WO2023096308A1 - Copolymère de polyoléfine ayant une transmittance de lumière et une productivité améliorées, et film préparé à l'aide de celui-ci - Google Patents

Copolymère de polyoléfine ayant une transmittance de lumière et une productivité améliorées, et film préparé à l'aide de celui-ci Download PDF

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WO2023096308A1
WO2023096308A1 PCT/KR2022/018513 KR2022018513W WO2023096308A1 WO 2023096308 A1 WO2023096308 A1 WO 2023096308A1 KR 2022018513 W KR2022018513 W KR 2022018513W WO 2023096308 A1 WO2023096308 A1 WO 2023096308A1
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catalyst
copolymer
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polyolefin copolymer
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이래하
신은혜
정종화
김혜선
채병훈
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롯데케미칼 주식회사
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films

Definitions

  • the present invention relates to a polyolefin copolymer having improved light transmittance and productivity and a molded product manufactured using the same, and more particularly, to a polyolefin copolymer having excellent transparency due to low crystallinity and a high crystallization peak temperature and short crystallization time, and a polyolefin copolymer having the same It relates to a film produced using
  • Catalysts used in such polyolefin polymerization can be classified into a Ziegler-Natta catalyst system and a metallocene catalyst system, and these two highly active catalyst systems have been developed according to their respective characteristics.
  • a Ziegler-Natta catalyst system is generally composed of a titanium or vanadium compound main catalyst component and an alkylaluminum compound cocatalyst component.
  • the Ziegler-Natta catalyst system is a multi-active point catalyst in which several active species are mixed, and is characterized by a wide molecular weight distribution of the polymer, but there is a limit to securing desired physical properties because the composition distribution of the comonomer is not uniform.
  • the metallocene catalyst system composed of metallocene compounds of transition metals of group 4 of the periodic table such as titanium, zirconium, and hafnium and methylaluminoxane as a cocatalyst is a homogeneous catalyst with a single catalytic active site, it is Compared to the Ziegler-Natta catalyst system, the molecular weight distribution of the polymer is narrow, the composition distribution of the comonomer is uniform, and the properties of the polymer can be changed according to the ligand structure modification of the catalyst.
  • the metallocene catalyst has better reactivity to comonomers than the conventional Ziegler-Natta catalyst system, a polymer having a high comonomer content can be obtained with high activity even with a small amount of comonomer. Even if the same amount of comonomer is used, it is possible to make a high molecular weight polymer with a more uniform composition distribution, so that it can be used as a film or elastic body with good physical properties. In addition, since low molecular weight waxy extracts are hardly generated inside the copolymer, it can be applied to applications requiring hygiene such as medical use.
  • a bisindenyl-based metallocene catalyst with a C 2 symmetry structure is generally used and exhibits a high isotactability (identity index) of 95% or more.
  • identity index identity index
  • a rac structure having iso-selectivity and a meso structure having no stereoregularity are generated at the same time, so there is a disadvantage in that the rac and meso structures must be separated.
  • metallocene catalysts with a C 1 symmetric structure do not simultaneously form rac and meso structures during catalyst production, which can increase catalyst production efficiency.
  • One aspect of the present invention is to provide a polyolefin copolymer having a relatively low crystallinity, high crystallization peak temperature and short crystallization time.
  • Another aspect of the present invention is to provide a film prepared using the polyolefin copolymer as described above.
  • the copolymer comprises 60 to 95% by weight of propylene and 5 to 40% by weight of a C 4 -C 20 alpha-olefin comonomer, wherein the copolymer is a) 160 ° C. using differential scanning calorimetry (DSC) Under the condition of cooling from -60.0°C at a rate of 20.0°C/min, the crystallization time until the maximum crystal is formed is 6.5 minutes or less, b) the crystallization peak temperature is 30°C or more, and c) the light transmittance is 86.0% At least one or more of the above is satisfied.
  • DSC differential scanning calorimetry
  • a molded article made of a resin composition containing the polyolefin copolymer is provided.
