Polyolefin-polystyrene multiblock copolymer, organozinc compound for producing same, and method for producing polyolefin-polystyrene multiblock copolymer

Abstract

To provide a polystyrene-polyolefin-polystyrene triblock copolymer and a method for producing the same.SOLUTION: There is provided a polystyrene-polyolefin-polystyrene triblock copolymer represented by the following chemical formula 7. (Ar is an aryl group having 6 to 20 carbon atoms; the average value of m is 20 to 10000; Y and Y' independently are any one of H, methyl, ethyl, butyl, hexyl and octyl and Y and Y' are not identical to each other; p and 1-p are a molar fraction of each repeating unit constituting a repeating unit body n and the value of p is 0 to 1; the average value of n is 40 to 10000; R2 to R3 independently are H or hydrocarbyl having 1 to 20 carbon atoms; and z is an integer of 0 to 10.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyolefin-polystyrene multiblock copolymer having a structure in which polystyrene chains are attached to both ends of a polyolefin chain, an organozinc compound for producing the same, and a method for producing the polyolefin-polystyrene multiblock copolymer. [Background technology]

[0002] Polyolefin-polystyrene block copolymers, such as Styrene-Ethylene / Butylene-Styrene (SEBS) or Styrene-Ethylene / Propylene-Styrene (SEPS), are currently on the global market in the hundreds of thousands of tons. In addition, they have advantages over Styrene-Butadiene-Styrene (SBS) or Styrene-Isoprene-Styrene (SIS) in terms of heat resistance and light resistance, and are used as materials for grips and handles that provide a soft and strong touch, elastic materials for diapers, oil-gels used in medical and communication materials, impact modifiers for engineering plastics, plasticizers or tougheners for transparent polypropylene, etc. Conventional SEBS is manufactured through a two-step reaction in which SBS obtained by anionic polymerization of styrene and butadiene is hydrogenated. Conventional SEPS is also manufactured through a two-step reaction in which SIS obtained by anionic polymerization of styrene and isoprene is hydrogenated. Thus, the process of hydrogenating all the double bonds in the polymer backbone to saturate them is costly, and the unit price of SEBS and SEPS is much higher than that of SBS and SIS before hydrogenation. This may act as a limit to market expansion. In addition, it is virtually impossible to saturate all the double bonds in the polymer chain by hydrogenation, and commercialized SEBS and SEPS contain some remaining double bonds, the presence of which can often be problematic.

[0003] Therefore, the present inventors have developed a technique for producing a polyolefin-polystyrene diblock copolymer from an olefin and a styrene monomer in a one-pot process (Patent Document 1 and Non-Patent Document 1).

[0004] Industrially, more useful block copolymers are polyolefin-polystyrene multiblock copolymers with triblock or higher such as SEBS, which have thermoplastic elastomer properties due to their multiblock structure and can have a unique range of applications. However, no technology has been developed to date that can produce polyolefin-polystyrene multiblock copolymers in one pot from olefin and styrene monomers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent No. 1657925 [Non-patent literature]

[0006] [Non-Patent Document 1] JOURNAL OF POLYMER SCIENCE,PART A:POLYMER CHEMISTRY 2016,54,3110-3118. [Non-Patent Document 2] J.AM.CHEM.SOC.2005,127,9913-9923. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a polyolefin-polystyrene multiblock copolymer having a structure in which polystyrene chains are attached to both ends of a polyolefin chain.

[0008] Another object of the present invention is to provide an organozinc compound which can be easily used in the preparation of the polyolefin-polystyrene multiblock copolymer.

[0009] It is still another object of the present invention to provide a one-pot method for directly preparing the polyolefin-polystyrene multiblock copolymer from an olefin monomer and a styrene monomer.

[0010] Another object of the present invention is to provide a method for producing a polystyrene-polyolefin-polystyrene triblock copolymer by a one-pot reaction, which has a significantly low production cost and is suitable for realizing the physical properties of a thermoplastic elastomer by suppressing the formation of diblock and homopolymers.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0012] An embodiment of the present invention relates to a polyolefin-polystyrene multiblock copolymer including a repeating unit represented by the following Chemical Formula 1:

[0013] [ka]

[0014] In the above formula 1, Ar is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; n is 0 or has an average value of 10 to 1,000; m is an average value of 10 to 1,000; A is Substituted or unsubstituted with 6 to 20 carbon atomsis a meta-phenylene group or a para-phenylene group; R is any one of hydrogen, a methyl group, an ethyl group, a butyl group, and a hexyl group; the average value of a is 10 to 10,000; * is a terminal portion of a repeating unit or a portion connected to the Z portion by a covalent bond; Z is derived from an anionic polymerization initiator and is an alkyl group having 1 to 20 carbon atoms and containing a silicon atom, an alkyl group having 1 to 20 carbon atoms and not containing a silicon atom, an arylalkyl group having 7 to 20 carbon atoms and containing a silicon atom, an arylalkyl group having 7 to 20 carbon atoms and not containing a silicon atom, or a bonding portion connected to the * by a covalent bond.

[0015] In the above Chemical Formula 1, Z is derived from an anionic polymerization initiator and is a silicon-containing alkyl group having 1 to 20 carbon atoms, a silicon-containing arylalkyl group having 7 to 20 carbon atoms, or a bonding site that is covalently linked to the *.

[0016] In the above formula 1, Ar is an unsubstituted phenyl group; A is an unsubstituted meta-phenylene group or para-phenylene group; Z is (CH3)3SiCH2- or together with the above * These are binding sites that are linked by a bond.

[0017] Another embodiment of the present invention relates to an organozinc compound represented by the following Formula 2:

[0018] [ka]

[0019] In the above formula 2, A is Substituted or unsubstituted with 6 to 20 carbon atoms It is a meta-phenylene group or a para-phenylene group; the average value of a is 10 to 10,000; R is any one of hydrogen, a methyl group, an ethyl group, a butyl group, and a hexyl group; and p and q are each 0 or 1.

[0020] The organozinc compound may be represented by the following formula 2-1:

[0021] [ka]

[0022] The organozinc compound may be represented by the following formula 2-2:

[0023] [ka]

[0024] In the above chemical formulas 2-1 and 2-2, A is Substituted or unsubstituted with 6 to 20 carbon atoms It is a meta-phenylene group or a para-phenylene group; the average value of a is 10 to 10,000; and R is any one of a hydrogen atom, a methyl group, an ethyl group, a butyl group, and a hexyl group.

[0025] Yet another embodiment of the present invention relates to a method for preparing a polyolefin-polystyrene multiblock copolymer represented by the above-mentioned formula 1, comprising: a first step of preparing a compound represented by the above-mentioned formula 2-2 by coordination polymerization of an olefin monomer with a transition metal catalyst in the presence of an organozinc compound represented by the above-mentioned formula 2-1; and a second step of sequentially introducing an alkyllithium compound containing a silicon atom, a triamine compound, and a styrene monomer to perform anionic polymerization.

[0026] The alkyllithium compound containing a silicon atom may be represented by Chemical Formula 3:

[0027] [ka]

[0028] The triamine compound may be represented by the following formula 4:

[0029] [ka]

[0030] The olefin monomer may be ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene or a mixture thereof, and the styrenic monomer may be styrene.

[0031] The polymerization in the first step may be carried out by solution polymerization using a solvent containing one or more of isobutane, hexane, cyclohexane, and methylcyclohexane.

[0032] The molar ratio of the organozinc compound represented by chemical formula 2-1 added in the first step to the silicon-containing alkyllithium compound added in the second step (i.e., [Li] / [Zn]) may be 0.5 to 2.

[0033] The molar ratio of the triamine compound and the silicon-containing alkyllithium compound charged in the second step may be 1:0.5 to 1:1.

[0034] The molar ratio ([Styrene] / [Zn]) of the zinc atoms in the reaction solution to the styrene monomer added in the second step may be 250 to 1,000.

[0035] Yet another embodiment of the present invention relates to a polystyrene-polyolefin-polystyrene triblock copolymer represented by the following Chemical Formula 7.

[0036] [ka]

[0037] In the formula 7, Ar is an aryl group having 6 to 20 carbon atoms; the average value of m is 20 to 10,000; Y and Y' are each independently any one of hydrogen, methyl, ethyl, butyl, hexyl, and octyl, and Y and Y' are not the same; p and 1-p are mole fractions of each repeating unit constituting the repeating unit n, p being a value of 0 to 1; the average value of n is 40 to 10,000; R 2 ~R 3 each independently represents hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; and z represents an integer of 0 to 10.

[0038] In the above formula 7, Ar is phenyl; m has an average value of 20 to 200; Y is hydrogen; Y′ is methyl, ethyl, butyl, or hexyl; R 2 ~R 3 is hydrogen; z can be 0 or 2.

[0039] The polystyrene-polyolefin-polystyrene triblock copolymer may have a PDI of 1.2 to 1.5.

[0040] Yet another embodiment of the present invention relates to a method for preparing a polystyrene-polyolefin-polystyrene triblock copolymer, the method comprising: forming a polyolefin block by chain transfer polymerization of an olefin monomer using a polynuclear zinc compound as a chain transfer agent; and forming a polystyrene block by anionic polymerization of an alkyllithium compound containing a silicon atom, a triamine compound, and a styrene monomer.

[0041] The polynuclear zinc compound may be represented by the following formula 8:

[0042] [ka]

[0043] In the above formula 8, R 1 is a hydrocarbyl having 1 to 20 carbon atoms; R2 ~R 3 each independently represents hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; the average value of a is 1 to 10 and z is an integer from 0 to 10. .

[0044] The polynuclear zinc compound may be represented by any one of the following formulas 8-1 and 8-2.

[0045] [ka]

[0046] [ka]

[0047] The above formulas 8-1 and 8-2 In, the average value of a is 1 to 10.

[0048] The alkyllithium compound containing a silicon atom may be represented by the above formula 3.

[0049] The triamine compound may be represented by Chemical Formula 4.

[0050] In the step of forming the polystyrene block, the molar ratio of styrene monomer input per zinc atom ([Styrene] / [Zn]) may be 250 to 1,000.

