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WO2019190287A1 - Composition de copolymère séquencé - Google Patents

Composition de copolymère séquencé Download PDF

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Publication number
WO2019190287A1
WO2019190287A1 PCT/KR2019/003749 KR2019003749W WO2019190287A1 WO 2019190287 A1 WO2019190287 A1 WO 2019190287A1 KR 2019003749 W KR2019003749 W KR 2019003749W WO 2019190287 A1 WO2019190287 A1 WO 2019190287A1
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WIPO (PCT)
Prior art keywords
carbon atoms
block
alkyl
formula
aryl
Prior art date
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Ceased
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PCT/KR2019/003749
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English (en)
Korean (ko)
Inventor
신은지
이기수
사석필
홍윤기
이분열
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180117841A external-priority patent/KR102373305B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US16/976,236 priority Critical patent/US11414541B2/en
Priority to CN201980015877.9A priority patent/CN111770944B/zh
Priority to JP2020548802A priority patent/JP7094603B2/ja
Priority to EP19776273.5A priority patent/EP3747921B1/fr
Publication of WO2019190287A1 publication Critical patent/WO2019190287A1/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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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 comprising an olefinic polymer block and a styrene polymer 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 all the double bonds contained in the polymer main chain by saturating the process cost is high, and the cost of SEBS and SEPS is significantly higher than that 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 an olefin-based polymer block and a styrene-based polymer block.
  • the present invention includes a diblock copolymer and a triblock copolymer including an olefin polymer block and a styrene polymer block, and the content of the diblock copolymer is 19 wt% or less, and the olefin
  • the polymer block includes a repeating unit represented by Chemical Formula 1, and the styrene-based polymer block provides a block copolymer composition including at least one selected from the group consisting of Chemical Formula 2 and Chemical Formula 3 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 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,
  • n is an integer from 1 to 10,000
  • l and m are each independently an integer of 10 to 1,000.
  • the block copolymer composition according to the present invention includes a diblock copolymer and a triblock copolymer including an olefinic polymer block and a styrene polymer block, and the structure and properties of each block included in these copolymers are controlled and improved. It can exhibit physical properties.
  • 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 comprises a diblock copolymer and a triblock copolymer comprising an olefin-based polymer block and a styrene-based polymer block, and the content of the diblock copolymer is 19 wt% or less, and the olefin-based
  • the polymer block includes repeating units represented by Formula 1, and the styrene-based polymer block includes at least one selected from the group consisting of Formula 2 and Formula 3 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 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,
  • n is an integer from 1 to 10,000
  • l and m are each independently an integer of 10 to 1,000.
  • R 1 is hydrogen; Or alkyl having 3 to 12 carbon atoms.
  • R 2 and R 3 are each independently phenyl; Or phenyl 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, wherein R 2 is hydrogen; Alkyl having 3 to 20 carbon atoms; Alkyl having 3 to 20 carbon atoms substituted with silyl; Arylalkyl having 8 to 20 carbon atoms; Or arylalkyl having 8 to 20 carbon atoms substituted with silyl.
  • R 2 may be hydrogen or alkyl having 4 to 12 carbon atoms
  • R 2 and R 3 may be phenyl.
  • N is an integer of 10 to 10,000, specifically may be an integer of 500 to 7,000, and m is an integer of 10 to 1,000, specifically may be an integer of 50 to 700.
  • n and m satisfy the above range simultaneously, the block copolymer may exhibit both high tensile strength and high elastic modulus.
  • the l may be an integer of 10 to 1,000, specifically, may be an integer of 50 to 700, and when the l is in the above range, the viscosity of the block copolymer may have an appropriate level.
  • the olefinic polymer block when the olefinic polymer block includes two or more repeating units represented by Formula 1, the olefinic polymer block may include a repeating unit represented by the following Formula 4.
  • 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; R 1 'and R 1 "are different from each other,
  • n ' may be an integer from 10 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 ′′ may be hydrogen, and the other one may be a substituent other than hydrogen.
  • the olefin polymer block in this case comprise a repeating unit of two or more kinds represented by the above formula 1, R 1 having 1 to 20 carbon atoms of any other structure and R 1 is hydrogen hydrogen alkyl ; 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 olefin-based polymer 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 olefin-based polymer block.
  • the polymer 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 Chemical Formula 1 are randomly connected.
