiblock Copolymers. Technical solutions

In order to solve the above-mentioned problems, the present invention provides a method for preparing a polyolefin-polystyrene-based multi-block copolymer, the method comprising: (S1) by performing coordination polymerization of ethylene and an α-olefin-based monomer and simultaneously The hafnium compound, the organic zinc compound, the organic solvent, the ethylene gas and the α-olefin-based monomer are continuously injected into the continuous reactor to prepare the polyolefin, and the polyolefin is transported to the batch reactor; and (S2) in the batch reactor In a type reactor, anionic polymerization of polyolefin and styrenic monomer is carried out in the presence of an alkyl lithium compound. favorable effect

The polyolefin-polystyrene-based multi-block copolymer of the present invention can be obtained by increasing the polyolefin chain through continuous polymerization of ethylene and α-olefin-based monomers, and then performing batch polymerization with styrene-based monomers. Excellent productivity, mass production, and lower manufacturing costs compared to conventional techniques to increase economic viability and commercial usefulness. In addition, the polyolefin-polystyrene-based multiblock copolymer thus prepared exhibits improved physical properties and can be used in various industrial fields.

Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

It will be understood that words or terms used in the description and claims of the present invention should not be construed as defined in common dictionaries. Based on the principle that the inventor can properly define the meaning of words to best explain the present invention, it is to be understood that such words or terms should be construed as having meanings consistent with their meanings in the technical concept of the present invention.

In the present invention, in the case of preparing polyolefin-polystyrene-based multi-block copolymers through coordination polymerization of ethylene and α-olefin monomers and anionic polymerization with styrene-based monomers, in order to solve the problem of batch-type multi-block copolymers The productivity of the polyolefin block is lowered and the physical properties of the polyolefin-polystyrene-based multi-block copolymer are deteriorated in the case of performing the coordination polymerization, and the coordination polymerization of the olefin-based monomer is performed by continuous polymerization. In particular, an olefin-based monomer system is coordinated polymerized in a continuous reactor to form a polyolefin block, and then the polyolefin block is transferred to a batch reactor, and anionization with the styrenic monomer is carried out therein. polymerization.

In addition, in order to improve the efficiency of the continuous coordination polymerization reaction and further improve the physical properties of the final prepared copolymer, the injection flow rate of the hafnium compound, organic solvent, ethylene gas, and α-olefin monomer into the continuous reactor is controlled. and coordination polymerization time.

In particular, the method of the present invention comprises: (S1) by carrying out the coordination polymerization of ethylene and the α-olefin-based monomer while simultaneously continuously connecting the hafnium compound, the organozinc compound, the organic solvent, the ethylene gas and the α-olefin-based monomer injecting into a continuous reactor to prepare polyolefin, and transferring the polyolefin to a batch reactor; and (S2) in the batch reactor, performing polyolefin and styrenic monomer in the presence of an alkyl lithium compound anionic polymerization.

Through this preparation method, the polyolefin-polystyrene-based multi-block copolymer can form a target polyolefin chain from an olefin-based monomer by using an organozinc compound as a chain transfer agent, and then react with the styrene-based monomer by It is prepared by anionic polymerization to form a polystyrene block at the end of the polyolefin chain. In particular, by applying continuous polymerization and batch polymerization together, the realization of thermoplastic elastomer properties of the copolymer can be further increased, and copolymers having excellent physical properties such as tensile properties can be obtained.

Step (S1)

This is to prepare polyolefin by performing coordination polymerization of ethylene and α-olefin-based monomer while continuously injecting hafnium compound, organozinc compound, organic solvent, ethylene gas and α-olefin-based monomer into a continuous reactor, and the step of delivering the polyolefin to the batch reactor.

In this case, the injection flow rate of the hafnium compound may be 0.16 to 1.5 µmol/min, and the injection flow rate of the organic solvent may be 6 to 48 mL/min per 1 L of continuous reactor volume, at 20°C and 1 bar. The injection flow rate of the ethylene gas under the conditions is 60 to 50,000 cc/min, and the injection flow rate of the α-olefin-based monomer is 5 to 15 mL/min.

A continuous reactor means a reactor for continuously injecting raw materials for the reaction, conducting the reaction, and continuously discharging the polymerized and manufactured products, and the continuous reactor may be, for example, a continuous stirred tank reactor (CSTR) (solution and slurry). material).

In the preparation method of the present invention, the coordination polymerization of the olefin-based monomer, which is carried out as a pre-step during the preparation of the polyolefin-polystyrene-based multi-block copolymer, is carried out in a continuous reactor, and compared with By the conventional method of performing the coordination polymerization of olefin-based monomers in a batch manner, excellent effects on the physical properties of the copolymer can be obtained. In particular, in the case of preparing a multi-block copolymer by first preparing a polyolefin by polymerizing an olefin-based monomer in a batch method, a semi-batch method can be performed, and this is to inject all the α-olefins at the polymerization initiation point Monomers are injected in a single manner, and as the polymerization progresses, the concentration of olefinic monomers in the reactor will gradually decrease. Therefore, in the same polymer chain, the content of the olefin-based monomer gradually decreases with time, and there are problems that the chain arrangement becomes non-uniform and the physical properties of the polymer cannot be controlled. In addition, if the coordination polymerization of the olefin-based monomer is carried out by batch method, it is greatly affected by parameters including the injection point of the catalyst, the injection rate of the olefin-based monomer, etc., the polymerization rate is fast, the calorific value is high, and There are problems that it may be difficult to control the physical properties of the polyolefin, reproducibility may be poor, and mass production and commercial application may be difficult.