[0051] The polystyrene-polyolefin-polystyrene triblock copolymer may have a number of polystyrene polymer chains generated per zinc atom ([PS-chains] / [Zn]) of 2.0 to 3.0. Effect of the Invention

[0052] The present invention has an effect of providing a polyolefin-polystyrene multiblock copolymer having a commercially useful structure, an organozinc compound for producing the same, and a method for directly producing the polyolefin-polystyrene multiblock copolymer from an olefin monomer and a styrene monomer in one pot. [Brief description of the drawings]

[0053] [Figure 1] 1 is a 1H NMR spectrum of an organozinc compound represented by chemical formula 2-1 prepared in Preparation Example 1 of the present invention. [Diagram 2] 1 is a graph showing the results of GPC analysis of a block copolymer prepared in Example 5 of the present invention. [Diagram 3] 1 is a TEM image of the block copolymer prepared in Example 3 of the present invention. [Figure 4] 1 is a TEM image of the block copolymer prepared in Example 4 of the present invention. [Diagram 5] 1 is a TEM image of the block copolymer prepared in Example 5 of the present invention. [Figure 6] 1 is a TEM image of the block copolymer prepared in Example 8 of the present invention. [Figure 7] 1 shows the results of repeated tensile tests of the block copolymers prepared in Examples 2, 3, 5, and 8 of the present invention and the copolymer used in Comparative Example 1. [Figure 8] 1 shows the results of GPC analysis of the triblock copolymer prepared in Example 9 of the present invention. [Figure 9] 1 shows transmission electron microscope images of the triblock copolymers prepared in Example 19(e), Example 11(a), Example 12(c), Example 13(b), Example 15(d) and Comparative Example 1(f) of the present invention. [Figure 10] 1 is a graph showing stress measurement results from tensile test results for Examples 9, 10, 12, and 15 of the present invention. [Figure 11]1 shows the results of repeated tensile tests of the triblock copolymer prepared in Example 12 of the present invention. [Figure 12] 1 shows the results of repeated tensile tests of the triblock copolymer of Comparative Example 1 of the present invention. [Figure 13] 1 shows the 1H NMR spectrum of the triblock copolymer prepared in Example 12 of the present invention. [Figure 14] 1 shows the DSC analysis result of the triblock copolymer prepared in Example 10 of the present invention. BEST MODE FOR CARRYING OUT THEINVENTION

[0054] Unless otherwise specified, alphabetic symbols in the chemical formulas described in this application represent the elements represented by those symbols, Me represents methyl, Et represents ethyl, PO represents polyolefin, PS represents polystyrene, PE represents polyethylene, and PP represents polypropylene.

[0055] Unless otherwise specified, the term "polymer" as used in this application is intended to include all of oligomers, homopolymers, and copolymers.

[0056] The symbol "*" in this application means an end group of a polymer chain.

[0057] Polyolefin-polystyrene multiblock copolymer

[0058] [ka]

[0059] In the above formula 1, Ar is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; n is 0 or has an average value of 10 to 1,000; m is an average value of 10 to 1,000; A is Substituted or unsubstituted with 6 to 20 carbon atomsis a meta-phenylene group or a para-phenylene group; R is any one of hydrogen, a methyl group, an ethyl group, a butyl group, and a hexyl group; the average value of a is 10 to 10,000; * is each independently an end portion of a repeating unit or a portion linked to the Z portion by a covalent bond; Z is derived from an anionic polymerization initiator and is an alkyl group having 1 to 20 carbon atoms and containing a silicon atom, an alkyl group having 1 to 20 carbon atoms and not containing a silicon atom, an arylalkyl group having 7 to 20 carbon atoms and containing a silicon atom, an arylalkyl group having 7 to 20 carbon atoms and not containing a silicon atom, or a bonding portion linked to the * by a covalent bond.

[0060] The polyolefin-polystyrene multiblock copolymer having the repeating unit of the structure represented by Chemical Formula 1 is the first compound disclosed by the preparation method of the present invention.

[0061] In this specification, the repeating unit a refers to a polyolefin block structurally contained in the multiblock copolymer of Formula 1. Similarly, the repeating unit n and the repeating unit m refer to each polystyrene block structurally contained in the multiblock copolymer of Formula 1. At the same time, a, n, and m may be values ​​indicating the degree to which each repeating unit in Formula 1 is repeated.

[0062] In typical polymer synthesis, a mixture of a, n, and m values ​​is obtained that has a distribution that is not a single integer, and therefore the average values ​​are measured and discussed in this application.

[0063] In the above Chemical Formula 1, each Ar is independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. When the aryl group having 6 to 20 carbon atoms is substituted, the substituent is not particularly limited, and specific examples thereof include hydrocarbyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and isomers thereof. The hydrocarbyl used as the substituent may be cyclic, acyclic, BranchedOr it may be in a straight-chained form.

[0064] Specifically, the aryl group having 6 to 20 carbon atoms may include a monocyclic aryl group, a polycyclic aryl group, or a heteroaryl group, and may include, for example, monocyclic aryl groups such as benzyl, phenyl, biphenyl, terphenyl, and tolyl; polycyclic aryl groups such as naphthyl, anthracenyl, and phenanthrenyl; and the like.

[0065] In the formula 1, the repeating unit n representing the polystyrene block (-[CH2-CH(Ar)] in the formula 1) n -) and repeating unit m (-[CH2-CH(A r)] m -) The length of each is a polyolefin-polystyrene multiblock copolymer. The amount of styrene monomer added as a reactant during the preparation of the copolymer can be adjusted.

[0066] In the formula 1, n is 0 or an average value of 10 to 1,000. When n is 0, the terminal group of the polyolefin chain (i.e., -[CH(R)CH2] a -*) can be covalently bonded to the Z moiety of Chemical Formula 1 of the same molecule or the Z moiety of Chemical Formula 1 of another molecule. This structure can be formed by reacting with a styrene group contained in an organozinc compound before the end group of a polyolefin chain reacts with an added styrene monomer in the second step of the method for producing a polyolefin-polystyrene multiblock copolymer described below.

[0067] Furthermore, the average value of each of n and m may be 10 to 1,000. Although there is no particular lower limit, if the average value of each of n and m exceeds 1,000, the viscosity is high and it is not easy to realize a compound having the structure of Chemical Formula 1. Specifically, the average value of each of n and m in Chemical Formula 1 may be 100 to 500. Within this range, the production of the multiblock copolymer of Chemical Formula 1 is more efficient, and the produced multiblock copolymer can be applied to more diverse fields.

[0068] In the above formula 1, A is Substituted or unsubstituted with 6 to 20 carbon atoms It is a meta-phenylene group or a para-phenylene group. When the meta-phenylene group or the para-phenylene group is substituted, the substituent is not particularly limited, and specific examples thereof include hydrocarbyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and isomers thereof. In addition, the hydrocarbyl used as the substituent may be in the form of a cyclic, acyclic, branched, or straight-chained.

[0069] The average value of a in Chemical Formula 1 can be adjusted according to the content of olefin monomer and organozinc compound input as reactants in the preparation method described below. The average value of a is 1 or more with no lower limit, but if the average value of a exceeds 10,000, the viscosity is high and it is difficult to realize a compound having the structure of Chemical Formula 1. Specifically, the average value of a in Chemical Formula 1 may be 10 to 10,000.

[0070] Specifically, the repeating unit a (-[CH(R)-CH2] in Chemical Formula 1) a -) can be produced by using olefin monomers including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. as reactants in the production process.

[0071] In a specific example, the repeating unit a can be prepared by using one of olefin monomers including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. as a reactant in the preparation method, or by using two of olefin monomers including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. as reactants. Specifically, the repeating unit a in formula 1 can be polyethylene, polypropylene, poly(ethylene-co-propylene), It may be poly(ethylene-co-1-butene), poly(ethylene-co-1-hexene), or poly(ethylene-co-1-octene).

[0072] In the formula 1, * is each independently an end group moiety of the formula 1 or a moiety connected to the Z moiety by a covalent bond. Specifically, when * is an end group moiety in the formula 1, it may vary depending on the conditions for terminating the reaction in the preparation method. For example, * may react with oxygen to become -OH or with water to become -H depending on the termination conditions. In addition, some of them may react with a styrene moiety contained in an organozinc compound in the styrene polymerization step of the preparation method described below to be connected to the Z moiety of the formula 1 of the same molecule or the Z moiety of the formula 1 of different molecules by a covalent bond.

[0073] In the above Chemical Formula 1, Z is derived from an anionic polymerization initiator and may be an alkyl group having 1 to 20 carbon atoms and containing a silicon atom, an alkyl group having 1 to 20 carbon atoms and not containing a silicon atom, an arylalkyl group having 7 to 20 carbon atoms and containing a silicon atom, an arylalkyl group having 7 to 20 carbon atoms and not containing a silicon atom, or a bonding moiety that is covalently linked to the *.

[0074] Specifically, in the above Chemical Formula 1, Z is derived from an alkyllithium compound containing a silicon atom among the anionic polymerization initiators, and may be an alkyl group containing a silicon atom and having 1 to 20 carbon atoms, an arylalkyl group containing a silicon atom and having 7 to 20 carbon atoms, or a bonding moiety that is covalently linked to the *.

[0075] More specifically, Ar in the formula (1) is an unsubstituted phenyl group; A is an unsubstituted meta-phenylene group or para-phenylene group; Z is (CH3)3SiCH2-; or The bond may be covalently linked to the repeat unit of another molecule or to the * site of the repeat unit of the same molecule. In this case, the cost is excellent, commercial utility is excellent, and reaction activity during production is excellent.

[0076] In a specific example, the copolymer consisting of the repeating unit represented by Chemical Formula 1 may be a polystyrene-polyolefin-polystyrene triblock copolymer, a polystyrene-polyolefin-polystyrene-polyolefin-polystyrene pentablock copolymer, a polystyrene-polyolefin-polystyrene-polyolefin-polystyrene-polyolefin-polystyrene heptablock copolymer, or a mixture thereof.

[0077] For example, when Z in formula 1 is an alkyl or arylalkyl group derived from an initiator and all of the * moieties are terminal groups, formula 1 may be a triblock copolymer.

[0078] For example, when Z in formula 1 is covalently linked to the terminal * of the polyolefin chain in the repeating unit of formula 1 of another molecule where n is 0, a pentagonal block copolymer structure is obtained. It can be formed.

[0079] For example, when the terminal Z of the pentablock copolymer is covalently linked to the terminal * of the polyolefin chain of a repeating unit of Formula 1 of another molecule in which n is 0, a heptagonal block copolymer structure can be formed.

[0080] Organozinc Compounds Another embodiment of the present invention relates to an organozinc compound represented by the following formula 2. The organozinc compound represented by the formula 2 has excellent suitability for preparing the polyolefin-polystyrene block copolymer of the present invention.

[0081] [ka]

[0082] In the above formula 2, A is Substituted or unsubstituted with 6 to 20 carbon atoms It is a meta-phenylene group or a para-phenylene group; the average value of a is 10 to 10,000; R is any one of hydrogen, a methyl group, an ethyl group, a butyl group, and a hexyl group; and p and q are each 0 or 1.

[0083] In one embodiment, the organozinc compound of formula 2 may be a compound represented by formula 2-1 or 2-2. The compound represented by formula 2-1 or 2-2 is the first compound disclosed by the present invention, and has easy supply and demand of raw materials, low process cost, excellent productivity, and excellent commercial applicability for mass production.

[0084] [ka]

[0085] [ka]

[0086] In the above chemical formulas 2-1 and 2-2, A is Substituted or unsubstituted with 6 to 20 carbon atoms It is a meta-phenylene group or a para-phenylene group; the average value of a is 10 to 10,000; and R is any one of a hydrogen atom, a methyl group, an ethyl group, a butyl group, and a hexyl group.

