WO2016060445A1 - Copolymère d'éthylène/1-hexène ou d'éthylène/1-butène présentant d'excellentes propriétés de travail et résistance à la fissuration sous contrainte environnementale - Google Patents

Copolymère d'éthylène/1-hexène ou d'éthylène/1-butène présentant d'excellentes propriétés de travail et résistance à la fissuration sous contrainte environnementale Download PDF

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Publication number
WO2016060445A1
WO2016060445A1 PCT/KR2015/010788 KR2015010788W WO2016060445A1 WO 2016060445 A1 WO2016060445 A1 WO 2016060445A1 KR 2015010788 W KR2015010788 W KR 2015010788W WO 2016060445 A1 WO2016060445 A1 WO 2016060445A1
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Prior art keywords
alkyl
ethylene
aryl
formula
substituted
Prior art date
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Ceased
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PCT/KR2015/010788
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English (en)
Korean (ko)
Inventor
김중수
권혁주
최이영
이기수
송은경
송낙규
홍대식
김우리
김시용
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to RU2016125864A priority Critical patent/RU2640045C1/ru
Priority to US15/035,099 priority patent/US9732172B2/en
Priority to JP2016541701A priority patent/JP6487924B2/ja
Priority to EP15850164.3A priority patent/EP3056524B1/fr
Priority to CN201580002923.3A priority patent/CN105814101B/zh
Priority claimed from KR1020150142491A external-priority patent/KR101726820B1/ko
Publication of WO2016060445A1 publication Critical patent/WO2016060445A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • linear low density polyethylene is prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short chain branch of a constant length, and a long chain branch.
  • the linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tearing strength and fall stratification strength, so that the use of stretch film or overlap film, which is difficult to apply to the existing low density polyethylene or high density polyethylene, increases. Doing.
  • Environmental stress crack resi st ance instantiated by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ° C; ESCR) is 400 hours to 20,000 hours,
  • the molecular weight distribution (Mw / Mn, PDI) of the ethylene / 1-nuxene copolymer is 2 to 30. According to the broad molecular weight distribution as described above, the ethylene / 1-nuxene copolymer may exhibit excellent processability. More preferably, the molecular weight distribution is 3 or more, 25 or less, 20 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, or 10 or less.
  • the ethylene / 1-nuxene copolymer of the present invention has a high molecular weight and a wide molecular weight distribution and has excellent physical properties and processability.
  • the melt flow rate ratio is 15 or more, 20 or more, 25 or more, or 30 or more, 180 or less, 150 or less, 100 or less, 50 or less, 40 or less, 35 or less, 34 or less, or 33 or less.
  • MFR 5 melt flow index measured at 190 ° C., 5 kg load based on ASTM D12378 of the ethylene / 1-butene copolymer is 0.1 to 5 g / 10 min, more preferably 0.1 To 3 g / 10 min.
  • the density of the ethylene / 1-butene copolymer is 0.930 to 0.950 g / cuf, preferably 0.935 to 0.950 g / cirf.
  • D is -E, -S-, -N (R)-or -Si (RR ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, d-20 alkyl, C 2 - 20 alkenyl, or C 6 - 20 aryl;
  • L is d- 10 straight or branched chain alkylene
  • C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that C 1 and C 2 are both Chemical Formula 2c;
  • Cp 1 and Cp 2 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
  • R a and ⁇ are the same or different, each independently represent hydrogen, alkyl, and (10 alkoxy, C 2 of each other - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 - 10 aryloxy, C 2 - 20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 8 - 40 arylalkenyl, or C 2 - 10 alkynyl;