On the contrary, in the preparation method of the present invention, the coordination polymerization is carried out in a continuous reactor, and through this, the reaction mixture can be uniformly mixed, and the concentration of the monomers can be kept at a constant level during the coordination polymerization, so , which can prevent the problem of changing the physical properties of the polymer (including the content of α-olefin monomers in the polyolefin chain), and the arrangement of α-olefin monomers will become random and improve the attraction between polymer chains. And an improvement in the mechanical properties of the final prepared copolymer can be expected.

Furthermore, with regard to productivity, the production method of the present invention has advantages in mass production and commercial application by performing coordination polymerization in a continuous manner. In particular, in the case of batch polymerization, as the polymerization progresses, and as the initially injected catalyst is reused, the activity gradually decreases, and the efficiency of the polymerization reaction decreases. On the contrary, in the case of continuous polymerization, continuous supply of new catalysts as reactants shows that the total catalyst activity of coordination polymerization is high, and ethylene and α-olefin monomers can be polymerized with high efficiency.

Furthermore, during the polymerization of polyolefin-polystyrene-based multi-block copolymers by CCTP, the polymerization of ethylene and alpha-olefin-based monomers starts with the hafnium compound and the organozinc compound itself, which do not contain polymer chains. At the beginning of the reaction, the reaction proceeds in a mode in which the organozinc compound is unilaterally provided and the polymer chain grows on the hafnium compound, and after a certain period of time, in a state in which both the hafnium compound and the organozinc compound contain the polymer chain. Efficiently conduct CCTP. Therefore, there is a problem that an extra time is required before full-speed CCTP is performed. Furthermore, with regard to operating the actual process, batch polymerization must require wash time after a batch is performed. As mentioned above, in batch polymerization, due to various factors, the total time spent in the process increases compared to the time required for actual polymerization, which becomes a factor that reduces productivity.

Conversely, in the case of continuous polymerization, both the hafnium compound and the organozinc compound contain polymer chains after reaching a steady state, efficient CCTP can be performed while showing excellent productivity, and operation can be performed without operation stop The polymerization process shows high productivity.

In the present invention, a continuous reactor may be one or may mean two or more continuous reactors arranged in series, and in this case, the reactants may be injected into the first reaction among the reactors arranged in series and transport to the final reactor. After the polymerization is completed, the polyolefin can be discharged and conveyed to a batch reactor, which will be explained later.

As long as the hafnium compound can form a polyolefin block through coordination polymerization with an olefin-based monomer, the hafnium compound can be used in the present invention without limitation, preferably, a homogeneous (metallocene) catalyst containing hafnium can be used, and More preferably, a hafnium pyridylamide-based catalyst can be used without limitation.

By using hafnium compounds, unnecessary beta elimination procedures can be prevented, homogeneous polyolefin chains can be efficiently grown from organozinc compounds to prepare high molecular weight polyolefins with various block compositions, and coordination chain transfer polymerization can be performed (CCTP).

As the hafnium compound, an activated hafnium compound having a cocatalyst compound can be used. In this case, the cocatalyst compound may use one known in the art, for example, one or more selected from the following Formula 2 to Formula 4.

[Formula 2] -[Al(R _a )-O] _m -

[Formula 3] D(R _a ) ₃

[Formula 4] [LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-

In the above formula,

each R is independently _a halogen group; a hydrocarbyl group of 1 to 20 carbon atoms; or a halogen-substituted hydrocarbyl group of 1 to 20 carbon atoms,

m is an integer of 2 or more,

D is aluminum or boron,

L is a neutral or cationic Lewis acid,

Z is a group 13 element,

each A is independently an aryl group of 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; or an alkyl group of 1 to 20 carbon atoms, and

The substituents of A are halogen; hydrocarbon groups of 1 to 20 carbon atoms; alkoxy groups of 1 to 20 carbon atoms; or aryloxy groups of 6 to 20 carbon atoms.

The compound represented by Formula 2 is not particularly limited as long as it is an alkylaluminoxane. Preferred embodiments include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc. A particularly preferred compound is methylaluminoxane.

The compound represented by formula 3 is not particularly limited, but preferred embodiments include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, trimethylaluminum Isopropylaluminum, tri-tertiary butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisoamylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, trimethyl boron Butylboron, etc., particularly preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

、四(五氟苯基)硼酸三苯基

等。 Examples of the compound represented by Formula 4 include dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- , triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl)borate, tetra (o,p-Dimethylphenyl)borate trimethylammonium, tetrakis (p-trifluoromethylphenyl)borate tributylammonium, tetrakis (p-trifluoromethylphenyl)borate trimethylammonium, tetrakis (Pentafluorophenyl)borate tributylammonium, tetrapentylboronic acid N,N-diethylanilinium, tetraphenylboronic acid N,N-diethylanilinium, tetrakis (pentafluorophenyl)boronic acid N, N-diethylanilinium, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminum, tributyl Tetraphenylaluminum trimethylammonium, tetraphenylaluminum trimethylammonium, tetraphenylaluminum tripropylammonium, tetrakis(p-tolyl)aluminum Ethylammonium tetra(o, p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum Butylammonium tetrakis(pentafluorophenyl)aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrakis (Pentafluorophenyl) aluminum, diethylammonium tetrakis (penta (tetraphenyl)) aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triethylammonium tetraphenyl aluminum, Tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, tripropylammonium tetrakis(p-tolyl)borate , triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethyl ammonium tetrakis (o, p-dimethylphenyl) borate, tributyl tetrakis (p-trifluoromethylphenyl) borate ammonium, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetraphenylborate, tetraphenylboronic acid N,N-diethylanilinium, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetraphenylborate, Triphenyl tetrakis(p-trifluoromethylphenyl)borate

, triphenyl tetrakis (pentafluorophenyl) borate

Wait.