  • the present invention it is possible to prepare a high molecular weight polypropylene copolymer having a high comonomer unit content by applying a specific catalyst, and when the copolymer is mixed with a polypropylene resin to produce a composite resin film, excellent transparency due to low crystallinity Since it has a high crystallization peak temperature and a short crystallization time, it is possible to shorten the processing time when manufacturing a heat-sealing film, thereby contributing to economic efficiency and productivity improvement.
  • the method for preparing the polypropylene resin composition of the present invention is to polymerize propylene and at least one C 4 -C 20 alpha-olefin comonomer in the presence of a catalyst containing a transition metal compound represented by Formula 1 to prepare a polypropylene copolymer doing; and mixing the polypropylene copolymer and polypropylene.
  • the polyolefin copolymer of the present invention includes 60 to 95% by weight of propylene and 5 to 40% by weight of a C 4 -C 20 alpha-olefin comonomer, and the copolymer is a) tested at 160° C. using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the crystallization time until the peak is formed is 6.5 minutes or less
  • the crystallization peak temperature is 30 ° C or more under the same conditions as in a) above
  • the copolymer of the present invention has a1) crystallization time until crystals are formed to the maximum under the condition of cooling from 160 ° C to -60.0 ° C at a rate of 20.0 ° C / min using differential scanning calorimetry (DSC) 6.1 minutes or less, b1) crystallization peak temperature of 39° C. or higher under the same conditions as a1) above, and c1) light transmittance of 86.1% or higher, at least one of the above conditions a1) to c1) are satisfied, more preferably satisfies all of the above a1) to c1).
  • DSC differential scanning calorimetry
  • alkyl refers to a monovalent straight-chain or branched saturated hydrocarbon radical composed of only carbon and hydrogen atoms.
  • alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, pentyl, hexyl, octyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.
  • alkenyl refers to a straight-chain or branched-chain hydrocarbon radical containing at least one carbon-carbon double bond, and includes ethenyl, propenyl, butenyl, pentenyl, and the like, It is not limited to this.
  • alkynyl refers to a straight-chain or branched-chain hydrocarbon radical containing at least one carbon-carbon triple bond, and includes methynyl, ethynyl, propynyl, butynyl, pentynyl, and hexy. but is not limited to yl, heptynyl, octynyl, and the like.
  • aryl described in the present invention is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and includes single or fused ring systems. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.
  • alkylaryl described in the present invention means an organic group in which one or more hydrogens of an aryl group are substituted with an alkyl group, and includes methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, iso butylphenyl, t-butylphenyl, and the like, but are not limited thereto.
  • arylalkyl refers to an organic group in which one or more hydrogens of an alkyl group are substituted by an aryl group, and includes, but is not limited to, phenylpropyl, phenylhexyl, and the like.
  • alkylidene refers to a divalent aliphatic hydrocarbon group in which two hydrogen atoms are removed from the same carbon atom of the alkyl group, and includes ethylidene, propylidene, isopropylidene, butylidene, and pentylidene. and the like, but are not limited thereto.
  • acetal refers to an organic group formed by a bond between an alcohol and an aldehyde, that is, a substituent having two ether (-OR) bonds on one carbon, and includes methoxymethoxy, 1-methyl Toxyethoxy, 1-methoxypropyloxy, 1-methoxybutyloxy, 1-ethoxyethoxy, 1-ethoxypropyloxy, 1-ethoxybutyloxy, 1-(n-butoxy)ethoxy, 1-(iso-butoxy)ethoxy, 1-(sec-butoxy)ethoxy, 1-(tert-butoxy)ethoxy, 1-(cyclohexyloxy)ethoxy, 1-methoxy -1-methylmethoxy, 1-methoxy-1-methylethoxy and the like, but are not limited thereto.
  • ether described in the present invention is an organic group having at least one ether linkage (-O-), and includes 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, and 2-phenoxyethyl. , 2-(2-methoxyethoxy)ethyl, 3-methoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 2-methoxy-1-methylethyl, 2-methoxy-2-methylethyl , 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, and the like, but are not limited thereto.
