WO2022210845A1 - エチレン系樹脂組成物および成形体 - Google Patents

エチレン系樹脂組成物および成形体 Download PDF

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Publication number
WO2022210845A1
WO2022210845A1 PCT/JP2022/015848 JP2022015848W WO2022210845A1 WO 2022210845 A1 WO2022210845 A1 WO 2022210845A1 JP 2022015848 W JP2022015848 W JP 2022015848W WO 2022210845 A1 WO2022210845 A1 WO 2022210845A1
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Prior art keywords
group
ethylene
olefin copolymer
resin composition
olefin
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PCT/JP2022/015848
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English (en)
French (fr)
Japanese (ja)
Inventor
真也 松原
一輝 波戸
修平 辰巳
直也 田村
陽一 田中
千尋 堅固山
雄大 植松
翔太 吉野
雄大 田中
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Mitsui Chemicals Inc
Prime Polymer Co Ltd
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Mitsui Chemicals Inc
Prime Polymer Co Ltd
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Priority to CN202280025148.3A priority Critical patent/CN117083336B/zh
Priority to US18/284,005 priority patent/US20240191068A1/en
Priority to JP2023511467A priority patent/JP7660662B2/ja
Priority to EP22781056.1A priority patent/EP4317215A4/en
Publication of WO2022210845A1 publication Critical patent/WO2022210845A1/ja
Anticipated expiration legal-status Critical
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00Resin or rubber layer containing a blend of at least two different polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/72Density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/70Food packaging
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00Metallocene catalysts
    • C08F2420/07Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised 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
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/40Applications used as motor oil additive
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

Definitions

  • the ethylene-based resin composition (Z) of the present invention it is possible to suitably produce a molded article (especially a film) with excellent moldability and excellent mechanical strength. Further, according to the ethylene-based resin composition (Z) of [2] according to the present invention, a molded article ( In particular, a film) can be suitably produced. Furthermore, according to the ethylene-based resin composition (Z) of [3] according to the present invention, it is possible to suitably produce a molded article (especially a film) having particularly excellent moldability and excellent mechanical strength. .
  • melt flow rate of 0.1 g/10 min or more and 10 g/10 min or less, preferably 0.5 g/10 min or more and 5.0 g/10 min or less, more preferably 0.8 g/10 min or more; It is in the range of 3.0 g/10 minutes or less.
  • the ethylene-based resin composition (Z) consists essentially of the ethylene- ⁇ -olefin copolymer (A) and the ethylene- ⁇ -olefin copolymer (B).
  • the ethylene-based resin composition (Z) consists essentially of the ethylene- ⁇ -olefin copolymer (A) and the ethylene- ⁇ -olefin copolymer (B).
  • the ethylene- ⁇ -olefin copolymer A thermoplastic resin other than the coalescence (A) and the ethylene- ⁇ -olefin copolymer (B) hereinafter referred to as "another thermoplastic resin" may be included.
  • the ethylene-based resin composition (Z) of the present invention contains a weather stabilizer, a heat stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, Additives such as pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, and antioxidants may be blended as necessary.
  • oxygen-containing group examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group and benzyloxy group.
  • Examples of the conjugated diene derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), and a 2,4-hexadienyl group. , 1,4-diphenyl-1,3-pentadienyl group and cyclopentadienyl group, preferably 1,3-butadienyl group and 1,3-pentadienyl group.
  • Q is a carbon atom or a silicon atom, preferably a silicon atom.
  • R 1 to R 14 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, or an oxygen-containing group having 1 to 20 carbon atoms.
  • it is a nitrogen-containing group having 1 to 20 carbon atoms, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group having 1 to 20 carbon atoms.
  • Cyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, and a 2-adamantyl group; Phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3, 5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-ter
  • Silicon-containing groups having 1 to 20 carbon atoms as R 1 to R 14 include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group and cyclopentadienyl.
  • dimethylsilyl group dimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, fluorenyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 3 , 5-bis(trimethylsilyl)phenyl group and the like are preferred, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group , 3,5-bis(trimethylsilyl)phenyl groups.
  • the nitrogen-containing groups having 1 to 20 carbon atoms as R 1 to R 14 are amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethyl aminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group,
  • adjacent substituents among R 1 to R 6 may combine with each other to form a ring which may have a substituent.
  • the ring formed in this case is composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon, optionally having a substituent, condensed to the indenyl ring portion.
  • ⁇ 8 membered rings are preferred.
  • these may mutually be the same or different.
  • the ring is more preferably a 5- or 6-membered ring.
  • a nyl ring, a tetrahydroindacene ring, and a cyclopentatetrahydronaphthalene ring can be mentioned, and a benzoindenyl ring and a tetrahydroindacene ring are preferred. These rings may have a substituent.
  • adjacent substituents among R 7 to R 12 may combine with each other to form a ring which may have a substituent.
  • the ring formed in this case consists of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon, optionally having a substituent, condensed to the indenyl ring portion.
  • a 5- to 8-membered ring is preferred.