[0087] Specifically, the organozinc compound of the formula 2-1 can be prepared by reacting the organozinc compound of the formula 2-1 with the reaction product of the following reaction formula 1: In this step, excess CH2=CH-C6H4-CH=CH2 is reacted with Et2BH, and then reacted with Et2Zn to produce CH2=CH-C6H4-CH=CH2. When producing H2CH2-Zn-CH2CH2-C6H4-CH=CH2 compounds, the yield is excellent. In particular, the organozinc compound produced without a purification process can be used directly. In addition, the organozinc compound of formula 2-1 acts as a polymerization inhibitor, preventing unintended polymerization with styrene groups, and thus does not cause problems during storage and transportation.

[0088] [ka]

[0089] In this case, CH2=CH-C6H4-CH= used as a reactant in Reaction Scheme 1 CH2 and Et2Zn compounds are currently used in large quantities in the industrial sector, and the supply and demand of raw materials is favorable, which can reduce the process cost and further improve commercial productivity. In addition, Et2BH used as a reactant in Reaction 1 is obtained by simply mixing BH3 and Et3B. BH3 is a substance that can be easily purchased in large quantities commercially, and Et3B is produced as a by-product of this reaction and can be recovered and used. This is very advantageous in terms of raw material supply and demand, and can further reduce the process cost and improve commercial productivity.

[0090] Specifically, the organozinc compound of formula 2-2 can be prepared, for example, by the first step of the method for preparing a polyolefin-polystyrene multiblock copolymer using formula 2-1, which will be described later. The organozinc compound of formula 2-2 thus prepared has one end group of a polyolefin repeating unit linked to zinc, and the other end group linked to a styrene repeating unit. Due to such structural characteristics, the organozinc compound of formula 2-2 has the characteristic that it can be very useful for preparing polyolefin blocks and functionalizing polyolefin end groups when preparing the polyolefin-polystyrene multiblock copolymer of formula 1.

[0091] For example, a method for producing an organozinc compound having a polyolefin group attached thereto by inserting an olefin between the zinc-ethyl group through coordination polymerization of an olefin in the presence of an organozinc compound such as diethylzinc, which is commercially mass-produced, is already known (Non-Patent Document 2). However, there has been no report of a method for producing a structure having a styrene group at one end and zinc attached at the other end by using an organozinc compound containing a styrene group (Zn-[CH2CH2-C6H4-CH=CH2]2) as a precursor, such as the organozinc compound of Chemical Formula 2 of the present invention.

[0092] Specifically, the repeating unit a of Chemical Formula 2 (-[CH(R)-CH2] a -) can be produced by using olefin monomers including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. as reactants in the production process.

[0093] In a specific example, the repeating unit a in formula 2 is an olefin monomer including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. It can be produced by using one of the olefin monomers as a reactant, or by using two of the olefin monomers including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. as reactants.

[0094] Specifically, the repeating unit a in Chemical Formula 2 may be polyethylene, polypropylene, poly(ethylene-co-propylene), poly(ethylene-co-1-butene), poly(ethylene-co-1-hexene), or poly(ethylene-co-1-octene).

[0095] Method for producing polyolefin-polystyrene multiblock copolymer Yet another embodiment of the present invention relates to a method for preparing a polyolefin-polystyrene multiblock copolymer represented by the above-mentioned formula 1, comprising: a first step of preparing a compound represented by the above-mentioned formula 2-2 by coordination polymerization of an olefin monomer with a transition metal catalyst in the presence of an organozinc compound represented by the above-mentioned formula 2-1; and a second step of sequentially introducing an alkyllithium compound containing a silicon atom, a triamine compound, and a styrene monomer to perform anionic polymerization.

[0096] The polyolefin-polystyrene multiblock copolymer represented by Chemical Formula 1 produced by this method is obtained by growing the desired polyolefin chain from the organozinc compound represented by Chemical Formula 2-1 to form an organozinc compound represented by Chemical Formula 2-2, and then performing anionic polymerization of styrene to form polystyrene blocks at the end groups of the polyolefin chains, thereby further enhancing the realization of thermoplastic elastomer properties of the polyolefin-polystyrene multiblock copolymer.

[0097] First step In the first step, an olefin monomer is subjected to coordination polymerization with a transition metal catalyst in the presence of an organozinc compound represented by the above formula 2-1 to produce a compound represented by the above formula 2-2.

[0098] Specifically, the olefin monomer introduced as a reactant in the first step may be ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, or a monomer formed from a mixture thereof, etc. The olefin monomer may be used alone or in combination of two or more.

[0099] In the first step, when ethylene, propylene, 1-butene, or the like having a relatively low boiling point is used as the olefin monomer, the polymerization reaction can be carried out under a predetermined pressure.

[0100] In one embodiment, the olefin monomer input as a reactant in the first step may be a monomer containing a mixture of two or more of ethylene, propylene, 1-butene, 1-hexene, and 1-octene. In this case, the organozinc compound of formula 2-2 produced may have, for example, a repeating unit a having a structure such as HDPE, MDPE, LLDPE, VLDPE, POE, or EP.

[0101] The transition metal catalyst used in the first step is not limited, but may be a homogeneous (metallocene) catalyst or a non-homogeneous Ziegler catalyst, which may typically include a transition metal catalyst as a main catalyst and / or an organoaluminum or boron compound as a co-catalyst. In a specific example, the use of a homogeneous catalyst is preferred because it has better catalytic activity.

[0102] Specifically, the transition metal catalyst may include a compound represented by the following Formula 5 or Formula 6:

[0103] [ka]

[0104] In the above formula 5, R 51 is hydrogen or methyl, and R 52 is hydrogen or phenyl.

[0105] When the compound represented by Formula 5 is used as the transition metal catalyst, it may be more efficient to grow polyolefin chains from the organozinc compound. In addition, the transition metal catalyst may be activated with methylaluminoxane (MAO), methylaluminoxane (MAO) or a boron-based cocatalyst.

[0106] [ka]

[0107] When the compound represented by Formula 6 is used as the transition metal catalyst, it can be more efficient in preventing the beta-elimination process from occurring unnecessarily and in growing uniform polyolefin chains from the organozinc compound. In addition, the transition metal catalyst has a molecular weight of [(C 18 H 37 )2MeNH] + [B(C6F5)4] - , methylaluminoxane (MAO), methylaluminoxane (MAO) or one activated with a boron-based cocatalyst can be used.

[0108] The first step may be carried out, for example, in a homogeneous solution state. In this case, the solvent may be a hydrocarbon solvent or an olefin monomer itself. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents having 4 to 20 carbon atoms, specifically isobutane, hexane, cyclohexane, methylcyclohexane, etc. The solvent may be used alone or in combination of two or more.

[0109] The polymerization temperature of the first step may vary depending on the reactants, reaction conditions, etc., but may be specifically 70 to 170 degrees Celsius. Within this range, the solubility of the polymer can be increased while the catalyst can be thermally stabilized.

[0110] The first step polymerization can be carried out batchwise, semi-continuously or continuously, and can also be carried out in two or more steps having different reaction conditions.

[0111] The compound represented by the formula 2-1 prepared in the first step of the above embodiment can act as a precursor for preparing the polyolefin-polystyrene multiblock copolymer represented by the formula 1 through the anionic polymerization reaction in the second step described below.

[0112] Second step In the first step, an alkyl lithium compound, a triamine compound and a styrene monomer are successively added and an anionic polymerization step is carried out to prepare a polyolefin-polystyrene multiblock copolymer.

[0113] In the second step, the styrene monomer can be continuously inserted between the zinc-carbon bonds contained in the compound of formula 2-2 formed in the first step, and at the same time, the styrene group present in the terminal group of the compound represented by formula 2-2 can participate in the copolymerization site with the styrene monomer and be linked to the polystyrene chain. This allows the polyolefin-polystyrene multiblock copolymer of formula 1 to be produced in a one-pot production method.

[0114] Specifically, the styrene-based monomer may be a styrene-based monomer having a carbon number of 6 to 20. More specifically, the styrene-based monomer may be a styrene-based monomer including ethylene substituted with an aryl group having a carbon number of 6 to 20, ethylene substituted with a phenyl group, or the like, for example, styrene.

[0115] It is a well-known fact that organic zinc compounds cannot act as initiators in styrene polymerization. That is, if only styrene monomers are added after the first step of coordination polymerization, the polymerization reaction does not proceed at all. Also, if styrene polymerization is carried out in a hydrocarbon solvent using an alkyllithium compound containing silicon atoms as an initiator in the presence of an organic zinc compound, polystyrene blocks are formed only between the zinc-carbon bonds in the direction in which the polyolefin block is formed, and styrene monomers are not inserted between the zinc-carbon bonds on the side of the terminal group where silicon atoms exist. In this case, the organic zinc compound does not participate in the polymer chain formation reaction and remains as it is, which is also a well-known fact.

[0116] In the second step of the present invention, a silicon-containing alkyllithium compound, a triamine compound, and a styrene-based monomer are successively added to the first step to carry out anionic polymerization, whereby the styrene-based monomer is inserted between the zinc-carbon bonds of formula 2-2 formed in the first step, resulting in the multiblock copolymer represented by formula 1. In the second step, a silicon-containing alkyllithium compound and a triamine compound are used as initiators in combination. This can reduce the amount of polystyrene homopolymer that may be generated when using conventional initiators.

[0117] Specifically, the alkyllithium compound containing a silicon atom may be a compound represented by the following formula 3:

[0118] [ka]

[0119] Such silicon-containing alkyllithium compounds are widely used as initiators for anionic polymerization, are easily available, and can be easily used in the present invention.

[0120] Specifically, the triamine compound may be a compound represented by the following chemical formula 4:

[0121] [ka]

[0122] The compound of formula 4 is easily coordinated to lithium and is used for the purpose of improving the reactivity of an alkyllithium compound containing a silicon atom as a base or as a nucleophile, and is easily available and has a low unit price.

[0123] The present inventor has developed and publicized a method for growing polystyrene chains from zinc-carbon bonds of an organic zinc compound (Patent Document 1 and Non-Patent Document 1). In this prior invention, styrene polymerization was performed by adding nBuLi·(TMEDA) (TMEDA; tetramethylethylenediamine) as an initiator. At this time, the unique orange color of the styryl anion observed initially gradually changes to yellow-brown, and finally turns opaque black, and the anion that grows the polymer chain is destroyed. In addition, the molecular weight distribution of the produced polystyrene is somewhat broad (Mw / Mn, ~1.5). In addition, in the prior invention, when the molar ratio of the zinc atom in the organic zinc compound to the added styrene monomer (i.e., [styrene] / [Zn]) is small, such as 500 or less, polystyrene chains cannot grow from all the Zn-C bonds of the organic zinc compound present, and polystyrene chains grow only from a part of them. If polystyrene chains grow only from some of the Zn-C bonds in the organozinc compound, polystyrene-polyolefin diblocks or polyolefin homopolymers are produced, which is an obstacle to realizing thermoplastic elastomer properties.