The hafnium compound may be injected into the continuous reactor at a volume of 0.16 to 1.5 µmol/min per 1 L of the continuous reactor volume. If the hafnium compound is injected in this range, the reactivity of the coordination polymerization reaction and the control of the heat of reaction can be appropriately reconciled, the growth and uniformity of the copolymer chain can be ensured at the same time, and a copolymer with a narrow molecular weight distribution can be obtained, and Reproducibility of the reaction can be achieved. In addition, the advantages of suppressing ultra-high molecular weight generation and preventing fouling in the reactor can be expected.

The organozinc compound is a material used as a chain transfer agent and a material for initiating the preparation of a copolymer by performing chain transfer during the preparation in a polymerization reaction, and in particular, may be a compound represented by the following formula 1.

[Formula 1]

In formula 1,

A is an alkyl group of 1 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a halogen, an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, 1 alkoxy of up to 8 carbon atoms or aryl of 6 to 20 carbon atoms substituted by an aryl group of 6 to 12 carbon atoms, and

B is an aryl group of 6 to 12 carbon atoms substituted with an alkenyl group of 2 to 12 carbon atoms.

In addition, A can be an alkylene group of 1 to 12 carbon atoms; an aryl group of 6 to 12 carbon atoms; or a halogen, an alkyl group of 1 to 12 carbon atoms, a cycloalkane of 3 to 12 carbon atoms alkoxy groups of 1 to 8 carbon atoms or aryl groups of 6 to 12 carbon atoms substituted by aryl groups of 6 to 12 carbon atoms, and

B can be an aryl group of 6 to 12 carbon atoms substituted with an alkenyl group of 2 to 8 carbon atoms.

Formula 1 may have a structure in which both ends of the formula have double bonds, for example, if B is an alkenyl-substituted aryl group, the aryl group can be attached to A, and the double bond in the aryl-substituted alkenyl group can be located in the outermost part of formula 4.

In the case where the organozinc compound is reacted with one or more olefin-based monomers in the presence of the catalyst composition, the polymerization may be inserted between the zinc (Zn) of the organozinc compound and the organic group (A) of the olefin-based monomer when carried out.

The amount of the organozinc compound used may be 1 to 200 equivalents based on 1 equivalent of the hafnium compound, and particularly 10 to 100 equivalents based on 1 equivalent of the hafnium compound.

The organozinc compound does not contain THF and impurities, such as a large amount of magnesium salts, and can be supplied in high purity, and thus can be used as a chain transfer agent, and advantageously in olefin polymerization.

In addition, the molar ratio Zn/Hf of the hafnium element in the hafnium compound and the zinc element in the organozinc compound may be 1 or higher, particularly 100 or higher, and 200 or lower, or 150 or lower. If the Zn/Hf value is 1 or more and 200 or less, the amount of the chain transfer agent relative to the hafnium compound is suitable, the use of Zn in excess of the necessary amount can be prevented to improve economic feasibility, CCTP can be performed efficiently, and A decrease in the molecular weight distribution of the copolymer can be expected.

The organic solvent is injected to perform the coordination polymerization of ethylene and the α-olefin monomer in a uniform solution state, and a hydrocarbon solvent can be used. As the hydrocarbon solvent, an aliphatic hydrocarbon solvent of 4 to 20 carbon atoms, for example, isobutane, hexane, cyclohexane, methylcyclohexane, or a mixture thereof, can be used without limitation.

The organic solvent can be injected into the continuous reactor at a volume of 6 to 48 mL/min per 1 L of the continuous reactor. If the injection flow rate is 6 mL/min or more and 48 mL/min or less, the produced copolymer can be sufficiently dissolved, the heat removal effect can be excellent, and the residence time can be ensured to ensure sufficient copolymer grow.

In the present invention, ethylene and α-olefin-based monomers may be included as reactants for coordination polymerization. In this case, the ethylene can be injected in gaseous form.

The alpha-olefin-based monomer may be particularly an aliphatic olefin of 3 to 20 carbon atoms, more particularly an aliphatic olefin of 4 to 12 carbon atoms, and more particularly an aliphatic olefin of 5 to 12 carbon atoms. As aliphatic olefins, for example, 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, etc., and any one of them, or their A mixture of two or more of them.

Ethylene gas can be injected at 20°C and 1 bar at a volume of 60 to 50,000 cc/min per 1 L of continuous reactor volume.

In addition, the α-olefin-based monomer may be injected at a volume of 5 to 15 mL/min per 1 L of the continuous reactor volume.

If the injection flow rate of the α-olefin-based monomer is controlled within the above-mentioned range, the concentration of the α-olefin-based monomer in the reactor is sufficient, the amount of insertion into the polymer chain can become excellent, and the reduction of the residence time can be prevented. The problem of inhibiting polymer growth. In addition, if the flow rate of the α-olefin-based monomer and the flow rate of the organic solvent are controlled at the same time, the concentration of the α-olefin-based monomer in the reactor can be maintained at an appropriate level, and a polyolefin with a better composition can be obtained. Removal of heat of reaction can also be achieved efficiently, and polymerization can be performed stably.

In coordination polymerization, the residence time of ethylene and α-olefin-based monomers may be within 5 minutes to 2 hours, particularly 18 minutes or more, 20 minutes or more, and 24 minutes or less, 22 minutes or more. short. Adopting an appropriate residence time within the above range can ensure sufficient time for dissolving the olefin-based monomer, and can ensure an increase to an ultra-high viscosity of the reactant, thereby contributing to increased productivity and production of polyolefins with excellent physical properties.