  • these may mutually be the same or different.
  • the ring is more preferably a 5- or 6-membered ring.
  • a nil ring, a tetrahydroindacene ring, a cyclopentatetrahydronaphthalene ring, a tetrahydrofluorene ring, and a fluorene ring can be mentioned, and a benzoindenyl ring and a tetrahydroindacene ring are preferred. These rings may have a substituent.
  • R 13 and R 14 may combine with each other to form a ring containing Q, and these rings may have a substituent.
  • the ring formed in this case preferably forms an optionally substituted 3- to 8-membered saturated or unsaturated ring. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 4- to 6-membered ring.
  • the structure together with Q may be, for example, a cyclobutane ring, a cyclopentane ring, a fluorene ring, or a silacyclobutane (siletane) ring.
  • silacyclopentane silane
  • silacyclohexane sinane
  • silafluorene ring preferably cyclopentane ring, silacyclobutane ring, and silacyclopentane ring. These rings may have a substituent.
  • the transition metal compound (1) is represented by 2-indenyl ring moiety, 1-indenyl ring moiety, indenyl ring moiety R 1 , R 6 and R 8 substituents, indenyl ring moieties R 2 , R 5 , R 9 and R 12 substituents; indenyl ring moieties R 3 , R 4 , R 10 and R 11 substituents; 1-indenyl ring moieties R 7 substituents; It is divided into seven parts of the structure.
  • the abbreviation of the 2-indenyl ring moiety is ⁇
  • the abbreviation of the 1-indenyl ring moiety is ⁇
  • the abbreviation of the substituents of the indenyl ring moiety R 1 , R 6 and R 8 is ⁇
  • the abbreviation for the R 12 substituent is ⁇
  • the abbreviation for the R 3 , R 4 , R 10 and R 11 substituents in the indenyl ring portion is ⁇
  • the abbreviation for the R 7 substituent in the 1-indenyl ring portion is ⁇
  • the abbreviation for the structure of the bridging portion. is ⁇
  • abbreviations of each substituent are shown in [Table 1] to [Table 7].
  • R 1 , R 6 and R 8 substituents in [Table 3] may be the same or different in combination.
  • R 2 , R 5 , R 9 and R 12 substituents in [Table 4] may be the same or different in combination.
  • R 3 , R 4 , R 10 and R 11 substituents in [Table 5] may be the same or different in combination.
  • the 2-indenyl ring moiety is ⁇ -1 in [Table 1]
  • the 1-indenyl ring moiety is ⁇ -2 in [Table 2]
  • the indenyl ring moiety R 1 , R 6 and R 8 substituents are all ⁇ -1,2-indenyl ring moieties
  • R 2 and R 5 substituents in [Table 3] are both ⁇ -2,2-indenyl ring moieties R 3 and R 4 substituents in [Table 4]
  • the ⁇ -1,1-indenyl ring moiety in [Table 5] consists of a combination of the R 7 substituent of ⁇ -1 in [Table 6] and the bridging moiety of ⁇ -4 in [Table 7], and the metal moiety is Zr(NMe 2 ) 2 , the compound represented by the following formula [7] is exemplified.
  • the 2-indenyl ring moiety in [Table 1 ] is the ⁇ -3,1 - indenyl ring moiety in [Table 2] and the ⁇ -1,2-indenyl ring moiety in [Table 2] ⁇ -2, indenyl ring moieties R 2 , R 5 and R 12 substituents in [Table 3] are all the ⁇ -1,1-indenyl ring moieties R 7 substituents in [Table 4]
  • the ⁇ -12,1-indenyl ring moiety R 8 substituent in [Table 3] is the ⁇ -1,1-indenyl ring moiety
  • R 9 substituent in [Table 4] is the ⁇ -42,1-indenyl ring moiety in [Table 4]
  • the R 10 substituent is ⁇ -3 in [Table 5]
  • R 11 substituent is ⁇ -12 in [Table 5]
  • the bridging moiety is ⁇ -31 in [Table 7].
  • the 2-indenyl ring moiety in [Table 1] is the ⁇ -1,1-indenyl ring moiety in [Table 2] and the ⁇ - 1,2 - indenyl ring moiety in [Table 2] ⁇ -1,2-indenyl ring moieties R 2 substituents in [Table 3] and ⁇ -7,2-indenyl ring moieties R 3 , R 4 , R 10 and R 11 substituents in [Table 4]
  • the ⁇ -1,2-indenyl ring portion R 5 substituent in [Table 5] is the ⁇ -2,1-indenyl ring portion R 7 substituent in [Table 4] ⁇ -1 in [Table 6],
  • the 1-indenyl ring moiety R 8 substituent is ⁇ -9 in [Table 3]
  • the 1-indenyl ring moiety R 9 and R 12 substituents are both ⁇ -1 in [Table 4]
  • the bridging moiety is [Table 4] 7]
  • the transition metal compound (1) can be produced using a conventionally known method, and the production method is not particularly limited.
  • the starting substituted indene compound can be produced by a known method, and the production method is not particularly limited.