  • the olefinic polymer block When the olefinic polymer block includes two or more repeating units represented by Formula 1, the olefinic polymer block has a structure in which R 1 is hydrogen in Formula 1 and R 1 has a substituent other than hydrogen. It may be included in a weight ratio of 30:90 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 branch (branch) suitable degree in the block copolymer of the structure to be produced Since it has a high modulus value and elongation at break value of 300%, it can exhibit excellent elastic properties, and also exhibit a wide molecular weight distribution with high molecular weight, thereby having excellent processability.
  • the diblock copolymer and the triblock copolymer may each include a composite block represented by the following Formula 5 formed by combining the polyolefin block and the polystyrene block.
  • 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 10 to 10,000.
  • R 1 , R 2 , l and n are as defined in Formula 1 or Formula 2, respectively.
  • the composite block formed by combining the polystyrene-based block may be represented by the following formula (6).
  • R 1 ', R 1 ", p, l and n' are as defined in Formula 2 or 4, respectively.
  • the olefin-based polymer block including the repeating unit represented by Formula 1 is also represented as a first block, and each of the styrene-based polymer blocks including the repeating unit represented by Formulas 2 and 3 is a second block. And third block.
  • 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 complex block having a structure represented by Formula 5 or 6 above.
  • the block copolymer composition according to an example of the present invention includes a block copolymer including two first blocks, two second blocks, and one third block, the block copolymer Means that it contains two composite blocks and one third block.
  • the block copolymer when the block copolymer includes two or more complex blocks of Formula 5 or 6, the remaining complex blocks except for one complex block is connected to the other complex block, and May not be connected.
  • 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 Formula 7, specifically, a triblock copolymer.
  • 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 10 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 is hydrogen; Alkyl having 1 to 13 carbon atoms; Alkyl having 1 to 13 carbon atoms substituted with silyl; Arylalkyl having 7 to 13 carbon atoms; Or arylalkyl having 7 to 13 carbon atoms substituted with silyl,
  • R 2 may be 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,
  • R 3 is hydrogen; Or alkyl having 1 to 12 carbon atoms.
  • R 1 to R 3 , l, m, and n are the same as defined in Chemical Formulas 1 to 3, respectively.
  • block copolymer composition according to an embodiment of the present invention may include a block copolymer, specifically a triblock copolymer, having a structure represented by the following formula (8).
  • 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 10 to 10,000
  • a is an integer of 1-50.
  • R 1 ′, R 1 ′′, p, l, n ′, a are the same as defined in Formula 2, 4, or 7, respectively.
  • composition of the block copolymer of the present invention may include, for example, (1) 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 (2) reacting the intermediate obtained in step (1) with a styrene monomer in the presence of an alkyllithium compound to form a styrene polymer block.
  • the compound prepared in step (2) may be an organic zinc compound comprising a block copolymer comprising the repeating unit structure of Chemical Formulas 1 to 3 above, and additionally, the product prepared in step (2) is water (3). It can be converted to the block copolymer by the step of reacting with oxygen, or an organic acid to convert into a block copolymer.
  • the olefinic monomer may be inserted between Zn and A of the organic zinc compound to polymerize and form an olefinic polymer block including a repeating unit represented by Chemical Formula 1.
  • 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 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-eicosene, 4,4-dimethyl-1- Pentene, 4,4-diethyl-1-hexene or 3,4-dimethyl-1-hexene, and the like, and any one or a mixture of two or more thereof.
  • the organic zinc compound may be a compound represented by the following formula (9).
  • 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 9 may have a structure in which both ends of the formula is a double bond, for example, when B is arylene substituted with alkenyl, the arylene is linked to A, and a double of alkenyl substituted with 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 10 to 10,000.
  • R 1 and n are as defined in Formula 1, respectively, and A and B are as defined in Formula 9, respectively.
  • an example of the intermediate formed is It can be represented as 11.
  • R 1 ′, R 1 ′′, p and n ′ are as defined in Formula 2, respectively, and A and B are as defined in Formula 9, respectively.
  • step (2) reacting the intermediate obtained in step (1) with a styrene monomer in the presence of an alkyllithium compound to form a styrene polymer block
  • the styrene-based monomer is inserted between the Zn and the olefin-based polymer block of the intermediate may be polymerized to form a styrene-based polymer block.
  • the alkyllithium may be an alkyllithium compound including a silicon atom, for example Me 3 SiCH 2 Li.
  • step (2) the styrene monomer is inserted between 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 complex block represented by Chemical Formula 5 may be formed by combining a first block including and a second block including a repeating unit represented by Chemical Formula 2.
  • the styrene-based monomer in the step (2), is inserted between the Zn and the olefin-based 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 9 to polymerize to form a separate styrene-based polymer block.
  • a separate styrene-based polymer block bonded to the portion represented by B is polymerized as a third block, which corresponds to a repeating unit represented by Chemical Formula 3.