  • Z 1 is a halogen atom, d- 20 alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 - 20 aryl, optionally substituted d-20 alkylidene, substituted unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • Z 2 is a halogen atom, d- 20 alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 Arylalkyl, C 6 - 20 aryl, optionally substituted d- 20 alkylidene, substituted or unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, gtetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms And;
  • Z 3 is a halogen atom, alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 _ 20 aryl, substituted or unsubstituted (20 alkylidene, substituted or unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • T + is a + monovalent polyatomic ion
  • ⁇ is boron in +3 oxidation state
  • G is independently hydride, dialkylamido, halide, alkoxide, aryloxide hydrocarbyl, halocarbyl and Selected from the group consisting of halo-substituted hydrocarbyls, wherein G has up to 20 carbons, but at up to one position G is a halide.
  • the polymerization reaction may be performed by copolymerizing ethylene and 1-nuxene or 1-butene using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
  • the polymerization temperature may be about 25 to about 500 ° C, preferably about 25 to about 200 ° C, more preferably about 50 to about 15 C C.
  • the polymerization pressure may be about 1 to about 100 Kgf / cui 2 , preferably about 1 to about 50 Kgf / crf, more preferably about 5 to about 30 Kgf / ciif.
  • the reactor temperature was increased by about 4 to 5 ° C. with the addition of 6-t-subsilicate nucleus chloride, 12 hours under continuous addition of 6-t-butoxynucle chloride. After 12 hours of reaction, a black reaction solution was obtained, and 2 mL of the resulting black solution was taken, and water was added thereto to obtain an organic layer, and then purified by 6 H-NMR (6-t-buthoxyhexan). e) It was confirmed that the Gringanrd reaction proceeded well from the 6-t-butoxynucleic acid, thereby synthesizing 6-t-butoxynuxyl magnesium chloride. .
  • the supported catalyst was prepared in the same manner as in Comparative Examples 1-1 and 1-2, except that 314 mL of the metallocene compound / luluene solution of Preparation Example 3 was added in Comparative Examples 1-1 and 1-2. Prepared.
  • Example 1-3
  • reaction solution was decantat ion, the toluene slurry was transferred to a fil ter dryer and filtered, 3.0 kg of toluene was added and stirred for 10 minutes, the stirring was stopped and filtered. Stir for 10 minutes, then stir and And it was in. 50 ° C and dried under reduced pressure for 4 hours to prepare a 500g-Si0 2 catalyst.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un copolymère d'éthylène/1-hexène ou d'éthylène/1-butène présentant d'excellentes propriétés de travail. Le copolymère d'éthylène/1-hexène ou d'éthylène/1-butène selon la présente invention a un poids moléculaire élevé et une large distribution de poids moléculaire et présente d'exceptionnelles propriétés de travail et une excellente résistance à la fissuration sous contrainte environnementale, et peut par conséquent être utilisé dans une tuyauterie de chauffage haute pression, des tuyaux miniers ou des tuyaux à grand diamètre et analogue.
PCT/KR2015/010788 2014-10-13 2015-10-13 Copolymère d'éthylène/1-hexène ou d'éthylène/1-butène présentant d'excellentes propriétés de travail et résistance à la fissuration sous contrainte environnementale Ceased WO2016060445A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
RU2016125864A RU2640045C1 (ru) 2014-10-13 2015-10-13 Сополимер этилен/1-гексен или этилен/1-бутен, обладающий отличными технологическими свойствами и сопротивлением разрастанию трещин под действием факторов окружающей среды
US15/035,099 US9732172B2 (en) 2014-10-13 2015-10-13 Ethylene/1-hexene or ethylene/1-butene copolymer having excellent processibility and environmetal stress crack resistance
JP2016541701A JP6487924B2 (ja) 2014-10-13 2015-10-13 加工性および環境応力亀裂抵抗性に優れたエチレン／１−ヘキセンまたはエチレン／１−ブテン共重合体
EP15850164.3A EP3056524B1 (fr) 2014-10-13 2015-10-13 Copolymère d'éthylène/1-butène présentant d'excellente processabilité et résistance à la fissuration sous contrainte environnementale
CN201580002923.3A CN105814101B (zh) 2014-10-13 2015-10-13 具有优良可加工性和耐环境应力开裂性的乙烯/1‑己烯或乙烯/1‑丁烯共聚物