  • sil refers to a -SiH 3 radical derived from silane, and at least one of hydrogen atoms in the silyl group may be substituted with various organic groups such as alkyl and halogen.
  • trimethylsilyl triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimeroxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, triphenoxysilyl, and the like.
  • alkoxy refers to an -O-alkyl radical, where 'alkyl' is as defined above.
  • alkoxy radicals include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.
  • halogen described in the present invention means a fluorine, chlorine, bromine or iodine atom.
  • C n the number of carbon atoms is n.
  • a polypropylene copolymer preparation step comprising polymerizing propylene and at least one C 4 -C 20 alpha-olefin comonomer in the presence of a specific catalyst of the present invention yields a polypropylene copolymer, and thus according to the present invention
  • the polypropylene copolymer prepared according to the above has a high molecular weight and thus has a low melt index.
  • the catalyst may include a transition metal compound represented by Formula 1 below.
  • M is a Group 4 transition metal, and preferably may be titanium (Ti), zirconium (Zr), or hafnium (Hf).
  • Q 1 and Q 2 are each independently a halogen, a (C 1 -C 20 )alkyl group, a (C 2 -C 20 )alkenyl group, a (C 2 -C 20 )alkynyl group, and a (C 6 -C 20 )aryl group.
  • A is a Group 14 element, preferably carbon (C), silicon (Si) or germanium (Ge), more preferably silicon (Si).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently substituted with hydrogen, an acetal group or an ether group, or Unsubstituted (C 1 -C 20 )alkyl group, acetal group or ether group substituted or unsubstituted (C 2 -C 20 )alkenyl group, acetal group or ether group substituted or unsubstituted (C 1 -C 20 )alkyl (C 6 -C 20 ) substituted or unsubstituted with an aryl group, acetal group or ether group (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group, or substituted or unsubstituted with an acetal group or ether group (C 1 -C 20 ) A silyl group, and two or more groups of R 1 , R 2 ,
  • R 2 and R 3 may each independently be a hydrogen or an acetal group or an ether group-substituted or unsubstituted (C 1 -C 20 )alkyl group.
  • the R 8 and R 9 may combine with each other to form an aromatic ring, and thus the catalyst according to the present invention may include a naphthyl group.
  • At least one substituent of R 8 , R 9 , R 10 , R 11 and R 12 of the catalyst may include a naphthyl group or a phenyl group.
  • the transition metal compound as represented by Formula 1, contains a cyclopentadiene derivative ligand linked to each other by a bridge group of silicon or alkenylene and an indenyl derivative ligand in which aryl is necessarily substituted at the 4-position.
  • the transition metal compound has an indene derivative ligand in which an aryl is substituted at the 4-position, and thus has superior catalytic activity and copolymerizability compared to a transition metal compound having an aryl-substituted ligand at the 4-position of the indene. .
  • the catalyst may include a cocatalyst compound.
  • the cocatalyst compound activates the catalyst compound, and an aluminoxane compound, an organo-aluminum compound, or a bulky compound that activates the catalyst compound may be used.
  • the cocatalyst compound may be selected from the group consisting of compounds represented by Chemical Formulas 2 to 4 below.
  • Ra are each independently halogen; Or a halogen-substituted or unsubstituted (C 1 -C 20 )hydrocarbyl group,
  • n is an integer greater than or equal to 2)
  • Q is aluminum or boron
  • Rb is each independently halogen; or a halogen-substituted or unsubstituted (C 1 -C 20 )hydrocarbyl group);
  • [W] + is a cationic Lewis acid; or a cationic Lewis acid to which a hydrogen atom is bonded;
  • Z is a group 13 element
  • Rc is each independently a (C 1 -C 20 ) aryl group substituted with one or two or more substituents selected from the group consisting of a halogen, a (C 1 -C 20 ) hydrocarbyl group, an alkoxy group, and a phenoxy group; It is a (C 1 -C 20 )alkyl group substituted with one or two or more substituents selected from the group consisting of a halogen, a (C 1 -C 20 )hydrocarbyl group, an alkoxy group, and a phenoxy group).