  • the step (2 ) since the first block, the second block and the third block are symmetrically formed around the zinc (Zn) of the organic zinc compound represented by Formula 9, the step (2 ), A compound in which a triblock copolymer comprising three blocks around zinc is symmetrically formed can be prepared.
  • An example of such a block copolymer is represented by the following formula (12).
  • R 1 to R 3 , l, m and n are each as defined in Chemical Formulas 1 to 3, A is as defined in Chemical Formula 9, and B 'is a repeating unit of Chemical Formula 3, wherein B' is defined in Chemical Formula 9. It is combined with.
  • the first block includes a repeating unit represented by the formula (4)
  • an example of a compound in which a triblock copolymer including three blocks symmetrically formed based on zinc prepared in the step (2) May be represented by the following Chemical Formula 13.
  • R 1 ′, R 1 ′′, R 2 and R 3 , p, l, m and n ′ are as defined in Formulas 2, 3 and 4, respectively, A is as defined in Formula 9, and B ′ is B defined in Chemical Formula 9 represents a form combined with a repeating unit of Chemical Formula 3.
  • 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 the step (2), so that a triblock copolymer can be formed, and the second block or the third block is formed in the step (2). If no formation of any of the blocks is made, a diblock copolymer is formed.
  • the block copolymer composition of the present invention comprises a polystyrene-polyolefin-polystyrene triblock copolymer and a polyolefin-polystyrene diblock copolymer, wherein the content of the diblock copolymer is 19% by weight or less.
  • the content of the polyolefin-polystyrene diblock copolymer and polystyrene-polyolefin-polystyrene triblock copolymer is determined by the number of moles of the organic zinc compound used in step (1) and the number of moles of alkyllithium compound used in step (2). Affected by rain
  • the number of moles of the alkyllithium compound used in the step (2) when preparing the block copolymer composition of the present invention has a larger value than the number of moles of the organic zinc compound used in the step (1), that is, When the amount of lithium (Li) used in the manufacturing process of the block copolymer composition of the present invention is higher than that of zinc (Zn), the polymerization rate is further increased to increase the productivity, and both the zinc (Zn) and the olefin-based polymer terminals are started ( initiation) to effectively synthesize the triblock copolymer to increase the content of the triblock copolymer in the composition.
  • the amount of lithium (Li) used in the manufacturing process of the block copolymer composition of the present invention is higher than that of zinc (Zn)
  • the polymerization rate is further increased to increase the productivity, and both the zinc (Zn) and the olefin-based polymer terminals are started ( initiation) to effectively synthesize the triblock copolymer to increase
  • the number of moles of the alkyllithium compound used in the step (2) 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 (1), the organic used in the step (1)
  • the number of moles of the zinc compound and the number of moles of the alkyllithium compound used in the step (2) 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 may include the diblock copolymer in the copolymer composition in an amount of 19 wt% or less, specifically 18 wt% or less, and more specifically 17 wt% or less. Since the mechanical properties of the copolymer composition may decrease as the content of the diblock copolymer increases, the smaller the content of the diblock copolymer is, the better, but the lower limit of the content of the diblock copolymer may be 0.1% by weight.
  • the diblock copolymer may include a structure of Formula 5 or 6
  • the triblock copolymer may include a structure of Formula 7 or 8.
  • the diblock copolymer has a structure of a CH 3 form in which a unit derived from an organic zinc compound of Formula 9, that is, B and A defined in Formula 9, is bonded to one end of Formula 5 or 6, and the other end is terminated. It may have, and the triblock copolymer may have a structure of Formula 7 or 8.
  • 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.
  • the block copolymer composition of the present invention may include 10% by weight to 99% by weight of the polyolefin-based block, based on the entire composition, and may include 1% by weight to 90% by weight of the polystyrene-based block.
  • the polyolefin block may include 40 wt% to 85 wt%
  • the polystyrene block may include 15 wt% to 60 wt% in total, and more specifically, the polyolefin block 60 It may include a weight% to 80% by weight, and may comprise 20% to 40% by weight of the total polystyrene-based block.
  • the block copolymer composition according to the exemplary embodiment of the present invention may include a structure including a compound used in the preparation process between the third block and the first block, specifically, a unit derived from the organic zinc compound represented by Chemical Formula 9 above. It may be.
  • An example of such a block copolymer structure is shown in the following formula (14).
  • R 1 to R 3 , l, m, n, and a are as defined in Formulas 1 to 3 and 7, respectively, A is as defined in Formula 9, and B 'is defined in Formula 9 above. B represents the form combined with the repeating unit of Formula (3).
