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WO2019190289A1 - Composition de copolymère séquencé - Google Patents

Composition de copolymère séquencé Download PDF

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Publication number
WO2019190289A1
WO2019190289A1 PCT/KR2019/003751 KR2019003751W WO2019190289A1 WO 2019190289 A1 WO2019190289 A1 WO 2019190289A1 KR 2019003751 W KR2019003751 W KR 2019003751W WO 2019190289 A1 WO2019190289 A1 WO 2019190289A1
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Prior art keywords
carbon atoms
block
formula
block copolymer
copolymer composition
Prior art date
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PCT/KR2019/003751
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English (en)
Korean (ko)
Inventor
이현모
신은지
사석필
홍윤기
이기수
이분열
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180117839A external-priority patent/KR102379593B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2020547421A priority Critical patent/JP7199672B2/ja
Priority to CN201980017220.6A priority patent/CN111819212B/zh
Priority to US16/977,321 priority patent/US11312856B2/en
Priority to EP19776148.9A priority patent/EP3747920A4/fr
Publication of WO2019190289A1 publication Critical patent/WO2019190289A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond

Definitions

  • the present invention relates to a block copolymer composition, and more particularly, to a block copolymer composition comprising a diblock copolymer and a triblock copolymer including a polyolefin block and a polystyrene block.
  • Polyolefin-polystyrene block copolymers such as styrene-ethylene / butylene-styrene (SEBS) or styrene-ethylene / propylene-styrene (SEPS), currently have a market of several hundred thousand tons worldwide. In addition, they have the advantages of excellent heat resistance and light resistance compared to styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS), soft and strong touch of grip and handle, elastic material of diaper, medical and Oil-gels used in communication materials, impact modifiers in engineering plastics, flexibilizers or tougheners in transparent polypropylene, and the like.
  • SEBS styrene-ethylene / butylene-styrene
  • SEPS styrene-ethylene / propylene-styrene
  • SBS styrene-butadiene-st
  • SEBS is prepared through a two-step reaction of hydrogenating SBS obtained by anionic polymerization of styrene and butadiene.
  • SEPS is similarly prepared through a two-step reaction of hydrogenating SIS obtained by anionic polymerization of styrene and isoprene.
  • the process of saturating the unsaturated bonds contained in the polymer main chain by saturating all of them has a high process cost, and the unit costs of SEBS and SEPS are significantly higher than those of SBS and SIS before the hydrogenation reaction. This may limit market expansion.
  • the problem to be solved of the present invention is to provide a block copolymer composition comprising a diblock copolymer and a triblock copolymer comprising a polyolefin-based block and a polystyrene-based block with improved heat resistance.
  • the present invention provides a block copolymer composition
  • a block copolymer composition comprising a diblock copolymer and a triblock copolymer including a polyolefin-based block and a polystyrene-based block, and a polyolefin-based block of 45% by weight to 90% by weight, and 10 wt% to 55 wt% polystyrene-based block, wherein the difference between the thermal decomposition start temperature and the thermal decomposition end temperature ( ⁇ T) measured by Thermo-Gravimetric Analysis (TGA) is 55 ° C. or more, It provides a block copolymer composition, characterized in that no residual unsaturated bonds in the triblock copolymer and diblock copolymer.
  • the block copolymer composition according to the present invention is a block copolymer composition comprising a diblock copolymer and a triblock copolymer including a polyolefin block and a polystyrene block, and does not include an unsaturated bond in the molecular structure of the block copolymer. Excellent heat resistance can be exhibited.
  • composition' as used herein includes a mixture of materials comprising the composition as well as reaction and decomposition products formed from the material of the composition.
  • the term 'residual unsaturated bond' refers to an unsaturated bond, such as a double bond, a triple bond, present in the polymer chain of the block copolymer included in the block copolymer composition, and the polymer chain is a block copolymer. It includes the main chain and branched chain of, and includes unsaturated bonds generated in the polymerization process as well as unsaturated bonds contained in or derived from raw materials such as monomers, multimers, initiators, catalysts and the like used to prepare the block copolymer do.
  • halogen means fluorine, chlorine, bromine or iodine, unless stated otherwise.
  • alkyl means a straight, cyclic or branched hydrocarbon moiety unless stated otherwise.