[0124] In the method for preparing a polyolefin-polystyrene multiblock copolymer according to the present invention, Me3SiCH2Li·(PMDETA) (PMDETA: pentamethyldiethylenetriamine), an exemplary compound of Formula 3 and Formula 4, is added as an initiator to perform anionic polymerization, and it is confirmed that the yellow color is maintained without color change during the polymerization process, which indicates that the anions at the growth points of the polymer chains are alive and not destroyed. This allows the molecular weight distribution of the prepared polystyrene chains to be relatively lowered. In this case, the molecular weight distribution (PDI) value of the prepared multiblock copolymer may be specifically 1.2 to 1.5, more specifically Mw / Mn 1.3.

[0125] In the following examples and experimental examples of the present invention, the compounds of Formula 3 and Formula 4 are used as initiators. When used as a catalyst, it has been confirmed that polystyrene chains grow from all Zn-C bonds of the zinc compound added, and therefore, it can be confirmed that the production of polystyrene-polyolefin diblock or polyolefin homopolymer is suppressed, and the selectivity of multiblock is further improved.

[0126] It was also confirmed that only a very small amount of polystyrene chains grew from the lithium compound containing silicon atoms, and that this partially suppressed the production of undesired polystyrene homopolymer (polystyrene chains grown from Zn-C bonds are block copolymers, while polystyrene chains grown from Me3SiCH2Li are undesired polystyrene homopolymers).

[0127] That is, the present invention relates to the compounds of Formula 3 and Formula 4 (e.g., Me3SiCH2 By using Li·(PMDETA) as a new initiator, the production of PS homopolymer, PO homopolymer, and PO-PS diblock copolymer is suppressed, while the production of polyolefin-polystyrene multiblock copolymer, which is the objective of the present invention, is maximized, thereby ensuring the realization of thermosetting elastomer properties.

[0128] Typically, the transition metal catalyst used in olefin polymerization to form the polyolefin block in step 1 is in a very small amount compared to the alkyllithium compound added to form the polystyrene block in step 2, and does not affect the anionic polymerization in step 2. On the other hand, if an organoaluminum-based cocatalyst is further used in the olefin polymerization in step 1, this amount is not negligible compared to the alkyllithium compound added in step 2.

[0129] Typically, organoaluminum compounds form complexes with alkyllithium compounds in a 1:1 ratio (Al:Li ratio), which cannot initiate anionic polymerization. However, when the Li / Al ratio is 1 or more, anionic polymerization is initiated, and styrene chains can grow from all the alkyllithium compounds added, including the alkyllithium that formed a 1:1 complex.

[0130] That is, when the first step is carried out using an organoaluminum compound as a cocatalyst, followed by the second step of anionic polymerization, the number of moles of the alkyllithium compound containing silicon atoms to be added must be equal to or greater than the number of moles of aluminum contained in the organoaluminum compound added in the first step. In order to efficiently grow polystyrene chains between the organic-zinc bonds in consideration of the reaction rate, the number of moles of the alkyllithium compound containing silicon atoms remaining after reaction with the organoaluminum (i.e., "the number of moles of Li minus the number of moles of Al") may be 0.2 times or more the number of moles of the zinc compound of Chemical Formula 2.

[0131] In one embodiment, the molar ratio of the organozinc compound introduced in the first step to Me3SiCH2Li·(PMDETA) (i.e., [Li] / [Zn]) may be 0.5 to 2.0. In such a case, Me3SiCH2Li and PMDETA are mixed to form Me3Si The CH2Li·(PMDETA) complex can also be formed and introduced into the reactor, or They may also be added to the reactor sequentially.

[0132] In another embodiment, the compound of Formula 4 can be used in a molar ratio of 1:0.5 to 1:1.0, for example, 1:1, relative to the silicon-containing alkyllithium compound of Formula 3.

[0133] In another specific example, the molar ratio ([Styrene] / [Zn]) of zinc atoms in the reaction solution to the styrene monomer added in the second step may be 250 to 1,000, more specifically 250 to 500.

[0134] Specifically, the silicon-containing alkyllithium compound of Chemical Formula 3 and the compound of Chemical Formula 4 can be mixed in an aliphatic hydrocarbon solvent and then added to a reactor, or the silicon-containing alkyllithium compound of Chemical Formula 3 and the compound of Chemical Formula 4 can be added sequentially to a reactor.

[0135] The anionic polymerization temperature of the polystyrene block formation step may vary depending on reactants, reaction conditions, etc., but may be specifically 40° C. to 170° C., more specifically 100° C. to 110° C. Within this range, the multiblock copolymer represented by Chemical Formula 1 is efficiently produced.

[0136] The anionic polymerization of the polystyrene block forming step can be carried out in a batch, semi-continuous or continuous manner, and can also be carried out in two or more steps having different reaction conditions.

[0137] The anionic polymerization time of the polystyrene block formation step may vary depending on reactants, 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 all of the styrene monomer input into a multiblock copolymer.

[0138] The present invention is characterized in that a block copolymer having a specific structure represented by Chemical Formula 1 is produced by growing a polyolefin chain through olefin polymerization using an organozinc compound represented by Chemical Formula 2, and then continuously carrying out styrene anionic polymerization. In this case, the improved production method is more economical in terms of production cost and more commercially useful, and the reaction activity is improved during production.

[0139] In addition, the present invention provides a method for producing a polyolefin-polystyrene multiblock copolymer in a one-pot reaction, which has high selectivity and prevents decomposition of anions that act as polymer chain growth points, thereby realizing a higher water content.

[0140] Polystyrene-polyolefin-polystyrene triblock copolymer Yet another embodiment of the present invention relates to a polystyrene-polyolefin-polystyrene triblock copolymer represented by the following Chemical Formula 7.

[0141] [ka]

[0142] In the formula 7, Ar is an aryl group having 6 to 20 carbon atoms; the average value of m is 20 to 10,000; Y and Y' are each independently any one of hydrogen, methyl, ethyl, butyl, hexyl, and octyl, and Y and Y' are not the same; p and 1-p are mole fractions of each repeating unit constituting the repeating unit n, p being a value of 0 to 1; the average value of n is 40 to 10,000; R 2 ~R 3 each independently represents hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; and z represents an integer of 0 to 10.

[0143] Specifically, the aryl group having 6 to 20 carbon atoms may be substituted or unsubstituted, and when substituted, the substituent is not particularly limited, and specific examples thereof include hydrocarbyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and isomers thereof. In addition, the hydrocarbyl used as the substituent may be cyclic, acyclic, branched, or straight-chained.

[0144] Specifically, the aryl group having 6 to 20 carbon atoms may include a monocyclic aryl group, a polycyclic aryl group, or a heteroaryl group, for example, a monocyclic aryl group such as benzyl, phenyl, biphenyl, terphenyl, tolyl, etc.; a polycyclic aryl group such as naphthyl, anthracenyl, phenanthrenyl, etc.; and the like.

[0145] Specifically, m and n can be used as symbols to distinguish each repeating unit represented by Chemical Formula 7, and can also be used as symbols to mean the number of repeats of each repeating unit. In conventional polymer synthesis, the values ​​of m and n are not single integers but are a mixture having a certain distribution, and therefore, the average values ​​are measured and discussed.

[0146] When the average value of m is less than 20, the amount of polymer produced is small compared to the amount of zinc compound added, which causes problems in economic efficiency, and when the average value of m is too large, such as exceeding 10,000, the viscosity is high and the manufacturing method is not easy, making it difficult to realize a compound having the structure of Chemical Formula 7. Specifically, the average value of m in Chemical Formula 7 may be 20 to 10,000.

[0147] When the average value of n is less than 40, the amount of polymer produced is small compared to the amount of zinc compound added, which causes problems in economic efficiency, and when the average value of n is too large, such as exceeding 10,000, the viscosity is high and the manufacturing method is not easy, making it difficult to realize a compound having the structure of Chemical Formula 7. Specifically, the average value of n in Chemical Formula 7 may be 40 to 10,000.

[0148] Specifically, the repeating unit n can include olefin repeating units p and 1-p. In this application, p and 1-p are used as symbols to distinguish the olefin repeating units constituting the repeating unit n, and indicate the molar fractions of the repeating units p and 1-p present in the repeating unit n, respectively. The composition of the repeating units (p and 1-p) in the polyolefin chain can be adjusted by adjusting the amount of olefin monomer input during olefin polymerization (chain transfer polymerization) in the production method described below. The polyolefin formed by changing the input composition of the olefin monomer during the reaction can be adjusted by adjusting the amount of the olefin monomer input during the reaction. Within the olefin chain, the composition of the repeat units (p and 1-p) can be adjusted randomly, in gradients, or in blocks.

[0149] Specifically, the hydrocarbyl may be substituted or unsubstituted, and when substituted, the substituent is not particularly limited, and specific examples thereof include hydrocarbyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, etc. In addition, the hydrocarbyl may be cyclic, acyclic, branched, or straight-chained.

[0150] More specifically, the hydrocarbyl having 1 to 20 carbon atoms is an alkyl having 1 to 20 carbon atoms, an alkenyl having 1 to 20 carbon atoms, Carbon number 2-20 More specifically, alkynyl Alkyl with 2 to 10 carbon atoms , for example, methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl , nonyl, decanyl and their isomers, and the like.

[0151] Specifically, the z is not particularly limited, but may be an integer of 0 to 10. Although it is possible to use a compound in which the z value is an integer of 10 or more, since there is little benefit to be gained from using such a large molecule, the present invention limits the z value to a certain integer value of 0 to 10. Within this range, the efficiency of the production method can be increased and the effect of precisely controlling the reaction can be further improved. The z may be, for example, 0 to 8, 0 to 6, 0 to 4, 0, 1, 2, 3, or 4. Within this range, the supply and demand of reactants required for the production of the polynuclear zinc compound is easy.

[0152] In a specific example, in Formula 7, Ar is phenyl; the average value of m is 20 to 200; Y is hydrogen; Y' is methyl, ethyl, butyl, or hexyl; R 2 ~R 3 is hydrogen; z may be 0 or 2. In such a case, the polyolefin block It is possible to provide a polystyrene-block-polyolefin-block-polystyrene triblock copolymer which has absolutely no carbon-carbon double bonds in the block and is therefore more useful industrially.

[0153] The polystyrene-polyolefin-polystyrene triblock copolymer may have a PDI of 1.2 to 1.5. In this case, the polystyrene-polyolefin-polystyrene triblock copolymer is prepared by two processes of conventional anionic polymerization and hydrogenation, and has a molecular weight distribution of 1.2 or less. The polyolefin block does not have any carbon-carbon double bonds, and the polystyrene-block-polyolefin-block-polystyrene triblock copolymer is industrially more useful.