  • a block copolymer structure in which a compound derived from the compound used in the preparation process, specifically, the organic zinc compound of Formula 9, 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, n ′ and a are as defined in Formulas 2 to 4 and 7, respectively, A is as defined in Formula 9, B 'represents a form in which B defined in Chemical Formula 9 is combined with a repeating unit represented by Chemical Formula 3.
  • a compound including a block copolymer symmetrically formed around zinc is prepared using the organic zinc compound, and then water, oxygen, or an organic acid is added thereto. It is produced by a manufacturing method that includes a process, and does not require a saturation step of hydrogenating the block copolymer separately, and thus by a one-pot production method in which the saturation process of hydrogenating the block copolymer is omitted separately. It has the advantage of being done.
  • the block copolymer composition of the present invention does not use a monomer that can leave a residual unsaturated bond, such as a diene compound such as butadiene or isoprene in the manufacturing process of the polyolefin-based block containing, in the saturation process to hydrogenate it There is no problem that an unsaturated bond which is not saturated also remains.
  • a monomer that can leave a residual unsaturated bond such as a diene compound such as butadiene or isoprene
  • the block copolymer composition of the present invention prepared as described above may have a weight average molecular weight of 58,000 g / mol to 500,000 g / mol, specifically, a weight average molecular weight of 60,000 g / mol to 300,000 g / mol, more specifically 65,000 It may have a weight average molecular weight of g / mol to 200,000 g / mol.
  • the block copolymer composition may have a polydispersity index (PDI) value of greater than 1.1 but less than or equal to 3, specifically 1.2 to 2.5, and more specifically 1.3 to 1.8.
  • PDI polydispersity index
  • the block copolymer composition may have a tensile strength of 30 MPa or less, specifically 5 MPa to 28 MPa, and more specifically 10 MPa to 26 MPa.
  • the block copolymer composition may have a 300% modulus value of 2 MPa to 15 Mpa, specifically 2.5 MPa to 10 MPa, and more specifically 3 MPa to 8 MPa.
  • block copolymer composition may have an elongation at break of 800% to 2,000%, specifically 850% to 1,500%, and more specifically 870% to 1,300%.
  • 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 In the same manner as the polymer composition was prepared.
  • a polymer composition was prepared in the same manner as in Comparative Example 4, except that 35 mL of propylene was injected, ethylene was injected to have a pressure of 20 bar, and 20 bar was maintained.
  • 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.
  • 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.
  • GPC curves obtained by gel permeation chromatography were obtained by deconvolution assuming peaks with two Gaussian curves.
  • Example 1 51.5 20.1 28.4 102,700 1.7 1,201 26.4 6.7 14.8
  • Example 2 55.1 22.0 22.9 82,000 1.6 1,301 22.4 5.5 13.2
  • Example 3 49.0 21.3 29.7 98,500 1.5 1,253 25.4 5.9 11.8
  • Example 4 47.7 25.8 26.5 76,700 1.6 1,603 23.4 3.3 13.8
  • Example 5 50.8 20.7 28.5 77,900 1.6 1,356 30.6 6.2 11.5
  • Example 6 48.3 27.7 24 78,400 1.7 1,845 24.1 3.5 9.6
  • Example 7 49.1 20.9 30.1 101,200 1.7 1,139 29.3 6.1 11.8
  • Example 8 46.9 28.7 24.4 79,700 1.7 1,779 23.

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Abstract

La présente invention concerne une composition de copolymère séquencé comprenant un copolymère biséquencé et un copolymère triséquencé, qui comprennent un bloc à base de polyoléfine et un bloc à base de polystyrène, la quantité du copolymère biséquencé étant de 19 % en poids ou moins, le bloc à base de polyoléfine comprenant une unité de répétition de la formule chimique suivante 1, et le bloc à base de polystyrène comprenant un ou plusieurs éléments choisis dans le groupe constitué des formules chimiques suivantes 2 et 3.
PCT/KR2019/003749 2018-03-30 2019-03-29 Composition de copolymère séquencé Ceased WO2019190287A1 (fr)

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US16/976,236 US11414541B2 (en) 2018-03-30 2019-03-29 Block copolymer composition
CN201980015877.9A CN111770944B (zh) 2018-03-30 2019-03-29 嵌段共聚物组合物
JP2020548802A JP7094603B2 (ja) 2018-03-30 2019-03-29 ブロック共重合体組成物
EP19776273.5A EP3747921B1 (fr) 2018-03-30 2019-03-29 Composition de copolymère séquencé

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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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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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