  • 'aryl' refers to aromatic groups including phenyl, naphthyl anthryl, phenanthryl, chrysenyl, pyrenyl, and the like, unless stated otherwise.
  • silyl may be silyl unsubstituted or substituted with alkyl having 1 to 20 carbon atoms, for example, silyl, trimethylsilyl or triethylsilyl.
  • the block copolymer composition of the present invention is a block copolymer composition comprising a diblock copolymer and a triblock copolymer comprising a polyolefin-based block and a polystyrene-based block, and includes 45 to 90 wt% of a polyolefin-based block, and 10 A polystyrene-based block (wt% to 55 wt%), wherein the difference between the thermal decomposition initiation temperature and the thermal decomposition end temperature ( ⁇ T) measured by Thermo-Gravimetric Analysis (TGA) is 55 ° C. or more, Since there is no residual unsaturated bond in the triblock copolymer and the diblock copolymer, improved heat resistance can be exhibited.
  • TGA Thermal decomposition end temperature
  • the block copolymer composition of the present invention measures the temperature at which thermal decomposition starts and the temperature at which thermal decomposition ends using TGA (Thermo-Gravimetric Analysis), the temperature at which thermal decomposition ends and thermal decomposition occurs
  • the difference ⁇ T of the temperature starting to be made may have a large value of 55 ° C. or more, specifically 55 ° C. to 70 ° C., more specifically 57 ° C. to 65 ° C.
  • the block copolymer composition of the present invention is free from residual unsaturated bonds in the block copolymer, and includes 45% to 90% by weight of polyolefin-based blocks, and 10% to 55% by weight of polystyrene-based blocks. It can exhibit heat resistance.
  • the difference ( ⁇ T) between the temperature at which the thermal decomposition ends and the temperature at which thermal decomposition begins to be satisfied satisfies the above range, the block copolymer composition may exhibit excellent processability while exhibiting improved heat resistance.
  • the temperature at which the thermal decomposition ends is 440 ° C.
  • the temperature at which the thermal decomposition starts to be 385 °C to 405 °C specifically the temperature at which the thermal decomposition is finished is 445 °C to 465 °C
  • the temperature at which the thermal decomposition starts to be 388 °C To 405 °C more specifically, the temperature at which the thermal decomposition is finished may be 448 °C to 463 °C
  • the temperature at which the thermal decomposition starts to be may be 390 °C to 403 °C.
  • the block copolymer composition according to an example of the present invention may also (1) satisfy the weight average molecular weight (Mw) of 70,000 g / mol to 120,000 g / mol, specifically 72,000 g / mol to 110,000 g / mol, more Specifically, it may satisfy 74,000 g / mol to 103,000 g / mol.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is a polystyrene reduced molecular weight analyzed by gel permeation chromatography (GPC).
  • the block copolymer composition may have a polydispersity index (PDI) of 1.0 to 2.0, specifically 1.2 to 1.8, more specifically 1.4 to 1.7.
  • PDI polydispersity index
  • the polydispersity index means the ratio of Mw / Mn, Mw is the weight average molecular weight and Mn represents the number average molecular weight.
  • the block copolymer composition (3) the glass transition temperature (Tg) may satisfy -55 °C to -30 °C, specifically -55 °C to -39 °C, more specifically -52 °C to -39 °C Can be satisfied.
  • the glass transition temperature (Tg) can be measured using a Dynamic Mechanical Analyzer (DMA).
  • the block copolymer composition (4) melt index (MI, 230 °C, 5 kg load conditions) may satisfy 0.2 to 3.0 g / 10 minutes, specifically 0.3 to 2.5 g / 10 minutes, more specifically 0.3 to 2.1 g / 10 minutes may be satisfied.
  • the melt index (MI) affects the mechanical properties, impact strength, and formability of the block copolymer.
  • the melt index can be measured at 230 °C, 5 kg load conditions according to ASTM D1238 (ISO 1133).
  • the block copolymer composition of the present invention satisfies the conditions of the above (1) to (4) at the same time, it exhibits a high molecular weight and a wide molecular weight distribution, it can exhibit excellent processability with improved heat resistance as described above.