[0154] The triblock copolymer represented by Chemical Formula 7 may be, for example, a triblock copolymer such as n-polystyrene-block-poly(ethylene-co-propylene)-block-polystyrene, polystyrene-block-poly(ethylene-co-1-butene)-block-polystyrene, polystyrene-block-poly(ethylene-co-1-hexene)-block-polystyrene, or polystyrene-block-poly(ethylene-co-1-octene)-block-polystyrene.

[0155] Yet another embodiment of the present invention relates to a method for preparing a polystyrene-polyolefin-polystyrene triblock copolymer, the method comprising: forming a polyolefin block by chain transfer polymerization of an olefin monomer using a polynuclear zinc compound as a chain transfer agent; and forming a polystyrene block by anionic polymerization of an alkyllithium compound containing a silicon atom, a triamine compound, and a styrene monomer.

[0156] This allows a polyolefin block having a desired structure to be stably formed, and polystyrene blocks are also stably formed at both ends of the formed polyolefin structure, providing a production method with excellent selectivity for polystyrene-polyolefin-polystyrene triblock copolymers.

[0157] In addition, it is possible to provide a one-pot production method for directly producing the polystyrene-polyolefin-polystyrene triblock copolymer from an olefin monomer and a styrene monomer, and it is possible to provide a production method for a polystyrene-polyolefin-polystyrene triblock copolymer suitable for realizing thermoplastic elastomer properties by suppressing the formation of diblock and homopolymers.

[0158] Method for producing polystyrene-polyolefin-polystyrene triblock copolymer <Polyolefin block formation step> First, the step of forming the polyolefin block comprises chain-transferring a polynuclear zinc compound. As an agent, an olefin monomer can be subjected to a chain transfer polymerization reaction to form a polyolefin block constituting a polystyrene-polyolefin-polystyrene triblock copolymer.

[0159] Specifically, the polynuclear zinc compound may be an organozinc compound containing an alkanediyl group, more specifically, a compound represented by the following Chemical Formula 8.

[0160] [ka]

[0161] In the above formula 8, R 1 is a hydrocarbyl having 1 to 20 carbon atoms; R 2 ~R 3 each independently represents hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; the average value of a is 1 to 10 and z is an integer from 0 to 10. .

[0162] The hydrocarbyl may be substituted or unsubstituted, and when substituted, the substituent is not particularly limited, but specific examples include hydrocarbyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and isomers thereof. The hydrocarbyl may be cyclic, acyclic, branched, or straight-chained.

[0163] The hydrocarbyl having 1 to 20 carbon atoms can specifically include alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, alkynyl having 1 to 20 carbon atoms, more specifically alkyl having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decanyl, and isomers thereof.

[0164] In the above formula 8, z is not particularly limited, but may be an integer of 0 to 10. Although it is possible to use a polynuclear zinc compound in which the value of z is an integer of 10 or more, since there is little benefit to be gained from using such a large molecule, the present invention limits the value of z to a certain integer value of 0 to 10. The value of z may be, for example, 0 to 8, 0 to 6, 0 to 4, 0, 1, 2, 3, or 4. Within the above range, the supply and demand of reactants required for the production of a polynuclear zinc compound is easy.

[0165] In Chemical Formula 8, a is not particularly limited to a natural number exceeding 0, but the polynuclear zinc compound represented by Chemical Formula 8 may be expressed as a mixture having a certain distribution in which the value of a is not a single constant, and may have an average value of, for example, 1 to 10. When the average value of a in Chemical Formula 8 exceeds 10, the molecular weight of the polynuclear zinc compound produced when applied to olefin polymerization may become too large, resulting in high viscosity and difficulty in controlling the reaction.

[0166] In one embodiment, the polynuclear compound may be a compound represented by the following formula 8-1 or 8-2. 8-2 The compound represented by the formula (I) can be advantageously produced using Et2Zn or Me2Zn as a starting material, which are commercially produced and used in large quantities.

[0167] [ka]

[0168] [ka]

[0169] Formulas 8-1 and 8-2 In, the average value of a is 1 to 10.

[0170] In the step of forming the polyolefin block of the present invention, the olefin monomer to be added as a reactant is not particularly limited.2 The copolymer may include olefins having from 2 to 10 carbon atoms, more specifically, α-olefins having from 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 1-decene.

[0171] In a specific example, when ethylene, propylene, 1-butene, etc., which have a relatively low boiling point, are used as the olefin monomer, the polymerization reaction can be carried out under a certain pressure.

[0172] In the step of forming the polyolefin block of the present invention, a transition metal catalyst for olefin polymerization can be used for the chain transfer polymerization reaction. There is no particular limitation on the type of transition metal catalyst, but generally, a homogeneous (metallocene) catalyst containing a transition metal catalyst as a main catalyst and / or an organoaluminum or boron compound as a cocatalyst, or a heterogeneous Ziegler catalyst can be used. In an embodiment, the use of a homogeneous catalyst is preferred because it has better catalytic activity.

[0173] Specifically, the transition metal catalyst may include a compound represented by the above Formula 5 or Formula 6, which has been described above.

[0174] The step of forming the polyolefin block may be carried out, for example, in a homogeneous solution state. In this case, the solvent may be a hydrocarbon solvent or an olefin monomer itself. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents having 4 to 20 carbon atoms, specifically, isobutane, hexane, cyclohexane, methylcyclohexane, etc. The solvent may be used alone or in combination of two or more.

[0175] The polymerization temperature of the step of forming the polyolefin block may vary depending on the reactants, reaction conditions, etc., but may be specifically 40° C. to 170° C., more specifically 95° C. to 125° C. Within this range, the catalyst can be thermally stabilized while increasing the solubility of the polymer.

[0176] The olefin polymerization in the step of forming the polyolefin block can be carried out batchwise, semi-continuously or continuously, and can also be carried out in two or more steps having different reaction conditions.

[0177] The polynuclear zinc compound represented by formula 8 is not particularly limited, but can be prepared by reacting a diene compound with a boron-based inorganic compound to carry out hydroboration, and then reacting the product with a dialkylzinc compound to carry out an alkyl group exchange reaction.

[0178] More specifically, the method for preparing the polynuclear zinc compound represented by Chemical Formula 8 can be carried out according to the following Reaction Scheme 3.

[0179] [ka]

[0180] In the reaction scheme 3, the starting diene compound is converted into the target R 2 ~R 3 Various types can be used depending on the structure and z value of the above. Reaction Scheme 3 The value of z in the formula (8) is a value derived from the structure of the diene compound that is the starting material, and the value of z in the formula (8) can be determined. Reaction Scheme 3 In formula 8, z may have an integer value of 10 or more. However, when z is limited to a certain integer value of 0 to 10, the polynuclear zinc compound of formula 8 has better structural uniformity and is easy to supply and demand raw materials.

[0181] In the reaction formula 3, the diene compound is specifically a diene compound in which the value of z is 0 to 10, for example, 1, 3-Butadiene , 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, isoprene, and the like can be used.

[0182] In a specific example, the starting material for reaction scheme 3 is 1, 3-Butadiene or 1,5-hexadiene (R 2 ~R 3 When a compound in which x is hydrogen and z is 0 or 2 is used, the unit price of the raw material is low and it can be purchased in large quantities, which is advantageous from an economic and industrial standpoint.

[0183] In the reaction formula 3, the boron-based inorganic compound is not particularly limited as long as it can cause a hydroboration reaction with a diene compound, and may be specifically trihydroborane. In this case, the polynuclear zinc compound of the formula 8 is prepared. The structural uniformity is more excellent, and the production efficiency can be further improved.

[0184] In the above reaction formula 3, after the hydroboration reaction, the product produced contains dialkyl zinc (R 1 After reacting with the 2Zn compound, the trialkylboron (R 1 3B) The compound of formula 8 can be synthesized by continuously removing the compound by distillation (or vacuum distillation).

[0185] In the reaction scheme 3, the alkyl group exchange reaction not only occurs between zinc and boron, but also rapidly proceeds between zinc and other zinc compounds. The polynuclear zinc compound produced by the reaction scheme 3 is not a single type of compound, but can be produced as a mixture in which the value of a in the chemical formula 8 has a certain distribution.

[0186] In addition, the dialkyl zinc (R1 2Zn) Adjust the amount of compound In the above formula, the average value of a can be adjusted by adjusting the average value of a in the formula 8. The average value of a in the formula 8 is determined by the amount of dialkyl zinc (R 1 2Zn) compound.

[0187] In the reaction formula 3, dialkyl zinc (R 1 2Zn) is R 1 Has 1 to 20 carbon atoms or a hydrocarbyl having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a silicon atom.

[0188] In a specific example, the dialkyl zinc (R 1 2Zn) as Me2Zn or When Et2Zn is used, it is currently produced in large quantities in the industrial sector, and the supply and demand of the raw material is easy. In particular, when Me2Zn is used, the by-product Me3B has a boiling point of -20°C and is easy to remove, whereas when Et2Zn is used, the by-product Et3B has a boiling point of 95°C and the boiling point of Et2Zn is 117°C and can be selectively removed by distillation or vacuum distillation. This is advantageous for the preparation of the compound of formula 8. It is possible.

[0189] The polynuclear zinc compound of formula 8 prepared by the above method can be provided in high purity without impurities such as THF and large amounts of magnesium salts, since it is advantageous to remove the organometallic catalyst and the cocatalyst composed of aluminum or bromine element used in the preparation. Therefore, it can be used as a chain transfer agent and is advantageous for use in olefin polymerization.

[0190] In the olepine polymerization for producing the polynuclear zinc compound having the polyolefin chain, the specific polymerization conditions are not particularly limited, but may be, for example, as follows.

[0191] <Polystyrene block formation step> The polystyrene-polyolefin-polystyrene triblock copolymer can be produced by continuously adding an alkyl lithium compound, a triamine compound, and a styrene monomer to the step of forming the polyolefin block and carrying out an anionic polymerization to form a polystyrene block.

[0192] The polystyrene block forming step can continuously insert a styrene monomer between the zinc-carbon bonds contained in the compound of Formula 8 in which the polyolefin block is formed by the polyolefin block forming step. In addition, the triblock copolymer produced through the above process can be easily quenched by reacting the ends with water, oxygen or organic acid, and thus converted into an industrially useful polystyrene-polyolefin-polystyrene triblock copolymer.

[0193] Specifically, the styrene monomer may be an α-styrene monomer (ArCH=CH2) having 6 to 20 carbon atoms. More specifically, an aryl group having 6 to 20 carbon atoms may be substituted. The styrene monomer may be, for example, styrene, which includes ethylene substituted with a phenyl group, ethylene substituted with a phenyl group, or the like.

