KR970706311A - 단일 반응기에서 제조된 광범위한/이정 수지의 분자량 분포를 조절하는 방법(process for controlling the mwd of a broad/bimodal resin produced in a single reactor) - Google Patents

단일 반응기에서 제조된 광범위한/이정 수지의 분자량 분포를 조절하는 방법(process for controlling the mwd of a broad/bimodal resin produced in a single reactor)

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Publication number
KR970706311A
KR970706311A KR1019970701847A KR19970701847A KR970706311A KR 970706311 A KR970706311 A KR 970706311A KR 1019970701847 A KR1019970701847 A KR 1019970701847A KR 19970701847 A KR19970701847 A KR 19970701847A KR 970706311 A KR970706311 A KR 970706311A
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molecular weight
amount
resin
weight distribution
reagent
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KR1019970701847A
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KR100356099B1 (ko
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이반 밍크 로버트
에드워드 노린 토마스
데니스 쉬리젠버거 산드라
판듀랑 쉬로드카 프라디프
온키 치엔 그레이스
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데니스 피. 샌티니
모빌 오일 코오포레이숀
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61904—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with another component of C08F4/60
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Abstract

본 발명은 수지의 분자량 분포를 조절하는 방법에 관한 것이다. 2-금속 촉매는 광범위한, 또는 이정(bimodal) 분자량 분포를 가진 폴리올레핀 수지를 생산하며, 그 조성은 HMW 및 LMW 성분을 생성하는 촉매의 2가지 금속의 농도의 비율에 좌우된다. 2-금속 촉매는 광범위한/이정 MWD 수지를 생성하며, 그 수지의 HMW 및 LMW 성분은 촉매의 각각의 전이 금속 부위의 상대적인 생산율에 좌우된다. 물 및/또는 이산화탄소를, HMW 및 LMW 성분의 중량 분율을 개질하는데 필요한 농도로 중합 반응기에 동시공급하므로써, 목적하는 분자량 분포(MWD)를 달성한다. 본 발명에 의해 반응기내에서 수지 MWD를 조정할 수 있다. 본 발명은 물 및/또는 이산화탄소를 첨가하여 고분자량 성분의 중량 분율을 감소시키며, 전체적인 생성물의 FI는 생성물내의 HMW 성분의 중량 분율이 감소함에 따라서 증가한다.

Description

단일 반응기에서 제조된 광범위한/이정 수지의 분자량 분포를 조절하는 방법 (PROCESS FOR CONTROLLING THE MWD OF A BROAD/BIMODAL RESIN PRODUCED IN A SINGLE REACTOR)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (7)

  1. 고분자량 성분과 저분자량 성분을 포함하는 이정 분자량 분포를 갖는 수지 또는 광범위한 분자량 분포를 갖는 수지에서 상기 고분자량 성분과 저분자량 성분의 상대적인 양을 조절하는 방법으로서, -에틸렌을 포함하는 공급원료를 에틸렌 중합반응 조건하에서, 2가지 전이 금속 공급원을 함유하는 지지체를 포함하는 촉매와 접촉시키는 단계로서, 상기 촉매는 활성화된 전이 금속이 메탈로센 화합물 및 비-메탈로센 전이 금속 화합물을 포함하는 조성물을 함유한 건조된 무수 상태의 지지체를 포함하고, 상기 지지체는 (1) OH 기를 가지며, RMgR' : OH 몰 비율 0.5 : 1 내지 4 : 1을 제공하는 양으로 존재하는 화합물 RMgR'(식 중, R 및 R'는 각각 탄소원자수 4 내지 10의 알킬임)으로 함침된 실리카; 및 (2) 화학식 R″OH로 표시되고, 식 중 R″는 탄소원자수 1 내지 12의 알킬이며, 알코올/Mg 몰비율 0.5 내지 2.0을 제공하는데 유효한 양으로 사용되는 유기 알코올 시약과의 반응 생성물인 단계; -상기 이정 분자량 분포를 갖는 수지 또는 광범위한 분자량 분포를 갖는 수지를 생성시키는 단계; - 상기 촉매와의 접촉을 위해 추가량의 공급원료를 주입하며, 이때 상기 활성화된 메탈로센 화합물은 -비-메탈로센 전이 금속 화합물에 대한 제1의 생산율을 나타내는 단계; - 물, 이산화탄소 및 이들의 혼합물로 이루어진 군중에서 선택된 일정량의 시약을 첨가하는 단계로서, 상기 시약의 양은 상기 비-메탈로센 화합물에 대한 제1생산율을 변경시키는데 유효한 양인 단계; 및 - 상기 상대적인 양과는 상이한 상기 고분자량 성분과 상기 저분자량 성분의 제2의 상대적인 비율을 가진 개질된 생성물을 회수하는 단계를 포함하는 방법.
  2. 제1항에 있어서, 상기 시약의 양이 비-메탈로센 전이 금속 화합물의 생산율을 감소시키는데 유효한 양인 방법.
  3. 제2항에 있어서, 상기 시약이 상기 수지내의 고분자량 성분의 양을 감소시키는 작용을 하는 방법.
  4. 제1항에 있어서, 실리카 및 메탈로센을 포함하는 단일의 촉매 성분을 함유하는 조성물을 동시공급하는 단계를 추가로 포함하는 방법.
  5. 제1항에 있어서, 상기 시약의 양이 에틸렌을 기준으로 하여 0-20 ppm 범위의 H2O이고; 에틸렌을 기준으로 하여 0-10 ppm의 CO2인 방법.
  6. 제1항에 있어서, 상기 시약의 양이 에틸렌을 기준으로 하여 0.1 내지 1000ppm의 H2O 또는 에틸렌을 기준으로 하여 0.1 내지 50ppm의 CO2인 방법.
  7. 제1항에 있어서, 기체 상에서 수행하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019970701847A 1994-09-22 1995-07-17 단일반응기에서 제조된 광범위한 분자량분포/2모드의 분자량 분포를 가진 수지의 분자량 분포를 제어하는 방법 KR100356099B1 (ko)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US310,446 1994-09-22
US08/310,446 US5525678A (en) 1994-09-22 1994-09-22 Process for controlling the MWD of a broad/bimodal resin produced in a single reactor

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KR970706311A true KR970706311A (ko) 1997-11-03
KR100356099B1 KR100356099B1 (ko) 2003-02-17

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US (1) US5525678A (ko)
EP (1) EP0782586B1 (ko)
JP (1) JP4046348B2 (ko)
KR (1) KR100356099B1 (ko)
CN (1) CN1087300C (ko)
AU (1) AU691025B2 (ko)
DE (1) DE69520107T2 (ko)
ES (1) ES2153901T3 (ko)
WO (1) WO1996009328A1 (ko)
ZA (1) ZA957036B (ko)

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AU3233895A (en) 1996-04-09
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US5525678A (en) 1996-06-11
EP0782586A4 (ko) 1997-08-13
ES2153901T3 (es) 2001-03-16
CN1087300C (zh) 2002-07-10
EP0782586A1 (en) 1997-07-09
AU691025B2 (en) 1998-05-07
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