  • the block copolymer composition of the present invention includes, for example, (a) reacting an organic zinc compound with at least one olefinic monomer under a transition metal catalyst to form an olefinic polymer block to prepare an intermediate; And (b) reacting the intermediate obtained in step (a) with a styrene monomer in the presence of an alkyllithium compound to form a styrene polymer block.
  • the olefinic monomer may be inserted between Zn and A of the organic zinc compound to polymerize and form an olefinic polymer block.
  • the olefin-based polymer block formed by the polymerization of one or more of the olefinic monomers may include a repeating unit represented by the following formula (1), and the repeating unit represented by the following formula (1)
  • the said olefin type polymer block containing is shown as a 1st block.
  • the olefinic monomer may form a first block including one or more repeating units represented by the following Chemical Formula 1.
  • R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,
  • n can be an integer from 1 to 10,000.
  • R 1 is hydrogen; It may be alkyl having 3 to 20 carbon atoms.
  • n may be an integer of 10 to 10,000, specifically, may be an integer of 500 to 7,000.
  • the first block when the first block includes two or more repeating units represented by Formula 1, the first block may include a repeating unit represented by Formula 2 below.
  • R One 'And R One Are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl; R One 'And R One "Is different,
  • n ' may be an integer from 1 to 10,000.
  • R 1 ′ and R 1 ′′ may each independently be hydrogen or alkyl having 3 to 20 carbon atoms, specifically, each independently hydrogen or alkyl having 3 to 12 carbon atoms, More specifically, each may independently be hydrogen or alkyl having 4 to 12 carbon atoms.
  • n ′ may be an integer of 10 to 10,000, and more specifically, an integer of 500 to 7,000.
  • any one of R 1 ′ and R 1 ′′ in Formula 2 may be hydrogen, and the other may be a substituent other than hydrogen in the aforementioned substituents.
  • R 1 is hydrogen and R 1 is alkyl having 1 to 20 carbon atoms other than hydrogen; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or a silyl group of a carbon number of arylalkyl is a structure of 7 to 20 may be connected at random (random), specifically, R 1 is an alkyl structure of the structure and R 1 is 3 to 20 carbon atoms other than a hydrogen hydrogen substituted with May be randomly connected.
  • the first block may be one in which the structure in which R 1 is hydrogen and the structure in which R 1 is alkyl having 3 to 12 carbon atoms in Formula 1 is randomly connected, and more specifically, the first block. May be one in which the structure in which R 1 is hydrogen and the structure in which R 1 is alkyl having 4 to 12 carbon atoms in Formula 1 are randomly connected.
  • the first block When the first block includes two or more repeating units represented by Formula 1, the first block has a structure in which R 1 is hydrogen in Formula 1 and a structure in which R 1 has a substituent other than hydrogen: It may be included in a weight ratio of 90 to 70:10, specifically, may be included in a weight ratio of 40:60 to 60:40, and more specifically may be included in a weight ratio of 45: 75 to 55:25.
  • the prepared block copolymer includes a branch to an appropriate degree in the structure. Therefore, it has high 300% modulus value and elongation at break value, thereby exhibiting excellent elastic properties, and exhibiting broad molecular weight distribution with high molecular weight, thus having excellent processability.
  • the olefinic monomer which is inserted between Zn and A of the organic zinc compound to polymerize to form the olefinic polymer block (first block) comprises ethylene and at least one alpha-olefinic monomer. It may be included together, and specifically may include ethylene and one or more alpha-olefin monomers other than ethylene.
  • the alpha-olefin monomer may be specifically an aliphatic olefin having 3 to 20 carbon atoms, more specifically an aliphatic olefin having 4 to 12 carbon atoms, and more specifically an aliphatic olefin having 5 to 12 carbon atoms. have.
  • Examples of the aliphatic olefins include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1 -Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-icocene, 4,4-dimethyl-1-pentene, 4,4 -Diethyl-1-hexene, 3,4-dimethyl-1-hexene, and the like, and any one or a mixture of two or more thereof.
  • the block copolymer may include 45 wt% to 90 wt% polyolefin block, and specifically 50 wt% to 85 wt%, more specifically 57 wt% to 82 wt% polyolefin block. have.
  • the polyolefin block may include 35 wt% to 60 wt% of the repeating unit derived from the ethylene based on the entire block copolymer, and specifically 37 wt% to 55 wt%, and more specifically, 39 wt% to 50 wt% may be included.