  • the cocatalyst compound is included in the catalyst together with the metallocene compound represented by Chemical Formula 1 to activate the metallocene compound.
  • a ligand in the metallocene compound is extracted to cationize the central metal (M 1 or M 2 ) while counter ion having weak binding force, That is, the compound including the unit represented by Chemical Formula 2, the compound represented by Chemical Formula 3, and the compound represented by Chemical Formula 4 that can act as an anion act together as cocatalysts.
  • the 'unit' represented by Formula 2 is a structure in which n structures in [ ] are connected in a compound, and other structures in the compound are not particularly limited as long as they include the unit represented by Formula 2, and repetition of Formula 2 It may be a cluster type, for example, a spherical compound, in which units are linked to each other.
  • the compound represented by Formula 2 is not particularly limited as long as it is an alkylaluminoxane, but preferred examples are methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. oxane and the like, and a particularly preferred compound is methylaluminoxane.
  • the compound represented by Formula 3 is not particularly limited as an alkyl metal compound, and non-limiting examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triiso Propyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl Aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.
  • the metallocene compound one or two or more selected from the group consisting of trimethylaluminum, triethylaluminum and
  • the compound represented by Formula 4 is a dimethylanilinium cation when [W] + is a cationic Lewis acid bonded to a hydrogen atom, and [W] + is a cationic Lewis acid.
  • [(C 6 H 5 ) 3 C] + , and [Z(Rc) 4 ] - is [B(C 6 F 5 ) 4 ] - .
  • the compound represented by Formula 4 is not particularly limited, but non-limiting examples when [W] + is a hydrogen atom bonded cationic Lewis acid include triphenylcarbenium borate, trimethylammonium tetraphenylborate, and methyldioctadecylammonium tetraphenyl.
  • a catalyst can be prepared using the compounds of Formulas 1 to 4, and the method exemplified below can be used as a method for preparing the catalyst.
  • a catalyst may be prepared by contacting a mixture of a transition metal compound and a compound represented by Formulas 3 and 4, or a compound represented by Formulas 3 and 4 It is also prepared by directly introducing each of the polymerizers.
  • the addition amount of the cocatalyst compound may be determined in consideration of the addition amount of the transition metal compound represented by Formula 1 and the amount required to sufficiently activate the transition metal compound.
  • the content of the cocatalyst compound may be 1:1 to 100,000 based on the molar ratio of the metal contained in the cocatalyst compound with respect to 1 mol of the transition metal contained in the transition metal compound represented by Formula 1, and preferably 1: It may be 1 to 10,000, more preferably 1:1 to 5,000.
  • the compound represented by Formula 2 is preferably 1:10 to 5,000 molar ratio, more preferably 1:50 to 1,000 molar ratio, with respect to the transition metal compound represented by Formula 1, Preferably, it may be included in a molar ratio of 1:100 to 1,000.
  • the molar ratio of the compound represented by Formula 2 to the transition metal compound of Formula 1 is less than 1:10, the amount of aluminoxane is very small, and activation of the transition metal compound may not be completely performed. If it exceeds, the excess aluminoxane may act as a catalyst poison and the polymer chain may not grow well.
  • a of the cocatalyst compound represented by Formula 3 when A of the cocatalyst compound represented by Formula 3 is boron, 1:1 to 100, preferably 1:1 to 10, more preferably 1:1 to 10 with respect to the transition metal compound represented by Formula 1 Preferably, it may be used in a molar ratio of 1:1 to 4.
  • a of the cocatalyst compound represented by Formula 3 when A of the cocatalyst compound represented by Formula 3 is aluminum, it may vary depending on the amount of water in the polymerization system, but with respect to the transition metal compound represented by Formula 1, 1:1 to 1000, preferably 1: It may be used in a molar ratio of 1 to 500, more preferably 1:1 to 100.
  • the cocatalyst compound represented by Formula 4 may be included in a molar ratio of 1:0.5 to 30, preferably 1:0.7 to 20, and more preferably 1:1 to 10 with respect to the transition metal compound represented by Formula 1. .