[0194] In the polystyrene block forming step of the present invention, an alkyl lithium compound containing a silicon atom, a triamine compound, and a styrene-based monomer are continuously added to the polyolefin block forming step to carry out anionic polymerization, so that the styrene-based monomer is reacted with the (polyolefin)2Zn formed in the polyolefin block forming step through the zinc-carbon bond. As a result, a triblock copolymer represented by the above-mentioned Chemical Formula 7 is obtained. This reaction can be illustratively shown in the following Reaction Scheme 4.

[0195] [ka]

[0196] Specifically, the silicon-containing alkyllithium compound may be a compound represented by the above-mentioned Chemical Formula 3. The above-mentioned Chemical Formula 3 is as described above.

[0197] These alkyllithium compounds are easy to obtain or produce, and can be easily utilized in the present invention.

[0198] Specifically, the triamine compound may be a compound represented by the above-mentioned Chemical Formula 4. The above-mentioned Chemical Formula 4 is as described above.

[0199] The present inventor has developed and publicized a method for growing polystyrene chains from zinc-carbon bonds of an organic zinc compound (Patent Document 1 and Non-Patent Document 1). In the prior invention, styrene polymerization was performed by adding nBuLi·(TMEDA) (TMEDA; tetramethylethylenediamine) as an initiator. At this time, the unique orange color of the styryl anion observed initially gradually changes to yellow-brown, and finally turns opaque black, and the anion that grows the polymer chain is destroyed. In addition, the molecular weight distribution of the produced polystyrene is somewhat wide (Mw / Mn, ~1.5), which is a weakness. In addition, in the prior invention, if the molar ratio of the zinc atom in the organic zinc compound to the styrene monomer added (i.e., [styrene] / [Zn]) is small, such as 500 or less, polystyrene chains cannot grow from all the Zn-C bonds of the organic zinc compound present, and polystyrene chains grow only from some of them. In this way, if polystyrene chains cannot grow from all the Zn-C bonds of the organozinc compound, but grow only from some of them, a polystyrene-polyolefin diblock or polyolefin homopolymer will be produced, which will prevent the realization of thermoplastic elastomer properties.

[0200] In the method for producing the polystyrene-polyolefin-polystyrene triblock copolymer of the present invention, Me3SiCH2Li·(PMDETA) (PMDETA: pentamethyldiethylenetriamine), which is a compound of Formula 3 and Formula 4, is added as an initiator to carry out anionic polymerization, and it can be confirmed that the yellow color is maintained without color change during the polymerization process, which indicates that the growth point anions of the polymer chains are not destroyed and are alive. This allows the molecular weight distribution of the produced polystyrene chains to be relatively lowered. In this case, the molecular weight distribution (PDI) of the produced polystyrene-polyolefin-polystyrene triblock copolymer may be specifically 1.2 to 1.5, more specifically Mw / Mn 1.3.

[0201] It has been confirmed that when the compounds of Formula 3 and Formula 4 are used as initiators, polystyrene chains grow from all Zn-C bonds of the polynuclear zinc compound added, and thus the production of polystyrene-polyolefin diblock or polyolefin homopolymer is suppressed, and the selectivity of polystyrene-polyolefin-polystyrene triblock is further improved. It can be confirmed that the improvement is

[0202] It was also confirmed that only a portion of the polystyrene chains grew from the Me3SiCH2Li added as an initiator, and that this partially suppressed the production of undesired polystyrene homopolymer (polystyrene chains grown from Zn-C bonds are block copolymers, while polystyrene chains grown from Me3SiCH2Li are undesired polystyrene homopolymers).

[0203] That is, by using Me3SiCH2Li·(PMDETA), which is the compound of Formula 3 and Formula 4, as an initiator, it is possible to suppress the production of PS homopolymer, PO homopolymer, and PO-PS diblock copolymer, while maximizing the production of PS-PO-PS triblock copolymer, which is the object of the present invention, and reliably realize the properties of a thermosetting elastomer.

[0204] Generally, the transition metal catalyst used in the olefin polymerization in the polyolefin block formation step is in a very small amount compared to the alkyllithium compound containing silicon atoms that is added in the polystyrene block formation step, and does not affect the anionic polymerization in the polystyrene block formation step. Meanwhile, when an organoaluminum-based cocatalyst is further added to the olefin polymerization in the polyolefin block formation step, its amount is not negligible compared to the alkyllithium compound added in the polystyrene block formation step. Generally, the organoaluminum compound forms a complex with the alkyllithium compound at a ratio of 1:1 (Al:Li ratio), which cannot initiate anionic polymerization. However, when the Li / Al ratio is 1 or more, anionic polymerization is initiated, and styrene chains grow from all the alkyllithium compounds added, including the alkyllithium complexed at 1:1.

[0205] That is, when an anionic polymerization step of the polystyrene block formation step is carried out after the polyolefin block formation step using an organoaluminum compound as a cocatalyst, the number of moles of the alkyllithium compound to be added must be equal to or greater than the number of moles of aluminum contained in the organoaluminum compound added in the polyolefin block production step. In order to efficiently grow polystyrene chains between the organic-zinc bonds in consideration of the reaction rate, the number of moles of the alkyllithium compound containing silicon atoms remaining after reaction with the organoaluminum (i.e., "the number of moles of Li - the number of moles of Al") may be equal to or greater than 0.2 times the number of moles of the polynuclear zinc compound of Chemical Formula 8.

[0206] In one embodiment, the compound of Formula 4 can be used in a molar ratio of 1:0.5 to 1:1.5, for example, 1:1, relative to the silicon-containing alkyllithium compound of Formula 3.

[0207] In another embodiment, the molar ratio of zinc atoms to styrene monomers ([Styrene] / [Zn]) added in the step of forming the polystyrene block may be 250 to 1,000, more specifically 250 to 500.

[0208] In another specific example, the polystyrene-polyolefin-polystyrene triblock copolymer may have a number of polystyrene polymer chains generated per zinc atom ([PS-chains] / [Zn]) of 2.0 to 3.0.

[0209] Specifically, the silicon-containing alkyllithium compound of Chemical Formula 3 and the compound of Chemical Formula 4 can be mixed in an aliphatic hydrocarbon solvent and then added to a reactor, or the silicon-containing alkyllithium compound of Chemical Formula 3 and the compound of Chemical Formula 4 can be added sequentially to a reactor.

[0210] The anionic polymerization temperature of the polystyrene block formation step may vary depending on the reactants, reaction conditions, etc., but may be specifically 40° C. to 170° C., more specifically 100° C. to 110° C. Within this range, the triblock copolymer represented by Chemical Formula 7 is efficiently produced.

[0211] The anionic polymerization of the polystyrene block forming step can be carried out in a batch, semi-continuous or continuous manner, and can also be carried out in two or more steps having different reaction conditions.

[0212] The anionic polymerization time of the polystyrene block formation step may vary depending on reactants, 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 the above range, the entire amount of the styrene monomer input can be converted into a triblock copolymer.

[0213] The present invention is characterized in that the method for producing a triblock copolymer includes a polystyrene block formation step in which styrene anionic polymerization is successively performed after olefin polymerization in the polyolefin block formation step, thereby simplifying the method for producing the triblock copolymer, lowering the production cost and making it easy to apply to commercial processes. In addition, the polystyrene-polyolefin-polystyrene triblock copolymer can be produced from styrene and olevin monomers in a one-pot reaction, and while the production cost is low, a production method suitable for realizing thermoplastic elastomer properties by suppressing the generation of diblocks and homopolymers can be provided.

[0214] Working Example Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention, but these are presented as preferred examples of the present invention and should not be construed as limiting the present invention in any way.

[0215] Preparation Example 1: Preparation of an organozinc compound represented by formula 2-1

[0216] [ka]

[0217] Borane dimethylsulfide (1.6 mL, 3.2 mmol) was gradually added to triethylborane (0.6 g) under stirring, and the mixture was allowed to react for 90 minutes. The mixture was gradually added to divinylbenzene (3.8 g) dissolved in anhydrous diethyl ether (10 mL) cooled to -20°C, and the mixture was allowed to stir overnight. The solvent was removed using a vacuum pump, and diethylzinc (0.8 g) was added. The reaction was continued for 5 hours at 0°C, while removing the triethylborane produced by distillation under reduced pressure. Excess divinylbenzene and diethylzinc were removed by distillation under reduced pressure at 40°C. Methylcyclohexane (150 mL) was added to dissolve the product again, and the solid compound produced as a by-product was removed by filtration using cellulose. The filtrate was used as is in the following examples, and a portion was set aside to remove the solvent.1 H NMR analysis was performed. The resulting spectrum is shown in FIG.

[0218] Preparation Example 2: Preparation of polynuclear zinc compounds containing alkanediyl groups

[0219] [ka]

[0220] In a glove box, sodium borohydride (5.55 g, 146.1 mmol) was placed in a two-neck flask, followed by diglyme (73 mL). In the other two-neck flask, 1,5-hexadiene (6.0 g, 73 mmol) was placed, followed by diethyl ether (17 g) and hexane (24 g). One inlet of the two-neck flask was blocked with a rubber septum, and a distillation tube was connected. Since this reaction is between diborane, which is a gas, and 1,5-hexadiene dissolved in the solvent, it is efficient for the inlet of the distillation tube to be immersed in the solvent. The connected distillation tube was taken outside and connected to a shrink line. Iodine (18.5 g, 73 mmol) was placed in a one-neck flask, which was then blocked with a rubber septum. The vacuum was maintained for a short period of 30 seconds to create a nitrogen atmosphere, and diglyme (73 mL) was then injected from the box using a syringe. After the iodine was completely dissolved, it was poured into the two-neck flask containing sodium borohydride over a period of 5 hours. At this time, it was confirmed via NMR that all of the double bonds in 1,5-hexadiene had disappeared. If they had not disappeared, more sodium borohydride was added. The reaction can be terminated by adding iodine again in the correct amount. The product was then reacted overnight under 20 bar of ethylene to obtain a yellow liquid, bis-1,6-(1-boracyloheptyl)hexane. The product obtained from the Schlenk flask and diethyl zinc (15.7 g, 127 mmol) were added, and distillation was carried out at 0°C for 4 hours to remove by-products. The flask receiving the by-products was cooled to -78°C. The freezing point of the by-product triethylboron is lower than -78°C, and the freezing point of diethyl zinc is higher than -78°C, so the reaction proceeds as liquid is produced over time. The flask receiving the by-products was then cooled with liquid nitrogen for 1 hour to cool the by-products remaining in the distillation tube. The reaction was terminated, and the reactor was moved to a glove box, where it was dissolved in hexane and filtered to obtain a gray liquid. For high purity, the same mass of diethyl zinc was added as above, and distillation was carried out twice. In the final third distillation, in order to increase the a of the compound of Formula 8-1, volatile substances were removed as much as possible through vacuum distillation until a solid was obtained, to obtain a dark gray solid product. 1 H NMR analysis results It was confirmed that the average value of a was 6.5. 3.0 g of the compound prepared above was taken, and 0.396 g of diethyl zinc was added, and then heated and mixed to prepare a compound with an average value of a of 3.