  • the polyolefin-based block may include 10 wt% to 35 wt% of the repeating unit derived from the alpha-olefin, and specifically 15 to 33 wt% based on the entire block copolymer. More specifically, it may include 18 wt% to 32 wt%.
  • the polyolefin block may impart more appropriate elasticity to the block copolymer.
  • the organic zinc compound may be a compound represented by the following formula (3).
  • A is alkylene having 1 to 20 carbon atoms; Arylene having 6 to 20 carbon atoms; Or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms.
  • A is an alkylene having 1 to 12 carbon atoms; Arylene having 6 to 12 carbon atoms; Or arylene having 6 to 12 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • B may be arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 8 carbon atoms.
  • Formula 3 may have a structure in which both ends of the formula is a double bond, for example, when the B is arylene substituted with alkenyl, the arylene is connected to the A, and a double of alkenyl substituted with the arylene The bond may be located at the outermost part of the formula (3).
  • R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,
  • A is alkylene having 1 to 20 carbon atoms; Arylene having 6 to 20 carbon atoms; Or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms
  • n is an integer from 1 to 10,000.
  • R 1 and n are as defined in Formula 1, respectively, and A and B are as defined in Formula 3, respectively.
  • an example of the intermediate formed is It can be represented as 4A.
  • R 1 ′, R 1 ′′, p and n ′ are as defined in Formula 2, respectively, and A and B are as defined in Formula 3, respectively.
  • step (b) reacting the intermediate obtained in step (a) with a styrene monomer in the presence of an alkyllithium compound to form a styrene polymer block
  • the styrene monomer may be inserted between the Zn of the intermediate and the olefin polymer block to polymerize and form a styrene polymer block.
  • the alkyllithium compound may be an alkyllithium compound including a silicon atom, for example, Me 3 SiCH 2 Li.
  • the styrene-based polymer block formed by the polymerization of the styrene-based monomer may include a repeating unit represented by the following formula (6), and includes a repeating unit represented by the following formula (6) Said styrene-based polymer block is shown as a second block.
  • R 2 is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • l is independently an integer of 10 to 1,000.
  • R 2 is phenyl; Or phenyl unsubstituted or substituted with halogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, alkoxy of 1 to 8 carbon atoms, or aryl of 6 to 12 carbon atoms, and wherein R 2 may be phenyl. have.
  • l is an integer of 10 to 1,000, specifically may be an integer of 50 to 700, when the l is in the above range the viscosity of the polyolefin-polystyrene block copolymer prepared by the production method of the present invention may have an appropriate level. have.
  • the styrene monomer is inserted between the Zn of the intermediate and the olefin polymer block to polymerize and form a styrene polymer block (second block), thereby repeating unit represented by the formula (1)
  • a first block including and a second block including a repeating unit represented by Formula 6 may be combined to form a complex block represented by Formula 7 below.
  • R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,
  • R 2 is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • l is an integer from 10 to 1,000
  • n is an integer from 1 to 10,000.
  • R 1 , R 2 , l, and n are as defined in Chemical Formula 1 and Chemical Formula 6, respectively.
  • a complex block formed by combining a second block including the repeating unit represented by Formula 6 may be represented by the following Formula 8.
  • R 1 ′, R 1 ′′, p, l and n ′ are the same as defined in Formula 2 or 6, respectively.
  • the styrene monomer in the step (b), is inserted between the Zn and the olefin polymer block of the intermediate to form a styrene polymer block (second block) while polymerization is carried out
  • the styrene-based monomer may be bonded to a portion represented by B of the organic zinc compound represented by Formula 4 to polymerize to form a separate styrene-based polymer block.
  • a separate styrene-based polymer block bonded to the portion indicated by B and polymerized is represented as a third block.
  • the third block is formed at the same time as the second block is formed, a triblock copolymer can be formed.
  • the third block may include a repeating unit represented by Formula 9 below.
  • R 3 is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • n is independently an integer of 10-1,000.
  • R 3 is phenyl; Or phenyl unsubstituted or substituted with halogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, alkoxy of 1 to 8 carbon atoms, or aryl of 6 to 12 carbon atoms, and R 3 is phenylyl.