  • the ratio of the cocatalyst compound represented by Formula 4 is less than 1:0.5, the amount of the activator is relatively small, so that the metal compound cannot be fully activated, resulting in a problem in that the activity of the resulting catalyst composition is reduced. If it exceeds 30, the metal compound is completely activated, but the unit price of the catalyst composition may be uneconomical or the purity of the resulting polymer may be low due to the remaining excess activator.
  • the catalyst according to the present invention can be used without being included separately, and can also be used alone for preparing a polypropylene copolymer without mixing with other catalysts.
  • the copolymer produced through the polymerization process carried out by directly contacting propylene and at least one C 4 -C 20 alpha-olefin comonomer compound has a relatively insoluble and/or fixed catalyst site, so that the polymer chain According to these information, it can be produced by olefin polymerization under rapidly immobilizing conditions.
  • immobilization can be effected, for example, by using a solid insoluble catalyst, carrying out the polymerization in a medium in which the resulting polymer is generally insoluble, and maintaining the polymerization reactants and products below the crystallization temperature (T c ) of the polymer. .
  • the aforementioned catalyst is preferably applicable to the copolymerization of propylene and 1-butene.
  • a method for producing a polypropylene copolymer comprising polymerizing propylene and at least one C 4 -C 20 alpha-olefin comonomer in the presence of the catalyst will be described.
  • the method for producing a polypropylene copolymer according to the present invention comprises a transition metal compound represented by Chemical Formula 1, an aluminum compound represented by Chemical Formula 2, an alkyl metal compound represented by Chemical Formula 3, and boron represented by Chemical Formula 4 Polymerizing a propylene or ethylene compound in the presence of a transition metal catalyst composition comprising at least one cocatalyst compound selected from the group consisting of compounds is performed.
  • Propylene polymerization processes are well known in the art and include bulk polymerization, solution polymerization, slurry polymerization and low pressure gas phase polymerization.
  • Metallocene catalysts are particularly useful in known types of operation using fixed bed, moving bed or slurry processes carried out in single, series or parallel reactors.
  • a solvent or propylene or ethylene monomer itself may be used as a medium.
  • the catalyst presented in the present invention exists in a homogeneous form in a polymerization reactor, it is preferable to apply it to a solution polymerization process carried out at a temperature equal to or higher than the melting point of the corresponding polymer.
  • a non-uniform catalyst composition obtained by supporting the transition metal catalyst and cocatalyst on a porous metal oxide support may be used in a slurry polymerization or gas phase polymerization process. Therefore, when the catalyst of the present invention is used together with an inorganic carrier or an organic polymer carrier, it can be applied to a slurry or gas phase process. That is, the transition metal compound and the cocatalyst compound may be used in a form included (supported) in an inorganic carrier or an organic polymer carrier.
  • the carrier may include inorganic or organic materials used in the manufacture of catalysts in the art to which the present invention belongs without limitation. can be used
  • the carrier is SiO 2 , Al 2 O 3 , MgO, MgCl 2 , CaCl 2 , ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , SiO 2 -Al 2 O 3 , SiO 2 - MgO, SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , SiO 2 -TiO 2 -MgO, bauxite, zeolite, starch, cyclodextrin, or It may be a synthetic polymer.
  • the carrier has a hydroxyl group on its surface, and is selected from the group consisting of silica (SiO 2 ), silica-alumina (SiO 2 -Al 2 O 3 ) and silica-magnesia (SiO 2 -MgO). There may be more than one species.
  • a method of including the catalyst including the main catalyst compound and the cocatalyst compound in the carrier a method of directly including the main catalyst compound in a dehydrated carrier; a method of including the main catalyst compound after pre-treating the carrier with the co-catalyst compound; a method of post-treating with the cocatalyst compound after including the main catalyst compound in the carrier; A method of reacting the main catalyst compound with the cocatalyst compound and then adding the carrier to the reaction may be used.
  • the method of including the carrier is carried out at a temperature of -70 to 200°C, preferably -50 to 150°C, and more preferably 0 to 100°C.