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20140137867 2014-10-13
KR20140137868 2014-10-13
KR10-2014-0137867 2014-10-13
KR10-2014-0137868 2014-10-13
KR1020150142491A KR101726820B1 (ko) 2014-10-13 2015-10-13 가공성 및 환경 응력 균열 저항성이 우수한 에틸렌/1-헥센 또는 에틸렌/1-부텐 공중합체
KR10-2015-0142491 2015-10-13

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10155830B2 (en) 2014-12-08 2018-12-18 Lg Chem, Ltd. Ethylene/alpha-olefin copolymers having excellent processability
CN109415451A (zh) * 2016-04-27 2019-03-01 韩华化学株式会社 利用负载型混杂茂金属催化剂的高密度乙烯类聚合物及其制备方法
JP2019524963A (ja) * 2016-11-08 2019-09-05 エルジー・ケム・リミテッド エチレン／アルファ−オレフィン共重合体

Citations (9)

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Publication number Priority date Publication date Assignee Title
US4935474A (en) 1983-06-06 1990-06-19 Exxon Research & Engineering Company Process and catalyst for producing polyethylene having a broad molecular weight distribution
US5914289A (en) 1996-02-19 1999-06-22 Fina Research, S.A. Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution
JP2002504958A (ja) * 1997-06-16 2002-02-12 ボレアリス エー／エス 異なる触媒活性部位を有する触媒を用いる多段階重合プロセス
KR20030012308A (ko) 2001-07-31 2003-02-12 주식회사 예스아이비 배팅형 복권 시스템 및 배팅 방법
KR20040037067A (ko) * 2001-08-24 2004-05-04 아토피나 리서치 사출 취입 성형된 단층 메탈로센 폴리에틸렌 용기
US6828394B2 (en) 2001-07-19 2004-12-07 Univation Technologies, Llc Mixed metallocene catalyst systems containing a poor comonomer incorporator and a good comonomer incorporator
US6841631B2 (en) 1999-10-22 2005-01-11 Univation Technologies, Llc Catalyst composition, method of polymerization, and polymer therefrom
KR100646249B1 (ko) * 2004-04-08 2006-11-23 주식회사 엘지화학 혼성 담지 메탈로센 촉매를 이용한 가공성 및 내압 특성이뛰어난 급수관 파이프용 폴리에틸렌 및 그의 제조방법
KR101154507B1 (ko) * 2009-07-31 2012-06-13 주식회사 엘지화학 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하여 제조된 올레핀계 중합체

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US5914289A (en) 1996-02-19 1999-06-22 Fina Research, S.A. Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution
JP2002504958A (ja) * 1997-06-16 2002-02-12 ボレアリス エー／エス 異なる触媒活性部位を有する触媒を用いる多段階重合プロセス
US6841631B2 (en) 1999-10-22 2005-01-11 Univation Technologies, Llc Catalyst composition, method of polymerization, and polymer therefrom
US6894128B2 (en) 1999-10-22 2005-05-17 Univation Technologies, Llc Catalyst composition, method of polymerization, and polymer therefrom
US6828394B2 (en) 2001-07-19 2004-12-07 Univation Technologies, Llc Mixed metallocene catalyst systems containing a poor comonomer incorporator and a good comonomer incorporator
KR20030012308A (ko) 2001-07-31 2003-02-12 주식회사 예스아이비 배팅형 복권 시스템 및 배팅 방법
KR20040037067A (ko) * 2001-08-24 2004-05-04 아토피나 리서치 사출 취입 성형된 단층 메탈로센 폴리에틸렌 용기
KR100646249B1 (ko) * 2004-04-08 2006-11-23 주식회사 엘지화학 혼성 담지 메탈로센 촉매를 이용한 가공성 및 내압 특성이뛰어난 급수관 파이프용 폴리에틸렌 및 그의 제조방법
KR101154507B1 (ko) * 2009-07-31 2012-06-13 주식회사 엘지화학 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하여 제조된 올레핀계 중합체

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10155830B2 (en) 2014-12-08 2018-12-18 Lg Chem, Ltd. Ethylene/alpha-olefin copolymers having excellent processability
CN109415451A (zh) * 2016-04-27 2019-03-01 韩华化学株式会社 利用负载型混杂茂金属催化剂的高密度乙烯类聚合物及其制备方法
JP2019524963A (ja) * 2016-11-08 2019-09-05 エルジー・ケム・リミテッド エチレン／アルファ−オレフィン共重合体
US10858465B2 (en) 2016-11-08 2020-12-08 Lg Chem, Ltd. Ethylene/alpha-olefin copolymer

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