[0221] Experimental Example 1: Performance evaluation of initiators in anionic polymerization processes Styrene polymerization was carried out using Me3SiCH2Li·(PMDETA) initiator in the presence of dihexylzinc compound to evaluate the performance of the initiator in anionic polymerization process.

[0222] In a single-neck flask, dihexylzinc compound (22.6 mg, 0.096 mmol), Me3 SiCH2Li (6.3mg, 0.067mmol, [Li] / [Zn]=0.70), PMDETA (11.7 mg, 0.067 mmol) was dissolved in methylcyclohexane (27 g) and added. After stirring for 15 minutes in a 90°C thermostatic bath, styrene monomer (5.0 g, 48.0 mmol, [Styrene] / [Zn]=500) was added and anionic polymerization was carried out at 90°C for 3 hours.

[0223] During the polymerization, the color of the solution did not change and continued to remain the initial yellow color. After confirming the conversion to polystyrene by NMR spectrum, HCl 2N aqueous solution (0.3 mL) was added to decompose the polystyrene-containing organozinc compound and silicon-containing alkyllithium compound, which were then dissolved in toluene and passed through a silica gel pad to obtain pure polystyrene. The mass of the obtained pure polystyrene was consistent with the amount of styrene monomer added. When the molecular weight of the obtained polystyrene was measured using gel permeation chromatography, the number average molecular weight (Mn) was 23,000. From the measured Mn value, the number of polystyrene polymer chains generated per molecule of the organozinc compound can be calculated using the following equation, Equation 1.

[0224]

number

[0225] Experimental Examples 2-6 and Comparative Experimental Examples 1-2: Performance evaluation of initiators in anionic polymerization processes Among the experimental conditions, [Styrene] / [Zn] and [Me 3 SiCH 2 Li·(PMDETA)] The results of experiments with varying the ratio of / [Zn] and a comparative experiment example are shown below. [Me 3 SiCH 2 Li·(TMEDA)] The results of the experiment are shown in Table 1. The experimental conditions were the same as those in Experimental Example 1, except that they were changed according to the contents shown in Table 1.

[0226] The results of Experimental Examples 1 to 6 and Comparative Experimental Examples 1 and 2 were interpreted and expressed in Reaction Scheme 2.

[0227] [ka]

[0228] [Table 1]

[0229] As can be seen from the results of the above experimental examples and comparative experimental examples, the polystyrene produced in Experimental Examples 1 to 4, which was carried out by carrying out anionic polymerization reaction while fixing the [styrene] / [Zn] ratio at 500 and varying the [Me3SiCH2Li·(PMDETA)] / [Zn] ratio to 1.0, 0.70, 0.50, or 0.30, 1 In the H NMR spectrum, the Me3Si-* end group signal was observed at ~0 ppm as a very weak signal. The value of [Zn-C chains] / [Zn] is in the range of 2.24 to 2.50, which indicates that polystyrene chains grow preferentially from all Zn-C bonds, and then, some Me3S It can be seen that PS chains grow from the iCH2-* site. The molecular weight distribution of the polystyrene was also favorably narrow (Mw / Mn, 1.23-1.30). In addition, as in Experimental Examples 5-6, even when the [styrene] / [Zn] ratio was low at 250, 1 No Me3SiCH2- end group signal was observed in the H NMR spectrum. The [PS-chains] / [Zn] values ​​were 1.97 and 2.08, indicating that polystyrene chains grew from all Zn-C bonds, and no PS chains grew from the Me3SiCH2-* sites.

[0230] On the other hand, instead of [Me3SiCH2Li·(PMDETA)] in Experimental Examples 1 to 6, [Me3 In Comparative Experiments 1 and 2, SiCH2Li·(TMEDA)] was added as an initiator.1 Although no Me3SiCH2-* end group signal was observed in the 1H NMR spectrum, the [PS-chains] / [Zn] value was 1.85 or 1.67, and polystyrene chains did not grow from some Zn-C bonds.

[0231] In addition, when nBuLi·(PMDETA) was used as an initiator, it was found to be rapidly decomposed at high temperatures (90°C) in cyclohexane and was therefore not suitable for use as an initiator. It was confirmed that.

[0232] Example 1: Preparation of a multiblock copolymer represented by formula 1 with polystyrene chains attached to both ends of polyolefin

[0233] [ka]

[0234] A solution of trimethylaluminum (14.4 mg, 200 umol-Al) dissolved in methylcyclohexane (17 g) was poured into the high-pressure reactor. The catalyst poison in the high-pressure reactor was purified at 100° C. for 1 hour, and the solution was removed using a cannula.

[0235] The organozinc compound represented by formula 2-1 (49.1 mg, 150 μmol) was dissolved in methylcyclohexane (40 g) and added to a high-pressure reactor, and the temperature was raised to 80°C. 18 H 37 )N(Me)H + [B(C6F5)4] - (4.0 μmol) The solution was stirred in a kettle for 2 hours and then diluted with a solution (1.0 g) of trioctyl aluminum (50 μmol, 18.3 mg) dissolved in methylcyclohexane (15 g). Immediately after injecting the catalyst solution into the high-pressure reactor, ethylene-propylene mixed gas was injected at a pressure of 20 bar. Even though the reactor was cooled with a fan, the temperature rose to ~115°C within 5 minutes due to an exothermic reaction. The temperature gradually decreased and was adjusted to a range of 95~115°C. The pressure gradually decreased due to the consumption of monomer, and after the polymerization process was carried out for 60 minutes at 45°C, the remaining gas was discharged. During this process, the polymer solution expanded and clogged the valve, and this part of the sample did not participate in the following two-step reaction, and was subsequently taken out for GPC and 1 H.N.M. R analysis was performed.

[0236] Me3SiCH2Li (150μmol, 14.1mg) and PMDETA (150μmol, 26mg) were mixed with methylcyclohexane (1.0g) and injected into the reactor and stirred for 30 minutes. The stirring temperature was maintained between 90℃ and 100℃. Styrene (7.8g) was injected into the high pressure reactor and reacted for 5 hours while maintaining the temperature between 90℃ and 100℃, until all the styrene monomer was converted ( 1 (Confirmed by 1 H NMR analysis). After the exchange, acetic acid and ethanol were continuously injected. The obtained polymer was dried overnight in a vacuum oven at 180℃. After lowering the temperature to room temperature, the produced block copolymer (2.8g) was transferred to a flask, chloroform (30.3g) was added, and the mixture was stirred at 75℃ for 20 minutes under reflux, and then acetone (60.6g) was poured in to precipitate the polymer material. The solution containing the polymer material was filtered, and the filtrate was obtained by removing the solvent using a vacuum pump to obtain homopolystyrene (0.49g). During this extraction process, some of the block copolymer was eluted together with homopolystyrene, and the molecular weight distribution was observed to be bimodal and wide in the GPC analysis.

[0237] Preparation of block copolymers having polystyrene chains attached to both ends of polyolefin represented by Chemical Formula 1 in Examples 2 to 8 Except for changing the polymerization conditions as shown in the following [Table 2], copolymers were produced in the same manner as in Example 1. [Table 3] shows the production results of block copolymers in Examples 1 to 8.

[0238] [Table 2]

[0239] [Table 3]

[0240] Example 9: Preparation of polystyrene-polyolefin-polystyrene triblock copolymer A solution of trimethylaluminum (14.4 mg, 200 μmol-Al) dissolved in methylcyclohexane (17.0 g) was charged into a bomb reactor (125 mL). The temperature was adjusted to 100° C. using a heating mantle, and the mixture was stirred for 1 hour. The solution was then removed using a cannula to remove catalyst poisons.

[0241] The reactor was placed in an inert atmosphere and the polynuclear zinc compound (Et[Zn(CH2)6]3ZnEt) (21.5 mg, 1 The reactor was filled again with a solution of 50 μmol-Zn) and the temperature was set to 70° C. The catalyst stock solution was a Hf complex, represented by the following formula 6 (18.1 mg, 25.0 μmol) [(C 18 H 37 )2Me N.H. + [B(C6F5)4] - (30.4 mg, 25.0 μmol) in benzene (4.0 g ) was reacted with ethylene / propylene. The catalyst stock solution (583 mg, 4.0 μmol-Hf complex) was injected into the reactor using a syringe, and the ethylene / propylene mixture gas was immediately charged into the system at a pressure of 20 bar. Even though the reactor was cooled with a fan, the temperature rose to ~125°C within 5 minutes due to the exothermic reaction. The temperature gradually decreased and was adjusted in the range of 95-125°C. The pressure gradually decreased due to the consumption of the monomer, eventually reaching 16 bar, and the stirring speed was gradually decreased from 300 rpm to 40 rpm due to the formation of a thick viscous solution. After the polymerization process was carried out for 40 minutes, the remaining gas was discharged. During this process, the polymer solution expanded and blocked the valve, and the GPC and 1 The mixture was collected for H NMR analysis. The temperature reached 90 °C. Then, Me3SiCH2Li·(PMDETA) solution prepared by mixing Me3SiCH2Li (11.3 mg, 0.120 mmol) and PMDETA (20.8 mg, 0.120 mmol) in methylcyclohexane (1.0 g) was added. The temperature was kept at 90 °C for 30 minutes while stirring, and then styrene (7.8 g, 750 mmol) was added. The temperature was adjusted in the range of 100-110 °C using a mantle. The viscosity gradually increased and almost reached a thermostable state within 5 hours. 1 H NMR analysis showed that styrene was completely The conversion was confirmed. After complete conversion of styrene, acetic acid and ethanol were injected successively. The obtained polymer mass was dried overnight in a vacuum oven at 160°C (24.7g). The polymer (3.0g) was dissolved in chloroform (30.0g) at 60°C, and then acetone (60.0g) was added to precipitate the block copolymer. The preparation results are shown in Table 5 below.

[0242] [ka]

[0243] Examples 10 to 15 : Preparation of polystyrene-polyolefin-polystyrene triblock copolymer A copolymer was prepared in the same manner as in Example 9, except that the reaction conditions were changed as shown in Table 4 below. The preparation results are shown in Table 5 below.

[0244] [Table 4]

[0245] In addition, the triblock copolymer produced in Example 12 1 The H NMR spectrum is shown below. This is shown in Figure 12.

[0246] The results of DSC analysis of the triblock copolymer prepared in Example 10 are shown in FIG.

[0247] [Table 5]

[0248] In Table 5, the specific contents of b, c, d, e, f, and g are as follows:

[0249] b: 1 The mole fraction of propylene in POs measured by H NMR spectrum is shown.

[0250] In addition, [C2] represents the molar fraction of ethylene, and [C3] represents the molar fraction of propylene.

[0251] c: The weight of PS extracted with acetone and chloroform (2:1 weight ratio) divided by the weight of styrene consumed.