The temperature of the coordination polymerization may vary with the reaction materials and reaction conditions, but may be 70°C or higher, 90°C or higher, 110°C or higher, and 170°C or lower, 130°C or lower, 120°C or lower. Within the above range, the catalyst can be thermally stabilized while simultaneously increasing the solubility of the polymer.

After the thus prepared polyolefin is delivered to the batch reactor, the polyolefin can play the role of a precursor for the preparation of polyolefin-polystyrene-based multi-block copolymers by anionic polymerization, which will be Explained later.

Step (S2)

This step is used in a batch reactor to carry out anionic polymerization of polyolefins and styrenic monomers in the presence of an alkyl lithium compound, and through the polymer formed in step (S1) by batch anionic polymerization Olefin chains and styrene monomers can form polyolefin-polystyrene multi-blocks.

In particular, the styrene-based monomer can be continuously inserted between the zinc-carbon bonds of (polyolefin group) ₂ Zn contained in the compound formed by the step (S1), and at the same time, exist in the compound formed by the step (S1) ) at the terminal end of the compound formed can participate as a copolymerization moiety with the styrenic monomer to be linked to the polystyrene chain. In addition, the multi-block copolymers formed through this process can be easily inhibited by the reaction of the end groups with water, oxygen or organic acids, thereby converting into industrially usable polyolefin-polystyrene-based multi-block copolymers.

Different from the continuous method of step (S1), step (S2) is performed by batch method. In the case of anionic polymerization, the control of the block size is the key during the synthesis of multi-block copolymers, and the anionic polymerization is carried out through living polymerization, so the polymerization is carried out until all styrenic monomers are consumed until. Therefore, the reduction in the concentration of the reactants generated during the batch polymerization does not affect the size control of the block, and the polymerization can be carried out until the polymerization conversion ratio reaches the maximum value of 100%, and by controlling the injection amount of the styrene-based monomer , you can control the size of the block.

On the contrary, if the anionic polymerization of step (S2) is carried out in a continuous manner, the polymerization conversion ratio in the anionic polymerization cannot be increased to a maximum of 100% as in the batch polymerization, with residence time distribution, and it is difficult to inject monomers. The amount controls the size of the block and, therefore, has the disadvantage that it is difficult to control the size of the block of the copolymer. In addition, since the initiation time of the anionic polymerization initiator is additionally consumed in the anionic polymerization, if the continuous operation is performed, additional residence time is required to ensure uniform initiation of the polymerization reaction at all reaction sites.

An important feature of anionic polymerization is to control the molecular weight distribution of the polymer in a narrow range, which can be suitably achieved by batch reactors without residence time distribution. Conversely, if a continuous reactor is used, there is an inherent product residence time distribution which increases the molecular weight distribution of the polymer to the detriment of the physical properties of the polymer. Meanwhile, in order to improve polymer productivity in commercial reactors, anionic polymerization is sometimes carried out in continuous reactors, but if the residence time is not long, the application is extremely limited. In the preparation method of the polyolefin-polystyrene-based multi-block copolymer of the present invention, the anionic polymerization will require a long polymerization time, and if a continuous reactor is used, the volume of the reactor will be significantly increased or the number of the reactor will be increased. To meet the disadvantage of long residence time.

Taking these points into consideration, in the present invention, in the present invention, polyolefin-polystyrene multiblock copolymers are prepared by performing coordination polymerization of ethylene and α-olefin-based monomers and subsequent anionic polymerization of styrene-based monomers using CCTP In the case of , the coordination polymerization is carried out in a continuous manner, and the anionic polymerization is carried out in a batch mode, thereby achieving both control of the physical properties of the polymer and improved productivity.

In the present invention, the batch reactor in step (S2) can be connected in parallel with the continuous reactor in step (S1). After continuous polymerization with continuous injection of the reactants for continuous coordination polymerization, in order to transfer the obtained product to the batch reactor and proceed to the next step, the injection port of the batch reactor is blocked to prevent self-continuous The reactor continuously conveys the polyolefin. In this case, since the polyolefin is produced continuously in a continuous reactor, discarding the polyolefin can be avoided by transferring the polyolefin to another batch reactor.

Alkyllithium compounds are materials widely used as initiators for anionic polymerization, and triamine compounds have excellent coordination ability to lithium, and can be used for improving reactivity in the case where alkyllithium compounds are reacted as bases or nucleophiles. Purpose.

That is, in the present invention, the alkyl lithium compound can be used as an initiator through a complex action with a triamine compound. Through this, it is possible to maximize the production of the polyolefin-polystyrene-based multi-block copolymer, which is the object of the present invention, while suppressing polystyrene homopolymers, polyolefin homopolymers, and polyolefin homopolymers that would be generated by using conventional initiators. Production of polymers, and polyolefin-polystyrene diblock copolymers.

The alkyllithium compound may be a compound represented by the following formula 5.

[Formula 5]

In formula 5,

R ₁ is a hydrocarbon group of 1 to 20 carbon atoms, and

A series is represented by the following formula 6.

[Formula 6]

In formula 6,

R ₂ to R ₆ are each independently a hydrocarbon group of 1 to 20 carbon atoms, and

a and b are each independently an integer from 0 to 3.

R ₁ can be hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, or substituted or unsubstituted arylalkyl of 7 to 20 carbon atoms;

R ₂ to R ₆ may each independently be an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a substituted or unsubstituted 6 to Aryl of 20 carbon atoms, or substituted or unsubstituted arylalkyl of 7 to 20 carbon atoms; and

a and b may each independently be an integer from 0 to 2.