  • halogen alkyl of 1 to 8 carbon atoms
  • cycloalkyl of 3 to 12 carbon atoms alkoxy of 1 to 8 carbon atoms
  • aryl of 6 to 12 carbon atoms aryl of 6 to 12 carbon atoms
  • M is an integer of 10 to 1,000, specifically, may be an integer of 50 to 700.
  • the styrene-based monomer in the step (b) may form a second block comprising a repeating unit represented by the formula (6), and the third block represented by the formula (9), respectively have.
  • the block copolymer composition may include a first block including one or more repeating units represented by the following Formula 1; A second block including a repeating unit represented by Formula 6 below; And it may include a triblock copolymer comprising a third block comprising a repeating unit represented by the formula (9).
  • R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,
  • R 2 and R 3 is aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • n is an integer from 10 to 10,000
  • l and m are each independently an integer of 10 to 1,000.
  • R 1 , R 2 , R 3 , n, l and m are as defined in the formulas (1), (6) and (9), respectively.
  • step (b) since the first block, the second block and the third block are formed symmetrically around the zinc (Zn) of the organic zinc compound represented by the formula (3), in step (b) It is possible to prepare a compound in which a triblock copolymer comprising three blocks as a center is symmetrically formed.
  • An example of such a block copolymer is represented by the following formula (10).
  • R 1 to R 3 , l, m and n are the same as defined in Chemical Formulas 1, 5 and 7, A is the same as defined in Chemical Formula 3, and B 'is the same as defined in Chemical Formula 3, The form combined with a repeating unit is shown.
  • step (b) an example of a compound in which a triblock copolymer including three blocks is formed symmetrically based on the zinc produced May be represented as in Chemical Formula 8A.
  • R 1 ′, R 1 ′′, R 2 and R 3 , p, l, m and n ′ are as defined in Formulas 2, 5 and 7, respectively, A is as defined in Formula 3, and B 'is B defined in Chemical Formula 3 represents a form combined with a repeating unit of Chemical Formula 9.
  • the first block and the second block when two or more of the first block and the second block are included, the first block and the second block may be included as a repeating unit of a composite block having a structure represented by Formula 7 or 8
  • the block copolymer when the block copolymer includes two first blocks and two second blocks, and one third block as an example, the block copolymer includes two composite blocks and one third block. It means to include.
  • the block copolymer when the block copolymer includes two or more composite blocks of the formula (7), the remaining composite blocks except for one composite block is connected to the other composite block, it is connected to the third block It may not be.
  • the block copolymer when the block copolymer includes two or more of the composite blocks, one composite block is connected to the third block, and the composite block extends through a bond between the composite blocks to form a "third block-composite block-". Composite block-... ".
  • the first block and the second block included in the composite block may be connected.
  • the block copolymer according to an example of the present invention may include one third block and two composite blocks. If so, the structure may have a structure such as "third block-first block-second block-first block-second block-".
  • the block copolymer composition according to the exemplary embodiment of the present invention may include a block copolymer including a structure represented by the following Chemical Formula 12.
  • R 1 is hydrogen; Alkyl having 1 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl,
  • R 2 and R 3 are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • l and m are each independently an integer of 10 to 1,000,
  • n is an integer from 1 to 10,000.
  • a may be an integer of 1 to 50, specifically, an integer of 1 to 20, and more specifically, an integer of 1 to 10.
  • R 1 to R 3 , 1, m, and n are the same as defined in Formulas 1, 6, and 9, respectively.
  • block copolymer composition according to an example of the present invention may include a block copolymer including a structure represented by the following Formula (13).
  • R 1 ′ and R 1 ′′ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl; Arylalkyl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms substituted with silyl, wherein R 1 'and R 1 "are different from each other,
  • R 2 and R 3 are each independently aryl having 6 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms,
  • l and m are each independently an integer of 10 to 1,000,
  • n is an integer from 1 to 10,000.
  • a may be an integer of 1 to 50, specifically, an integer of 1 to 20, and more specifically, an integer of 1 to 10.
  • R 1 ′, R 1 ′′, R 2 and R 3 , p, l, m, and n ′ are the same as defined in Chemical Formulas 2, 6, and 9, respectively.
  • the styrene monomer is, for example, styrene unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms. It may be a system monomer.
  • the third block is formed at the same time as the second block is formed in step (b), so that a triblock copolymer can be formed, and in the step (b), the second block is formed.