  • the ethylene, olefin, and diene polymerization reaction of the present invention may be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase.
  • a solvent or ethylene, olefin and diene monomers themselves may be used as a medium.
  • the solvent usable during the polymerization reaction may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof.
  • the aliphatic hydrocarbon-based solvent is a non-limiting example, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane ), undecane, dodecane, cyclopentane, methylcyclopentane, or cyclohexane.
  • the aromatic hydrocarbon-based solvent is, but is not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, or chlorobenzene. (Chlorobenzene) and the like.
  • the halogenated aliphatic hydrocarbon solvent is, but is not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, or 1,2-dichloroethane (1,2-Dichloroethane) and the like.
  • the process of including the transition metal compound and the cocatalyst compound on the support is carried out at a temperature of -70 to 200 ° C, preferably -50 to 150 ° C, more preferably 0 to 100 ° C. advantageous in terms of efficiency.
  • the solvent usable in the inclusion method may be an aromatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof.
  • the solvent usable during the polymerization reaction may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof.
  • the aliphatic hydrocarbon-based solvent is a non-limiting example, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane (decane), undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, and the like.
  • the aromatic hydrocarbon solvent is a non-limiting example, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, chlorobenzene (Chlorobenzene) and the like.
  • the halogenated aliphatic hydrocarbon solvent is a non-limiting example, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane (1,2-Dichloroethane) and the like.
  • the polypropylene copolymer may be prepared by polymerizing propylene and C 4 -C 20 alpha-olefin comonomers, particularly propylene and 1-butene, in the presence of the above catalyst.
  • the transition metal compound and the cocatalyst component may be separately introduced into the reactor or mixed in advance and introduced into the reactor, and mixing conditions such as the order of addition, temperature, or concentration are not particularly limited.
  • 1-butene when preparing a copolymer of propylene and 1-butene, 1-butene may be included in an amount of 0.1 to 99.9% by weight based on the total weight of the copolymer, preferably 1 to 75% by weight, more preferably may be included in an amount of 5 to 50% by weight.
  • the addition amount of the catalyst may be determined within a range in which the polymerization reaction of monomers can sufficiently occur according to a slurry phase, liquid phase, gas phase or solution process, and is not particularly limited.
  • the addition amount of the catalyst is preferably 10 -8 to 1 mol / L based on the concentration of the central metal (M) in the transition metal compound per unit volume (L) of the monomer, and 10 -7 to 10 -1 mol /L is more preferable, and it is still more preferable that it is 10 -7 to 10 -2 mol/L.
  • the polymerization reaction of the present invention may be performed in a batch type, semi-continuous type or continuous type reaction, preferably in a continuous type reaction.
  • the temperature and pressure conditions of the polymerization reaction of the present invention may be determined in consideration of the efficiency of the polymerization reaction depending on the type of reaction and reactor to be applied, but the polymerization temperature is preferably 30 to 150 ° C., or 40 to 150 ° C. may be 60 to 100 ° C, and the pressure may be 1 to 300 atm, or 1 to 100 atm, preferably 5 to 50 atm.
  • the polypropylene copolymer prepared according to the present invention may increase polymerization activity of monomers and exhibit high molecular weight by using a catalyst including a transition metal compound and a cocatalyst compound.
  • the propylene-1-butene copolymer obtained according to the present invention may increase polymerization activity and exhibit high molecular weight by using a catalyst containing a main catalyst compound and the cocatalyst compound.
  • the propylene-1-butene copolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 30,000 to 800,000, and more preferably 60,000 to 500,000.
  • the propylene-1-butene copolymer may have a molecular weight distribution (Mw/Mn) of 1 to 15, preferably 1.5 to 10, and more preferably 1.5 to 5.
  • the propylene-1-butene copolymer may have a density of 0.880 to 0.920 g/cm 3 .
  • a film made of a resin composition comprising the polyolefin copolymer according to the present invention, wherein the method for producing the resin composition is the polypropylene copolymer of the present invention obtained above. and mixing crystalline polypropylene.