R ₁ to R ₆ may each independently be hydrogen or an alkyl group of 1 to 20 carbon atoms; and a may be 1 or 2, and b may be 0 or 1.

a and b may not be 0 at the same time, in particular a may be an integer from 1 to 3, and b may be an integer from 0 to 3, more particularly, a may be 1 or 2, and b may be an integer from 0 to 2, More particularly, a may be 1 or 2, and b may be 0 or 1.

In Formula 5, A may be particularly represented by the following Formula 6a or Formula 6b.

[Formula 6a]

[Formula 6b]

In the above formula,

R ₂ , R ₃ and R ₆ are each independently hydrogen or an alkyl group of 1 to 20 carbon atoms.

In addition, in one embodiment of the present invention, A in Formula 1 can be particularly represented by the following Formula 6a-1 or 6b-1.

[Formula 6a-1]

[Formula 6b-1]

An anionic polymerization initiator according to an embodiment of the present invention is an anionic polymer for polymerizing the polystyrene block of a polyolefin-polystyrene block copolymer, and can be used for permeation with polyolefin zinc compounds such as , (polyolefin-based) ₂ Zn) reaction is used to form an anionic polymerization initiator for polyolefin-polystyrene block copolymers.

(Polyolefin-based) ₂ Zn-based preparation via Coordination Chain Transfer Polymerization (CCTP), and additional growth of the polymer chain initiated by (poly-olefin-based) ₂ Zn can be used for the synthesis of polyolefin (PO)-based block copolymers . For example, the synthesis of polyethylene-block-polyester and polyethylene-block-polyether was attempted using PO functionalized with -OH end groups, and this -OH end group could be obtained by treating _CCTP with O The product (polyolefin-based) ₂ Zn is produced. In the same way, polyethylene-block-polystyrene block copolymers can be prepared by synthesizing polystyrene (PS) blocks from (polyolefin-based) ₂ Zn through a one-pot process, and by synthesizing polystyrene (PS) blocks in (polyolefin-based) When styrene monomer is polymerized using the anionic polymerization initiator of the present invention in the presence of ) ₂ Zn, PS chains can be efficiently grown from (polyolefin-based) ₂ Zn.

Further, the present invention provides an anionic polymerization initiator composition comprising a compound represented by the following formula 6 and a compound represented by the following formula 7.

[Formula 6]

[Formula 7]

In formula 6,

R ₂ to R ₆ are each independently a hydrocarbon group of 1 to 20 carbon atoms, and

a and b are each independently an integer from 0 to 3, and

In formula 7,

B is an alkyl group of 1 to 20 carbon atoms.

In one embodiment of the present invention, R ₂ to R ₆ can each independently be an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, and a cycloalkyl group of 3 to 20 carbon atoms , substituted or unsubstituted aryl groups of 6 to 20 carbon atoms, or substituted or unsubstituted arylalkyl groups of 7 to 20 carbon atoms;

B can be an alkyl group of 1 to 12 carbon atoms; and

a and b may each independently be an integer from 0 to 2.

In addition, in one embodiment of the present invention, R ₂ to R ₆ can each independently be hydrogen or an alkyl group of 1 to 20 carbon atoms; B can be an alkyl group of 1 to 8 carbon atoms; a can be an alkyl group of 1 to 8 carbon atoms an integer of 1 or 2, and b can be an integer of 0 or 1.

a and b may not be 0 at the same time, in particular a may be an integer from 1 to 3, and b may be an integer from 0 to 3, more particularly, a may be 1 or 2, and b may be an integer from 0 to 2, More particularly, a may be 1 or 2, and b may be 0 or 1.

In one embodiment of the present invention, the anionic polymerization initiator composition may additionally include a compound represented by the following formula 8.

[Formula 8]

R ₁ is a hydrocarbon group of 1 to 20 carbon atoms.

The anionic polymerization initiator composition may not contain a separate compound, which may be a solvent other than the compound represented by Formula 6, the compound represented by Formula 7, and the additional compound represented by Formula 8; or may contain The compound of formula 7 is a small number of individual compounds that react significantly.

If an anionic polymerization initiator composition containing a compound represented by Formula 6 and a compound represented by Formula 7 is injected as an anionic polymerization initiator, a structure such as Formula 5 can be formed, which can serve as an anionic polymerization initiator.

Further, the anionic polymerization initiator of the present invention includes a reaction procedure by injecting the compound represented by the following formula 6 and the compound represented by the following formula 7 in the presence of the compound represented by the following formula 8.

[Formula 6]

[Formula 7]

[Formula 8]

In the above formula,

R ₁ to R ₆ are each independently a hydrocarbon group of 1 to 20 carbon atoms;

a and b are each independently an integer from 0 to 3; and

B is an alkyl group of 1 to 20 carbon atoms.

In one embodiment of the present invention, R ₂ to R ₆ can each independently be an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, and a cycloalkyl group of 3 to 20 carbon atoms , substituted or unsubstituted aryl of 6 to 20 carbon atoms, or substituted or unsubstituted arylalkyl of 7 to 20 carbon atoms; and a and b may each independently be 0 to 2 and B may be an alkyl group of 1 to 12 carbon atoms.

In addition, in one embodiment of the present invention, R ₂ to R ₆ may each independently be hydrogen or an alkyl group of 1 to 20 carbon atoms; a may be an integer of 1 or 2, and b may be 0 or 1 and B may be an alkyl group of 1 to 8 carbon atoms.

a and b may not be 0 at the same time, in particular a may be an integer from 1 to 3, and b may be an integer from 0 to 3, more particularly, a may be 1 or 2, and b may be an integer from 0 to 2, More particularly, a may be 1 or 2, and b may be 0 or 1.