[0252] d: GPC measurement of PS-standards at 400℃ using toluene as a diluent Values ​​are shown (Measured with GPC at 40℃ eluting wi th toluene using PS-standards).

[0253] e: PS-standards using 1,2,4-trichlorobenzene as a diluent The GPC measurement results at 160°C are shown (Measured with GPC at 160°C eluting with 1,2,4-trichlorobenzene using PS-standards).

[0254] f: (PO(g)) / ((Et- and -(CH2)6- units (mol) in the chain transfer agent of formula 8-1) value.

[0255] g: Converted to PO equivalents by universal calibration.

[0256] Comparative Example 1 Conventional SEBS (product name: polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene) produced by producing SBS and then hydrogenating it was purchased from Aldrich and used.

[0257] <Evaluation method> (1) Universal calibration of the GPC data For the PE samples, the PS standard molecular weight (M PS ) to PE equivalent (M PE ) was converted to the following equation 1.

[0258]

number

[0259] For poly(ethylene-co-propylene) samples, the converted M PEThe values ​​were further converted to PO equivalents using Equation 2 below.

[0260]

number

[0261] In the formula 2, S is the CH3-side chain (i.e., S=(15×F C3 ) / [(1-F C3 )×28+(F C3 × 42)]); and F C3 is the mole fraction of propylene in the poly(ethylene-co-propylene) sample.

[0262] (2) Transmission electron microscopy (TEM) Sample preparation: Polyolefin-polystyrene multiblock copolymers (5 mg) of the examples and comparative examples were completely dissolved in toluene (5 mL) at 100°C. A drop of the hot solution was loaded onto a carbon-coated copper TEM grid (200 mesh). After allowing the solvent to slowly evaporate overnight at room temperature, the sample on the grid was annealed in an oven at 150°C for 6 h. The filter was then filtered for 30 min in a closed chamber containing an aqueous solution of RuO4, which was prepared by reacting RuO2 (30 mg) and NaIO4 (0.20 g) in water (5 ml) at 0°C for 4 h. The sample was then suspending a TEM grid coated with RuO4. Stained with.

[0263] (3) Tensile test The polyolefin-polystyrene multiblock copolymer samples of the examples and comparative examples were held between two hot plates at 135° C. under a pressure of 5 MPa for 20 minutes, and then compressed at a pressure of 10 MPa for 100 minutes. The film was cut into four pieces (100 x 10 mm 2 The tensile test was performed using the AS The test was performed in duplicate for each configuration using a UTM (WL2100) at a temperature of 25 (±2) °C and a humidity of 45 (±5%) with a gauge length of 50 mm and a pull rate of 500 mm / min according to TM D882. Each specimen was pulled for at least 10 cycles to half the break distance measured in the tensile test.

[0264] <Evaluation Results> (1) GPC data FIG. 2 shows the GPC analysis results of the multiblock copolymer prepared in Example 5. a is the molecular weight distribution of the sample taken after the first step of olefin polymerization, and b is the molecular weight distribution of the block copolymer obtained after the second step of anionic polymerization. After anionic polymerization, the number average molecular weight increased by 30,000 Da. In anionic polymerization, the total number of polystyrene chain growth points is 450 μmol (the number of moles of the anionic polymerization initiator Me3SiCH2Li added + the number of moles of zinc x 2), so it is expected that a polystyrene chain of 17000 Da (7.8 g / 450 μmol) will grow from one growth point. The increase in number average molecular weight of 30,000 Da after anionic polymerization implies that polystyrene chains are attached to both end groups of the polyolefin chain. In the other examples besides Example 5, the number average molecular weight increased by 33,000, 36,000, 31,000, 29,000, 36,000, 63,000, and 24,000 after anionic polymerization, which indicates that polystyrene chains are attached to both terminal groups of the polyolefin.

[0265] In addition, the GPC analysis result of the triblock copolymer prepared in Example 9 is shown in FIG.

[0266] As can be seen from the above results, in Example 9, after the step of forming a polystyrene block by anionic polymerization, the GPC curve showed a clear overall change in which the molecular weight (both Mn and Mw) increased by about 50 kDa after anionic styrene polymerization, which is about twice the Mn (20 kDa) of homo-PS.

[0267] (2) Transmission electron microscopy (TEM) 3, 4, 5, and 6 show the transmittance and current density of the polyolefin-polystyrene multiblock copolymers prepared in Example 3(a), Example 4(b), Example 5(c), and Example 8(d), respectively. The microscopic image is shown.

[0268] Since the PS chains are not mixed with the PO chains, phase separation occurs and the chains are selectively stained by RuO4. The PS domains can be clearly seen as dark areas in the thin film transmission electron microscope (TEM) images. From Figures 3 to 6, it can be seen that the PS domains appear uniformly, and the pattern of the PS domains changes from spherical to ripple-like as the PS content is increased to 32wt%, 37wt%, and 42wt%.

[0269] FIG. 9 shows transmission electron microscope images of the triblock copolymers prepared in Example 9(e), Example 11(a), Example 12(c), Example 13(b), Example 15(d) and Comparative Example 1(f).

[0270] Since the PS chains are not mixed with the PO chains, phase separation occurs and the chains are selectively stained by RuO4. The PS domains can be clearly seen as dark areas in the thin film transmission electron microscope (TEM) images. As shown in Figure 9, the morphological change in the PS domains changes from spherical to wavy as the PS content increases from 28wt% to 32wt%, 38wt%, and 44wt%.

[0271] However, although the patterns of Examples 9, 11, 12, and 13 are similar, differences in regularity can be seen when compared with the image of SEBS (Comparative Example 1) produced by hydrogenating conventional SBS having a narrow PDI (FIG. 9(f)).

[0272] In addition, the propylene fraction (F C3In Example 15(d) having a molecular weight of 0.22, it can be seen that the morphology of the PS domains is consistently maintained as spherical, despite the high PS content of 38 wt % due to the crystallinity.

[0273] (3) Tensile test results

[0274] [Table 6]

[0275] Table 6 shows the results of the tensile test and the repeated tensile test of the polyolefin-polystyrene block copolymers prepared in Examples 2, 3, 5, and 8. From the results, it is clear that the low propylene fraction (F C3 , 0.22) increases the tensile strength, and a low weight percentage of PS (32 wt%) increases the elongation.

[0276] 7a to 7d show the repeated tensile test results of the block copolymers prepared in Example 2(a), Example 3(b), Example 5(c), and Example 8(d), respectively, in comparison with the repeated tensile test results of conventional SEBS in Comparative Example 1. It was confirmed that the prepared multiblock copolymers had thermosetting elastomer properties.

[0277] [Table 7]

[0278] 10 is a graph showing the stress measurement results from the tensile test results shown in Table 7. It was confirmed that the triblock copolymers prepared in Examples 9, 10, 12, and 15 had low or similar stress without fracture compared to conventional SEBS.

[0279] FIG. 11 shows the results of repeated tensile tests of the triblock copolymer prepared in Example 12.

[0280] FIG. 12 shows the results of repeated tensile tests of the triblock copolymer of Comparative Example 1 of the present invention (conventional SEBS).

[0281] 11 and 12, it was confirmed that the triblock copolymer of Example 12 of the present invention, unlike the conventional SEBS (Comparative Example 1), exhibited thermosetting elastomer properties.

[0282] Simple modifications or alterations of the present invention can be easily implemented by a person having ordinary skill in the art, and all such modifications and alterations are considered to be included within the scope of the present invention.

Claims

1. The polystyrene-polyolefin-polystyrene triblock copolymer is represented by the following chemical formula 7. The polystyrene-polyolefin-polystyrene triblock copolymer has no carbon-carbon double bond in the polyolefin block, The polystyrene-polyolefin-polystyrene triblock copolymer has a PDI of 1.2 to 1.

5. Polystyrene-polyolefin-polystyrene triblock copolymer. 【Chemical 34】 In the above Chemical Formula 7, Ar is an aryl group having 6 to 20 carbon atoms; The average value of m is 20 to 10,000; Y and Y' are each independently any one of hydrogen, methyl, ethyl, butyl, hexyl, and octyl, and Y and Y' are not the same; p and 1-p are the mole fractions of each repeat unit constituting repeat unit n, where p is a value from 0 to 1; The average value of n is 40 to 10,000; R 2 ~R 3 each independently represents hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; and z is an integer from 0 to 10.

2. In the formula 7, Ar is phenyl; the average value of m is 20 to 200; Y is hydrogen; Y' is methyl, ethyl, butyl, or hexyl; R 2 ~R 3 2. The polystyrene-polyolefin-polystyrene triblock copolymer of claim 1, wherein: is hydrogen; and z is 0 or 2.

3. a chain transfer polymerization reaction of an olefin monomer using a polynuclear zinc compound as a chain transfer agent to form a polyolefin block; and adding an alkyllithium compound containing a silicon atom, a triamine compound and a styrene-based monomer to the polyolefin block, and anionically polymerizing the resulting mixture to form a polystyrene block.

4. The method for producing a polystyrene-polyolefin-polystyrene triblock copolymer according to claim 3, wherein the polynuclear zinc compound is represented by the following chemical formula 8: 【Chemistry 35】 In the above Chemical Formula 8, R 1 is a hydrocarbyl having 1 to 20 carbon atoms; R 2 ~R 3 each independently represents hydrogen or a hydrocarbyl having 1 to 20 carbon atoms; The average value of a is 1 to 10; and z is an integer from 0 to 10.

5. The method for producing a polystyrene-polyolefin-polystyrene triblock copolymer according to claim 3 or 4, wherein the polynuclear zinc compound is represented by any one of the following formulas 8-1 and 8-2. [Chemical formula 8-1] CH 3 CH 2 -[Zn-(CH 2 ) 6 ] a -Zn-CH 2 CH 3 [Chemical formula 8-2] CH 3 -[Zn-(CH 2 ) 6 ] a -Zn-CH 3 In the formulae 8-1 and 8-2, the average value of a is 1 to 10.

6. The method for producing a polystyrene-polyolefin-polystyrene triblock copolymer according to any one of claims 3 to 5, wherein the alkyllithium compound containing a silicon atom is represented by the following chemical formula 3: [Chemical formula 3] (CH 3 ) 3 SiCH 2 Li

7. The method for producing a polystyrene-polyolefin-polystyrene triblock copolymer according to any one of claims 3 to 6, wherein the triamine compound is represented by the following chemical formula 4: 【Chemical Formula 36】

8. The method for producing a polystyrene-polyolefin-polystyrene triblock copolymer according to any one of claims 3 to 7, wherein the molar ratio ([Styrene] / [Zn]) of zinc atoms to styrene monomers added in the step of forming the polystyrene block is 250 to 1000.

9. The method for producing a polystyrene-polyolefin-polystyrene triblock copolymer according to any one of claims 3 to 8, wherein the number of polystyrene polymer chains generated per zinc atom ([PS-chains] / [Zn]) is 2.0 to 3.0.

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