  • a diblock copolymer is formed.
  • the block copolymer composition of the present invention is a block copolymer composition comprising a diblock copolymer and a triblock copolymer including a polyolefin block and a polystyrene block, and the content of the diblock copolymer may be 19 wt% or less.
  • the content of the diblock copolymer satisfies 19% by weight or less, so that the block copolymer composition may exhibit excellent thermal stability while having excellent chemical durability, mechanical properties, and melt processability.
  • the diblock copolymer may be a polyolefin-polystyrene diblock copolymer
  • the triblock copolymer may be a polystyrene-polyolefin-polystyrene triblock copolymer
  • the amount of the diblock copolymer and the triblock copolymer is It is influenced by the ratio of the number of moles of the organic zinc compound used in step (a) and the number of moles of the alkyllithium compound used in step (b).
  • the number of moles of the alkyllithium compound used in the step (b) may have a larger value than the number of moles of the organic zinc compound used in the step (a). .
  • the amount of lithium (Li) used in the manufacturing process of the block copolymer of the present invention may be higher than that of zinc (Zn).
  • the polymerization rate is further increased to increase productivity, and zinc (Zn) and All of the olefinic polymer ends can be initiated to effectively synthesize the triblock copolymer.
  • the number of moles of the alkyllithium compound used in the step (b) is not particularly limited as long as it has a large value compared to the number of moles of the organic zinc compound used in the step (a), the organic used in the step (a)
  • the number of moles of the zinc compound and the number of moles of the alkyllithium compound used in step (b) may be 1: 1.05 to 1: 4, specifically 1: 1 to 1: 3, more specifically 1.1 to 2.5 days Can be.
  • the block copolymer composition of the present invention is 19 wt% or less, specifically 18 wt% or less of the diblock copolymer in the copolymer composition, More specifically, it may be included in an amount of 17 wt% or less.
  • the diblock copolymer may include a structure of Formula 7 or 8
  • the triblock copolymer may include a structure of Formula 12 or 13.
  • the diblock copolymer has a structure of a CH 3 form in which a unit derived from an organic zinc compound of Formula 3, that is, B and A defined in Formula 3, is bonded to one end of Formula 7 or 8, and the other end is terminated. It may have, and the triblock copolymer may have a structure of Formula 14 or 15.
  • an amine compound specifically a triamine compound
  • the triamine compound may be, for example, PMDETA (N, N, N ′′, N ′′). , N "-pentamethyldiethylenetriamine).
  • the alkyllithium compound and the amine compound may be used, for example, in a molar ratio of 0.5: 1 to 1: 1.
  • the amine compound may act as an initiator in combination with the alkyllithium compound. Can be.
  • Block copolymer composition may include 10% to 99% by weight of the first block, based on the entire composition, 1% to 90% by weight of the second block and the third block in total It may include weight percent.
  • the first block may include 40 wt% to 85 wt%
  • the second block and the third block may include 15 wt% to 60 wt% in total, and more specifically, 60 wt% to 80 wt% of the first block may be included, and 20 wt% to 40 wt% of the second block and the third block may be included in a total amount.
  • an example of the method for preparing a block copolymer composition of the present invention may further include (c) converting the product prepared in step (b) into a block copolymer by reacting with water, oxygen, or an organic acid. .
  • the product prepared in step (b) may be represented by the formula (8), as described above, water in the compound comprising a block copolymer formed symmetrically around the zinc (Zn) prepared in step (b) In the case of adding oxygen, an organic acid, or the like, two block copolymers may be formed between the zinc and the block bonded to the zinc.
  • the block copolymer composition according to an example of the present invention has a structure in which a compound derived from the compound used in the preparation process, specifically, an organic zinc compound of Formula 3, is included between the third block and the first block. It may also include.
  • An example of such a block copolymer structure is shown in the following formula (14).
  • R 1 to R 3 , l, m, and n are as defined in Formulas 1, 5, and 7, respectively, A is as defined in Formula 3, and B 'represents B as defined in Formula 3 above. The form combined with the repeating unit of Formula 9 is shown.
  • a block copolymer structure in which a compound derived from the compound used in the preparation process, specifically, the organic zinc compound of Formula 3, is included between the third block and the first block may be represented as in Formula 15 below. Can be represented.