The alkyllithium compound represented by Formula 7 can be, for example, n-BuLi, which is a material widely used as an initiator for anionic polymerization, is readily available, and has excellent unit price benefit.

In the preparation method of the anionic polymerization initiator according to an embodiment of the present invention, the procedure of reacting the compound represented by formula 8 and the compound represented by formula 7 can be performed first, and then the compound represented by formula 6 can be reacted. The compound represented by formula 5 is prepared. In particular, by reacting the compound represented by the formula 8 and the compound represented by the formula 7 to produce an alkyl lithium as an intermediate, and reacting the alkyl lithium with the compound of the formula 6, the anionic polymerization initiator of the formula 5 is finally formed .

In addition, in the preparation method of the anionic polymerization initiator according to an embodiment of the present invention, the compound represented by the formula 7 and the compound of the formula 6 by injecting in the presence of the compound of the formula 8 can be carried out without additional solvent Procedure for reacting compounds. The condition of no additional solvent means no separate compound, which can be a solvent other than the compound represented by formula 7 and the compound represented by formula 6 in the presence of the compound represented by formula 8; Small amounts of individual compounds that react significantly with compounds of formula 7.

If the reaction is performed without additional solvent, the reaction of the compound represented by Formula 8 and the compound represented by Formula 7 can be performed as a main reaction, and the anionic polymerization initiator of Formula 5 can be efficiently prepared. If there is a separate solvent, the anionic polymerization initiator of Formula 5, the compound produced by the reaction of the compound represented by Formula 7 and the compound represented by Formula 6, and the compound represented by Formula 7 and the compound represented by Formula 6 The decomposed compound of the compound produced by the reaction of , will exist in a mixed state, and it is not effective.

The anionic polymerization initiator or anionic polymerization initiator composition of the present invention can be used as an initiator for polymerizing styrene, and can be effectively used as a polyolefin, especially a (polyolefin-based) ₂ Zn-propagated polymer, from an organozinc compound. Initiator for styrene chains in which polyolefin chains grow with zinc (Zn) as the center.

The styrenic monomer may be a styrenic monomer having 6 to 20 carbon atoms, more particularly, an aryl group containing 6 to 20 carbon atoms is a substituted ethylene, a phenyl group is a substituted ethylene, etc. styrenic monomers such as styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene or mixtures thereof.

In particular, the alkyl lithium compound and the triamine compound may be mixed with an aliphatic hydrocarbon solvent and injected, or sequentially injected into a batch reactor.

The temperature of the anionic polymerization may vary depending on the reaction materials, reaction conditions, etc., and may specifically be 40°C or higher, 90°C or higher, and 170°C or lower, 120°C or lower.

The time of the anionic polymerization may vary depending on the reaction materials, reaction conditions, etc., and may be specifically 0.5 to 10 hours, 0.5 to 8 hours, 0.5 to 5 hours, or 0.5 to 2 hours. Within this range, it is advantageous to convert the entire amount of the injected styrenic monomer into a multi-block copolymer.

Through this reaction, polyolefin-polystyrene-based multi-block copolymers can be prepared, and can be, for example, polystyrene-poly(ethylene-co-propylene)-polystyrene block copolymers, polystyrene-poly( Ethylene-co-1-butene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-pentene)-polystyrene block copolymer, polystyrene-poly(ethylene- co-1-hexene)-polystyrene block copolymer, polystyrene-poly(ethylene-co-1-heptene)-polystyrene block copolymer, polystyrene-poly(ethylene-co- 1-octene)-polystyrene block copolymer, or a mixture thereof.

Example

Hereinafter, the present invention will be explained in more detail with reference to embodiments. However, these embodiments are for illustrating the present invention, and the scope of the present invention is not limited thereto.

1. Preparation of polyolefins

Example 1-1

In a 0.3 L continuous stirred tank reactor, [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B( C ₆ F ₅ ) ₄ ] ^- (45.0 μmol) activated hafnium compound, 0.17 mL/min (23 μmol/min) organozinc compound as chain transfer agent, 6 mL/min methylcyclohexane (MCH) as chain transfer agent While an organic solvent, 1500 cc/min of ethylene gas, and 2.7 mL/min of 1-hexene were used as α-olefin-based monomers, the pressure and temperature in the reactor were set to 25 bar and 90° C., and polymerization was carried out. A residence time of 24 minutes was reached to produce polyolefin.

Example 1-2 to 1-13

The preparation was carried out in the same manner as in Example 1-1, but the polymerization conditions in the continuous reactor were changed in Table 1 below.

[Table 1]

Comparative example 1-1

In a batch reactor, both coordination polymerization and anionic polymerization are performed to prepare polyolefin-polystyrene-based copolymers. Specifically, the Parr reactor (1 gallon) was vacuum dried at 120°C for 2 hours. A solution of Oc3Al (1466.4 mg, 1000 μmol _- Al) in methylcyclohexane (1200 g) was added to the reactor. The mixture was stirred at 120°C for 1 hour using a heating mantle, then the solution was removed using a cannular.