  • the polypropylene resin composition based on the total weight of the resin composition (a) 65 to 95% by weight of a propylene-ethylene-1-butene random copolymer; and (b) 5 to 35% by weight of a polyolefin copolymer.
  • the polyolefin resin composition of the present invention includes (a) 70 to 90% by weight of a propylene-ethylene-1-butene random copolymer; and (b) 10 to 30% by weight of a polyolefin copolymer, and when the component (a) is less than 70% by weight, the fluidity is lowered, resulting in poor molding processability, insufficient strength, or low heat resistance such as low heat distortion temperature.
  • the component (a) is more than 90% by weight, the thermal bonding temperature rises, the haze degree increases, and the flexibility and scratch resistance tend to decrease.
  • the polypropylene resin composition according to the present invention may further include additives and solvents known in the art within a range that does not impair the object of the present invention, and these components are performed in the mixing step or separately added. can be performed. Specifically, for example, antioxidants, nucleating agents, heat-resistant stabilizers, weathering stabilizers, antistatic agents, lubricants, slip agents, flame retardants, pigments, dyes, etc. may be used. An absorbent or the like may be added. The contents of the other additives may be appropriately adjusted by those skilled in the art within a range not impairing the object of the present invention.
  • the polypropylene copolymer, crystalline polypropylene, and other additive components added as described above may be selected and mixed in a desired order without particular order restrictions.
  • a kneader a roll, a kneader such as a Banbury mixer, or a single-screw / twin-screw extruder, etc. It may be manufactured by a method of kneading input raw materials using equipment, but is not limited thereto.
  • the polypropylene resin composition prepared above and the homo polypropylene resin are melt-molded through a multi-layer film molding machine at 220 ° C. to form a film.
  • a multilayer film having a thickness of 10 to 100 ⁇ m, for example, a multilayer film of about 40 ⁇ m may be prepared.
  • the multi-layer film may include a film of 2 to 10 layers.
  • the resin composition of the present invention, propylene-1-butene copolymer (b) and crystalline polypropylene (a) are mixed to prepare a layer entering the heat sealing layer, and then a homopolypropylene layer is formed using a multilayer film molding machine. It can be laminated with additional layers such as the like to produce a multi-layer film.
  • the homopropylene layer may be a core layer
  • the resin composition layer of the present invention prepared above may be a sealing layer.
  • the thickness ratio of the core layer and the seal layer of the multilayer film may be 3 to 10: 1, for example, about 4: 1.
  • the film thus prepared has a faster crystallization rate than a polypropylene resin composition having the same melting point, the film has excellent hot tack and transparency.
  • the film made of the resin composition containing the copolymer of the present invention may be used for a packaging material heat sealing layer, for example, a heat sealing film such as food packaging, filling packaging, component packaging, protective film, decorative sheet, It may be a film for a retort pouch or the like.
  • autoclave high-pressure reactor
  • n-hexane 500mL was added to dissolve the reactant, filtered through a celite filter, and the filtered solution was vacuum-dried to obtain dimethyl 2,3,4,5-tetramethylcyclopentadienyl chloro as a yellow oil. 70 g of silane was obtained (yield: 80%).
  • dimethyl 2,3,4,5-tetramethylcyclopentadienyl chlorosilane 38g obtained in 1.1 was added and stirred at room temperature for 12 hours to react made it After the reaction was completed, water (400 ml) was added, stirred again at room temperature for 1.5 hours, extracted with toluene and vacuum dried to obtain dimethyl 2,3,4,5-tetramethylcyclopentadienyl 2- 80 g of methyl-4-(4-t-butylphenyl)indenyl silane was obtained (95% yield).
  • 2-Methyl-4-naphthyl-indene was synthesized according to Non-Patent Document 1.
  • 2-methyl-4-naphthyl-indene (2.56 g, 10 mmol) was added and dissolved, and 4.4 mL of n-butyllithium (n-BuLi) (2.5 mL in hexane) was dissolved at 0 ° C. M solution) was slowly added dropwise to the flask above, stirred for 1 hour, stirred at room temperature for 12 hours, and after the reaction was completed, hexane was filtered and the obtained powder was dried.