  • R 1 ′, R 1 ′′, R 2 and R 3 , p, l, m and n ′ are as defined in Formulas 2, 6 and 9, respectively, A is as defined in Formula 3, and B ′ is B defined in Chemical Formula 3 represents a form combined with a repeating unit of Chemical Formula 9.
  • a monomer capable of leaving a residual unsaturated bond such as a diene compound such as butadiene or isoprene is not used in the process of preparing a polyolefin-based block to separate residual unsaturated bonds. Since no hydrogenation reaction is required and no unsaturated bonds remain unsaturated even by the hydrogenation reaction, the block copolymer composition of the present invention does not contain an unsaturated bond and can exhibit excellent heat resistance.
  • Example 1 except that the amount of 1-hexene, styrene, organic zinc compound, methylcyclohexane, transition metal compound / cocatalyst solution, and the amount of Me 3 SiCH 2 Li and PMDETA were changed as shown in Table 1 below
  • the polymer was prepared by the same method as described above.
  • a polymer was prepared in the same manner as in Example 10, except that 35 g of propylene was injected, ethylene was injected thereto to have a pressure of 20 bar, and 20 bar was maintained.
  • CH 3 of the content was calculated after identifying the CH 3 related triplet of the butyl branch with 1-hexene at around 0.96 ppm.
  • the content of styrene was calculated as an aromatic peak near 6.5 to 7.5 ppm.
  • the weight average molecular weight (Mw, g / mol) and the number average molecular weight (Mn, g / mol) were measured by gel permeation chromatography (GPC), and the weight average molecular weight was divided by the number average molecular weight.
  • the polydispersity index (PDI) was calculated.
  • thermo-Gravimetric Analysis is used to measure the temperature (T onset ) at which decomposition begins and the temperature (T end ) at which pyrolysis ends, and the temperature and thermal decomposition at which the thermal decomposition ends The difference ( ⁇ T) of the temperature at which it started to rise was calculated.
  • the temperature was measured at 10 ° C./min intervals in the temperature range of 20 ° C. to 700 ° C., and precisely measured in a nitrogen atmosphere.
  • GPC curves obtained by gel permeation chromatography were obtained by deconvolution assuming peaks with two Gaussian curves.
  • Example 1 47.7 25.8 26.5 76,700 1.6 0 391.62 / 449.41 57.43 13.8
  • Example 2 46.9 28.7 24.4 79,700 1.7 0 390.62 / 459.84 69.22 10.2
  • Example 3 42.6 27.9 29.5 65,800 1.7 0 390.41 / 458.66 68.25 11.7
  • Example 4 48.4 31.6 22.0 76,100 1.8 0 398.71 / 460.95 62.24 13.2
  • Example 5 49.1 25.3 25.5 98,000 1.8 0 401.34 / 464.35 63.01 13.7
  • Example 6 39.3 18.6 42.1 111,000
  • the block copolymer composition of Examples 1 to 7 is a difference between the thermal decomposition start temperature and the thermal decomposition end temperature measured by Thermo-Gravimetric Analysis (TGA) compared to Comparative Examples 1 to 4 ( ⁇ T) was large. As such, the block copolymer composition of Examples 1 to 7 does not include unsaturated bonds in the molecular structure, and thus, more improved heat resistance than the block copolymers of Comparative Examples 1 to 4 including unsaturated bonds. Exerted.
  • block copolymer composition of Examples 1 to 7 showed a large value of the polydispersity index (PDI) compared to the block copolymer of Comparative Examples 1 to 4, through which the block copolymer composition of Examples 1 to 7 It can be expected that while exhibiting improved heat resistance, they will exhibit relatively good processability.
  • PDI polydispersity index

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Abstract

La présente invention concerne une composition de copolymère séquencé comprenant un copolymère dibloc et un copolymère tribloc, contenant un bloc à base de polyoléfine et un bloc à base de polystyrène. La composition de copolymère séquencé selon la présente invention comprend de 45 % en poids à 90 % en poids du bloc à base de polyoléfine, et de 10 % en poids à 55 % en poids du bloc à base de polystyrène. La différence (△T) entre la température de début de décomposition thermique et la température de fin de décomposition thermique telle que mesurée par analyse thermogravimétrique (TGA) est supérieure ou égale à 55 °C, et il n'y a pas de liaison insaturée restant dans le copolymère tribloc et le copolymère dibloc.