Methylcyclohexane (1170 mL) containing Oc3Al (1098.3 mg, 749 μmol _- Al/25 wt% in hexane) was charged as scavenger in the reactor, and 1-hexene (639 mL) as the α-olefin-based monomer, and the temperature was set to 90°C. A solution of an organozinc compound (1000 μmol) in methylcyclohexane (3.85 g) was charged as a chain transfer agent, and then injected with a solution containing [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C _{6F5 )4 ]} ^- (10.0 μmol) A solution of activated hafnium compound (10.0 μmol-Hf) in methylcyclohexane (1.68 g). The pressure of the reactor was maintained at 25 bar by opening the valve of the ethylene tank, and the polymerization was carried out for 40 minutes to prepare polyolefin.

Comparative example 1-2 and 1-3

The preparation was carried out in the same manner as in Comparative Example 1-1, but the polymerization conditions in the batch reactor were changed in Table 2 below.

[Table 2]

In this table, the volume of ethylene is based on 20°C and 1 atm.

2. Polyolefin - Preparation of polystyrene-based multiblock copolymers

Example 2-1

Anionic polymerization was carried out in a batch reactor using styrenic monomers and the polyolefins prepared in Examples 1-8 as reactants.

The resulting products comprising the polyolefins prepared in Examples 1-8 were transferred to a batch reactor and injected therein by mixing Me3SiCH2Li (21.7 _{mg )} in methylcyclohexane (3.85 g). , 0.23 mmol) and PMDETA (43.8 _mg , 0.25 mmol) as a solution _of Me3SiCH2Li (PMDETA). After maintaining the temperature at 90°C for 30 minutes with stirring, styrene (7.8 g) was injected. Use a heating jacket to keep the temperature in the range of 90-100°C.

The viscosity gradually increased and reached a nearly invisible state within 5 hours. Complete conversion of styrene was confirmed ^by1H NMR analysis of an aliquot. After complete conversion of styrene, 2-ethylhexanoic acid and ethanol were injected continuously. The obtained polymer block (23 g) was dried in a vacuum oven at 80°C overnight.

Example 2-2 and 2-3

The polyolefin-polystyrene-based multi-block copolymer was prepared in the same manner as in Example 2-1, but the polyolefins of Examples 1-8 were respectively applied in Examples 1-11 and 1-12 instead of in Example 2-1. Olefins.

Comparative example 2-1

Anionic polymerization was carried out in a batch reactor using styrene-based monomer and the polyolefin prepared in Comparative Example 1-1 as reactants.

In the reactor containing the polyolefin prepared in Comparative Example 1-1, the temperature was controlled in the range of 90-120°C, and the remaining ethylene gas was discharged. If the temperature reached 90°C, add Me3SiCH2Li prepared by mixing Me3SiCH2Li (81.9 _mg , 0.87 mmol) and PMDETA ( _{165.7 mg} , 0.957 mmol) in methylcyclohexane (3.85 g ₎ (PMDETA) solution. After maintaining the temperature at 90°C for 30 minutes with stirring, styrene (69.0 g) was injected. Use a heating jacket to keep the temperature in the range of 90-100°C.

The viscosity gradually increased and reached a nearly invisible state within 5 hours. Complete conversion of styrene was confirmed ^by1H NMR analysis of an aliquot. After complete conversion of styrene, 2-ethylhexanoic acid and ethanol were injected continuously. The obtained polymer block (132 g) was dried in a vacuum oven at 80°C overnight.

Comparative example 2-2 and 2-3

The polyolefin-polystyrene-based multi-block copolymer was prepared in the same way as in Comparative Example 2-1, except that Comparative Examples 2-2 and 2-3 were respectively used to replace the polymer of Comparative Example 1-1 in Comparative Example 2-1. Olefins.

Experimental example 1 : Analysis of Polyolefins

(1) Measure the content of ethylene and α-olefin

Measurements are carried out by NMR. ¹ H NMR was measured using a Bruker 600 MHz AVANCE III HD NMR apparatus under conditions of ns=16, d1=3s, solvent=TCE-d2, and 373K, and the solvent peak of TCE-d2 was calibrated to 6.0 ppm. It was confirmed that the CH ₃ of 1-propene was at 1 ppm, the CH ₃ related peak (triplet state) of the butyl branch caused by 1-hexene was confirmed to be around 0.96 ppm, and the content was calculated. In addition, the styrene content was calculated from the aromatic peak around 6.5 to 7.5 ppm.

(2) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (polydispersity index, PDI)

The weight average molecular weight (Mw, g/mol) and the number average molecular weight (Mn, g/mol) were measured using gel permeation chromatography (GPC), respectively, and the molecular weight distribution (polydispersity index, PDI) was measured by weight average Molecular weight is calculated by dividing by the number average molecular weight.

- String: PL Olexis

- Solvent: Trichlorobenzene (TCB)

- Flow rate: 1.0 mL/min

- Sample concentration: 1.0 mg/mL

- Injection volume: 200 µL

- Column temperature: 160°C

- Detector: Agilent High Temperature RI Detector

- Standard: Polystyrene

- Molecular weights were calculated by Universal Calibration using the Mark-Houwink equation (K = 40.8 × 10 ^-5 , α = 0.7057).

(3) Polyolefin yield (ton/m ³ hrmol)

In the case of Examples 1-1 to 1-13, the amount of polyolefin discharged from the continuous reactor during the entire reaction period was measured, and the time, moles, and mass of the comparative volume were calculated, and in Comparative Example 1-1 In the case of 1-3, the polyolefin was calculated from the yields of the multi-block copolymers prepared in Comparative Examples 2-1 to 2-3 and the mass fractions of C2, 1-C6 measured by ¹ H NMR degree of productivity.