  • n-butyllithium n-butyllithium
  • NMR data of Chemical Formula 6 is shown in FIG. 1 .
  • a polymerization reaction was performed at 70 °C for 30 minutes. After the polymerization reaction was completed, the temperature was lowered to room temperature, and then excess gas was discharged. Subsequently, the copolymer polymerization solution dispersed in the solvent was transferred to a container, and then dried in a vacuum oven at 80° C. for 15 hours or more to prepare a propylene-1-butene copolymer.
  • a propylene-1-butene copolymer was prepared in the same manner as in Example 1, except that the main catalyst synthesized in Preparation Example 2 was used.
  • Example 2 Comparative Example 1 Mw 424K 395K 411K Tm(°C) 82 81 78 Tg(°C) -17 -22 -17 BN-1 (% by weight) 31 31 31 31 Activity (kg/mmol Cat Hr) 112 72 - Density (g/cm 3 ) 0.881 0.885 0.883 Melt index (g/10min) 3.7 4.1 3.8 Light transmittance (%) 86.1 87.9 85.1 crystallinity 22.6 19.8 23.2 Crystallization peak temperature (°C) 39.6 43.1 25.4 Crystallization time (Min.) 6.055 5.881 6.769
  • Tm Melting point
  • Tg glass transition temperature
  • DSC Differential Scanning Calorimeter
  • Comonomer content (BN-1, % by weight): analyzed by 1 H NMR (device name: Avance DRX400, manufacturer: Bruker).
  • Density After treating the copolymer with an antioxidant, a sheet with a thickness of 3 mm and a radius of 2 cm is prepared with a compression mold at 180 ° C. After cooling to room temperature, ASTM D1505 is obtained using a device (manufacturer: Toyoseiki, model name: T-001). It was measured as a standard.
  • MI Melt index
  • Light transmittance In accordance with ASTM D1003, the light transmittance of the film was measured in the visible ray region using a haze meter (NDH-5000, manufactured by Densoku Kogyo Co., Ltd., Japan).
  • Crystallinity which represents the degree of crystallization of a crystalline polymer, was measured according to Equation 1 below using the peak width at which the crystallization temperature appears.
  • Crystallization peak temperature and crystallization time Thermal analysis was performed under the following conditions using a Differential Scanning Calorimeter (DSC, device name: DSC8000, manufacturer: Perkinelmer) at the highest peak where crystals were formed in the second cycle The temperature and the time taken to reach it were measured.
  • DSC Differential Scanning Calorimeter
  • Figure 2 is a graph showing the crystallization time of Examples 1 and 2 and Comparative Example 1, Example 1 corresponds to a green graph, Example 2 to a red graph, and Comparative Example 1 to a blue graph.
  • FIG. 3 is a graph showing crystallization peak temperatures of Examples 1 and 2 and Comparative Example 1.
  • Example 1 corresponds to a green graph, Example 2 to a red graph, and Comparative Example 1 to a blue graph.

Abstract

La présente invention concerne un copolymère de polyoléfine ayant une transmittance de lumière et une productivité améliorées, et un article moulé préparé à l'aide de celui-ci. Plus spécifiquement, l'invention concerne un copolymère de polyoléfine comprenant de 60 % à 95 % en poids de propylène, et 5 % à 40 % en poids d'au moins un comonomère d'alpha-oléfine en C4-C20, le copolymère satisfaisant à au moins un état parmi a) le temps de cristallisation jusqu'à la valeur maximale de cristaux est de 6,5 minutes ou moins dans la condition d'un refroidissement à une vitesse de 20,0 °C/min de 160 °C à -60,0 °C par calorimétrie différentielle à balayage (DSC), b) la température de cristallisation maximale est de 30 °C ou plus, et c) la transmittance de la lumière est de 86,0 % ou plus.
PCT/KR2022/018513 2021-11-23 2022-11-22 Copolymère de polyoléfine ayant une transmittance de lumière et une productivité améliorées, et film préparé à l'aide de celui-ci WO2023096308A1 (fr)

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