  • Known production methods include, for example, "Organometallics 1994, 13, 954.”, “Organometallics 2006, 25, 1217.” WO2009/080216, “Organometallics 2011, 30, 5744.” JP 2012-012307, JP 2012-121882, JP 2014-196319, JP 2014-513735, JP 2015-063495, JP 2016-501952, JP 2019 -059933, etc., can be mentioned.
  • one type of transition metal compound may be used alone, two or more types may be used in combination, a mixture of structural isomers may be used, and structural isomers may be used. may be used alone, or a mixture of two or more structural isomers may be used.
  • the transition metal compound (1) alone is used as the transition metal compound constituting the catalyst for olefin polymerization to produce an ethylene-based polymer into which many long-chain branches are introduced with high catalytic activity.
  • one or more transition metal compounds other than the transition metal compound (1) may be used in combination as the transition metal compound as long as this effect is not impaired. At this time, the transition metal compound (1) may be in any of the above modes.
  • the solid carrier (S) contained in the olefin polymerization catalyst (X) is an inorganic compound or an organic compound, and is a granular or particulate solid.
  • inorganic compounds used as the solid carrier (S) include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds.
  • Such porous oxides have different properties depending on the type and manufacturing method. It is usually in the range of 50 to 1200 m 2 /g, preferably 100 to 1000 m 2 /g, and the pore volume is usually in the range of 0.3 to 30 cm 3 /g.
  • a carrier is calcined at, for example, 100 to 1000° C., preferably 150 to 700° C., if necessary.
  • r represents an integer of 2-500, preferably 6-300, and particularly preferably 10-100.
  • s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane remains substantially solid under the reaction environment employed.
  • an olefin polymerization catalyst e.g., an ethylene polymerization catalyst
  • an aluminoxane component as described later, and using the prepared olefin polymerization catalyst, It is that the aluminoxane component maintains a substantially solid state when the olefin (eg, ethylene) is polymerized (eg, suspension polymerization) in the presence of the aluminoxane component.
  • Visual confirmation is the easiest way to determine whether the aluminoxane component is in a solid state, but it is often difficult to visually confirm, for example, during polymerization. In that case, it is possible to determine, for example, from the properties of the polymer powder obtained after polymerization, the state of adhesion to the reactor, and the like. Conversely, if the polymer powder has good properties and little adhesion to the reactor, even if some of the aluminoxane component is eluted under the polymerization environment, it does not depart from the gist of the present invention. Indices for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymer. Polymer bulk density is preferable from the viewpoint of quantification. The bulk density is generally 0.01 to 0.9, preferably 0.05 to 0.6, more preferably 0.1 to 0.5.
  • the inorganic halides include MgCl 2 , MgBr 2 , MnCl 2 and MnBr 2 .
  • the inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing fine particles using a precipitating agent.
  • metal alkoxides such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4
  • Colloidal inorganic compounds such as substances, SiO 2 and the like can coexist.
  • pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.
  • M a AlR a 4 M a AlR a 4 (4)
  • M a represents Li, Na or K
  • R a represents a hydrocarbon group having 1 to 15 carbon atoms.
  • olefin polymerization catalyst (X) when an organoaluminumoxy compound such as methylaluminoxane is used as a cocatalyst component, not only does it exhibit extremely high polymerization activity for olefin compounds, but it also reacts with active hydrogen in the solid support.
  • Component (C) preferably contains at least the organoaluminum oxy compound (c-2), since a solid carrier component containing a co-catalyst component can be easily prepared.
  • Examples of the solvent used for preparing the olefin polymerization catalyst (X) include inert hydrocarbon solvents.
  • hydrocarbons alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; can be mentioned.
  • the reactive sites in the component (C) and the reactive sites in the component (S) are chemically bonded by reaction, and the component (C) and the component (S ) is formed.
  • the contact time between component (C) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. is done in When component (C) and component (S) are rapidly brought into initial contact with each other, component (S) collapses due to the reaction heat and reaction energy, and the morphology of the obtained solid catalyst component deteriorates. Continuous operation is often difficult due to poor polymer morphology.
  • the contact is made at a lower temperature for the purpose of suppressing the reaction heat generation, or the reaction heat generation is controlled and the reaction is made at a rate that can maintain the initial contact temperature. is preferred.
  • the contact weight ratio between component (C) and component (S) can be arbitrarily selected, but the higher the contact weight ratio, the more component (A ) can be contacted, and the catalytic activity per weight of the solid catalyst component can be improved.
  • component (C-1) the molar ratio [(C-1)/M] of component (C-1) to all transition metal atoms (M) in component (A) is usually 0.01 to 100, 000, preferably 0.05 to 50,000.
  • the drying of the prepolymerized catalyst (XP) is carried out by keeping the prepolymerized catalyst (XP) at a temperature of 70°C or less, preferably in the range of 20 to 50°C under inert gas flow.
  • the amount of volatile components in the obtained dry prepolymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less.
  • the drying time is usually 1 to 48 hours depending on the drying temperature.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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