[table 3]

In the case of Comparative Example 1-1, the coordination polymerization of ethylene and an α-olefin-based monomer was performed in a batch reactor, and the yield of polyolefin was 5,086 ton/m ³ ·hr·mol, which was the same as The examples and comparative examples in which the coordination polymerization is carried out by continuous reaction are significantly lower. Meanwhile, in the case of Example 1-13, the results were obtained by changing specific conditions (including the injection amount of the solvent, etc.) among the reaction conditions, and it was confirmed from the data that compared with Comparative Examples 1-1 to 1- At 3, the molecular weight of polyolefin is low and the molecular weight distribution is wide, but the production volume is obviously superior.

Experimental example 2 : Polyolefin - Analysis of Polystyrene Multiblock Copolymers

Regarding the polyolefin-polystyrene-based multi-block copolymers prepared in the Examples and Comparative Examples, physical properties were measured according to the following conditions and methods, and the results are shown in Tables 4 to 6.

(1) Measurement of ethylene, α-olefin and styrene content

The measurement was performed in the same manner as in Experimental Example 1. The styrene content was calculated using the aromatic peak around 6.5 to 7.5 ppm.

(2) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (polydispersity index, PDI)

The measurement was performed in the same manner as in Experimental Example 1.

(3) Tensile properties

Each specimen was fabricated according to the tensile test method of ASTM D412, and the tensile strength, elongation, and 300% modulus were measured, and the stress-strain curves are shown in Figures 1-3.

[Table 4]

[table 5]

[Table 6]

As shown in Tables 4 to 6, in the case of Comparative Examples 2-1 to 2-3 in which all polymerization procedures were carried out in batch reactors, the tensile properties were higher than those of the corresponding Examples 2-1 to 2- The poor tensile properties of 3, and these results would be negative evidence of non-uniform arrangement of monomers in the polymer chain and, structurally, an inability to effectively induce the distribution of the tensile properties in the polymer chain.

The differences in the physical properties of the polymers resulting from the polymerization procedure can be clearly recognized from Figures 1 to 3 . 1 to 3, it can be confirmed that the polyolefin-polystyrene-based multi-block copolymers of Examples 2-1 to 2-3 and the polyolefin-polystyrene-based multi-block copolymers of Comparative Examples 2-1 to 2-3 The segmented copolymers exhibited extremely high tensile strength in comparison, and it was confirmed that even with a low styrene content as in Example 2-1, extremely high tensile strength was exhibited. These results are considered to be due to the fact that even for polyolefins with similar molecular weight and composition polymerized by continuous polymerization, the effect of the arrangement of monomers in the polymer chain can be maximized compared to batch polymerization, and even more can be shown. best results.

In addition, from Examples 2-1 to 2-3, it can be confirmed that the tensile strength and the elongation can be controlled by controlling the content of α-olefin and styrene.

[ Fig. 1 ] shows stress-strain curves of the polyolefin-polystyrene-based multi-block copolymers of Example 2-1 and Comparative Example 2-1 according to the present invention.

[ Fig. 2 ] shows stress-strain curves of the polyolefin-polystyrene-based multi-block copolymers of Example 2-2 and Comparative Example 2-2 according to the present invention.

[ Fig. 3 ] shows stress-strain curves of the polyolefin-polystyrene-based multi-block copolymers of Example 2-3 and Comparative Example 2-3 according to the present invention.

Claims (10)

A method for preparing a polyolefin-polystyrene-based multi-block copolymer, the method comprising: (S1) Continuously injecting the hafnium compound, the organozinc compound, the organic solvent, the ethylene gas, and the α-olefin-based monomer into a continuous type reactor by performing coordination polymerization of ethylene and the α-olefin-based monomer at the same time ) to produce a polyolefin, and delivering the polyolefin to a batch type reactor; and (S2) In the batch reactor, the anionic polymerization of the polyolefin and the styrene-based monomer is carried out in the presence of an alkyl lithium compound. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the injection flow rate of the organic solvent is 6 to 48 mL/min per 1 L of the volume of the continuous reactor . The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the molar ratio Zn/Hf of the hafnium element in the hafnium compound and the zinc element in the organozinc compound is Zn/Hf 1 or higher. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the organozinc compound is a compound represented by the following formula 1: [Formula 1]

In formula 1, A is an alkyl group of 1 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a halogen, an alkyl group of 1 to 12 carbon atoms, a ring of 3 to 12 carbon atoms Alkyl, alkoxy of 1 to 8 carbon atoms or aryl of 6 to 12 carbon atoms substituted with aryl of 6 to 20 carbon atoms, and B is substituted by alkenyl of 2 to 12 carbon atoms An aryl group of 6 to 12 carbon atoms. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the organic solvent is one or more selected from the group consisting of: methylcyclohexane, Isobutane, hexane and cyclohexane. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the α-olefin-based monomer is selected from one or more of 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 alkene, 4,4-diethyl-1-hexene and 3,4-dimethyl-1-hexene. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the alkyllithium compound is a compound represented by the following formula 5: [Formula 5]

In Formula 5, R ₁ is a hydrocarbon group of 1 to 20 carbon atoms, and A is represented by the following Formula 6: [Formula 6]

In Formula 6, R ₂ to R ₆ are each independently a hydrocarbon group of 1 to 20 carbon atoms, and a and b are each independently an integer of 0 to 3. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the styrene-based monomer is one or more selected from the group consisting of: styrene, Alpha-methylstyrene, alpha-ethylstyrene and p-methylstyrene. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the coordination polymerization is carried out at a temperature of 70 to 170°C. The method for preparing a polyolefin-polystyrene-based multi-block copolymer according to claim 1, wherein the anionic polymerization is carried out at a temperature of 40 to 170° C. for 0.5 to 10 hours.

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