PCT/KR2019/003751 2018-03-30 2019-03-29 Composition de copolymère séquencé Ceased WO2019190289A1 (fr)

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JP2020547421A JP7199672B2 (ja) 2018-03-30 2019-03-29 ブロック共重合体組成物
CN201980017220.6A CN111819212B (zh) 2018-03-30 2019-03-29 嵌段共聚物组合物
US16/977,321 US11312856B2 (en) 2018-03-30 2019-03-29 Block copolymer composition
EP19776148.9A EP3747920A4 (fr) 2018-03-30 2019-03-29 Composition de copolymère séquencé

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4050013A4 (fr) * 2020-04-16 2023-01-11 LG Chem, Ltd. Composé de ligand, composé de métal de transition et composition de catalyseur les comprenant
JP2023511913A (ja) * 2020-04-16 2023-03-23 エルジー・ケム・リミテッド ポリオレフィン－ポリスチレン系多重ブロック共重合体及びこの製造方法
EP4169927A4 (fr) * 2020-07-31 2024-01-17 Lg Chem, Ltd. Procédé de production d'un composé organozincique, agent de transfert de chaîne, copolymère séquencé et composition de résine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101732418B1 (ko) * 2016-03-15 2017-05-24 아주대학교 산학협력단 폴리올레핀-폴리스티렌 다중블록 공중합체 및 그 제조 방법
KR101829382B1 (ko) * 2017-08-17 2018-02-20 아주대학교 산학협력단 폴리올레핀-폴리스티렌계 다중블록 공중합체, 이를 제조하기 위한 유기 아연 화합물 및 폴리올레핀-폴리스티렌계 다중블록 공중합체 제조 방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101732418B1 (ko) * 2016-03-15 2017-05-24 아주대학교 산학협력단 폴리올레핀-폴리스티렌 다중블록 공중합체 및 그 제조 방법
KR101829382B1 (ko) * 2017-08-17 2018-02-20 아주대학교 산학협력단 폴리올레핀-폴리스티렌계 다중블록 공중합체, 이를 제조하기 위한 유기 아연 화합물 및 폴리올레핀-폴리스티렌계 다중블록 공중합체 제조 방법

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Part A: Polymer Chemistry", JOURNAL OF POLYMER SCIENCE, vol. 40, 2002, pages 1253
KIM, C. S.: "Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers", POLYMERS, vol. 9, 2017, pages 481, XP055637559 *
KIM, D. H.: "Preparation of polystyrene-polyolefin multiblock copolymers by sequential coordination and anionic polymerization", RSC ADVANCES, 2017, pages 5948 - 5956, XP055612568, doi:10.1039/C6RA25848D *
POLYMER DEGRADATION AND STABILITY, vol. 95, 2010, pages 975
RABAGLIATI, F. M.: "Styrene/(Styrene Derivative) and Styrene/(1-Alkene) Copolymerization using Ph2Zn-Additive Initiator Systems", MACROMOLECULAR SYMPOSIA, 2004, XP055638799 *
See also references of EP3747920A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4050013A4 (fr) * 2020-04-16 2023-01-11 LG Chem, Ltd. Composé de ligand, composé de métal de transition et composition de catalyseur les comprenant
JP2023511913A (ja) * 2020-04-16 2023-03-23 エルジー・ケム・リミテッド ポリオレフィン－ポリスチレン系多重ブロック共重合体及びこの製造方法
JP2023513454A (ja) * 2020-04-16 2023-03-31 エルジー・ケム・リミテッド リガンド化合物、遷移金属化合物およびこれを含む触媒組成物
JP7446662B2 (ja) 2020-04-16 2024-03-11 エルジー・ケム・リミテッド ポリオレフィン－ポリスチレン系多重ブロック共重合体及びこの製造方法
JP7536333B2 (ja) 2020-04-16 2024-08-20 エルジー・ケム・リミテッド リガンド化合物、遷移金属化合物およびこれを含む触媒組成物
EP4169927A4 (fr) * 2020-07-31 2024-01-17 Lg Chem, Ltd. Procédé de production d'un composé organozincique, agent de transfert de chaîne, copolymère séquencé et composition de résine

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