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KR960022599A - 폴리에틸렌의 제조방법 - Google Patents

폴리에틸렌의 제조방법 Download PDF

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KR960022599A
KR960022599A KR1019950050380A KR19950050380A KR960022599A KR 960022599 A KR960022599 A KR 960022599A KR 1019950050380 A KR1019950050380 A KR 1019950050380A KR 19950050380 A KR19950050380 A KR 19950050380A KR 960022599 A KR960022599 A KR 960022599A
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polymerization
reactor
ethylene
reaction
polymer
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KR1019950050380A
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KR100411381B1 (ko
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팜루스 아리
할린 알리
아베나이넨 안테로
타카카루 유니
사일라 아이모
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카리 사란틸라
보레알리스 폴리머즈 오와이
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00171—Controlling or regulating processes controlling the density
    • B01J2219/00173—Physical density
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

본 발명은 에틸렌 중합반응 촉매와 보조촉매로 구성되는 촉매 시스템의 존재하에서 연속직인 액체상 및 기체상 중합반응으로 구성되는 다단계 반응순서를 이용하여 폴리에틸렌 조성물을 제조하는 방법에 관한 것이다.
상기 방법은 제1단계에서 에틸렌 및 임의로 수소 및 공단량체가 루으프 반응기 내의 에틸렌 중합반응 촉매 및 보조촉매 존재하의 저융점 탄화수소 매질 중에서 중합반응하고 〔이때 체류 시간 및 반응 온도는 상기 방법의 최종 생성물로부터 상기 반응기 내에서 제조되는 에틸렌 중합체의 비율이 1~20중량%가 되도록 선택하며〕, 상기 단계로부터 제거된 반응 혼합물을 제2단계로 이전하고, 여기서 에틸렌, 수소 및 임의로 불활성 탄화수소, 공단량체 및 촉매를 첨가하므로써 루우프 반응기 내에서 중합 반응을 계속하고, 이때 체류 시간은 10분 이상으로 하며, 반응 혼합물을 루으프 반응기로부터 제거하고, 반응 매질의 적어도 실질적인 부분을 제거하고, 첨가된 에틸렌 및 임의의 수소, 공단량체 및 보조촉매 존재하의 기체상 반응기에서 중합 반응이 수행되는 제3단계로 그 중합체를 이전시키는 하나 이상의 연속적인 반응 순서를 포함한다.
〔선택도〕제1도

Description

폴리에틸렌의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (13)

  1. 에틸렌 중합반응 촉매 및 보조촉매로 구성되는 촉매 시스템의 존재하에서 연속적인 액체상 및 기체상 중합반응으로 구성되는 다단계 반응 순서에 의해 폴리에틸렌 조성물을 제조하는 방법에 있어서, 상기 방법은 제1단계에서 에틸렌 및 임의로 수소 및 공단량체가 루으프 반응기 내의 에틸렌 중합반응 촉매 및 보조촉매 존재하의 저융점 탄화수소 매질 중에서 중합반응하고〔이때 체류 시간 및 반응 온도는 상기 방법의 최종 생성물로부터 상기 반응기 내에서 제조되는 에틸렌 중합체의 비율이 1-20중량%가 되도록 선택하며〕, 상기 단계로부터 제거된 반응 혼합물을 제2단계로 이전하고, 여기서 에틸렌, 수소 및 임의로 불활성 탄화수소, 공단량체 및 촉매를 첨가하여 루우프 반응기 내에서 중합반응을 계속하고, 이때 체류 시간은 10분 이상으로 하며, 반응 혼합물을 루으프 반응기로부터 제거하고, 반응 매질의 적어도 실질적인 부분을 제거하고, 첨가된 에틸렌 및 임의의 수소, 공단량체 및 보조촉매 존재하의 기체상 반응기에서 중합반응이 수행되는 제3단계로 그 중합체를 이전시키는, 하나 이상의 연속적인 반응 순서를 포함함을 특징으로 하는 방법.
  2. 제1항에 있어서, 촉매는 제1중합반응 단계에만 공급되고, 보조촉매는 상기 제1중합반응 단계, 임의로 제2 및/또는 제3단계의 루으프 반응기 및/또는 기체상 반응기에 공급함을 특징으로 하는 방법.
  3. 제1항 또는 제2항에 있어서, 제1중합반응 단계의 루으프 반응기에서, 제조된 중합체의 용융 지수가 이후의 중합반응 단계의 루으프 반응기에서 제조된 중합체의 용융 지수보다 작음을 특징으로 하는 방법.
  4. 제3항에 있어서, 제1중합반응 단계에서 중합반응의 조건을 제조된 에틸렌 중합체의 용융지수 MFR2가 0.01~50이 되도록 선택하고, 제2중합반응 단계에서 상기 조건을 에틸렌 중합체 분획의 용융 지수 MFR2가 10~2000이 되도록 선택함을 특징으로 하는 방법.
  5. 전술한 항 중 어느 한 항에 있어서, 제1중합반응 단계에서 제조한 에틸렌 중합체의 분자량 대 제3중합반응 단계로부터 제거한 최종 생성물의 분자량의 비가 0.25~5임을 특징으로 하는 방법.
  6. 전술한 항 중 어느 한 항에 있어서, 제1중합반응 단계의 루으프 반응기의 반응 온도가 20~100℃, 바람직하게는 40∼80℃이고, 체류 시간이 10분 내지 2시간임을 특징으로 하는 방법.
  7. 전술한 항 중 어느 한 항에 있어서, 루으프 반응기 내의 불활성 탄화수소로서 프로판을 이용하고, 제2단계 루으프 반응기 내의 반응 온도 및 압력을 불활성 탄화수소, 단량체 및 수소에 의해 형성된 반응 유체가 초임계 상태에 존재하도록 선택함을 특징으로 하는 방법.
  8. 전술한 항 중 어느 한 항에 있어서, 제1단계 루으프 반응기에서 분자량이 150,000 내지 600,000이고, 밀도가 940 내지 970kg/m2인 폴리에틸렌을 제조하고, 제2중합반응 단계의 루으프 반응기에서 분자량이 500 내지 50,000이고, 밀도가 950 내지 980kg/m2인 폴리에틸렌을 제조함을 특징으로 하는 방법.
  9. 제3항에 있어서 제1중합반응 단계의 루으프 반응기에서 분자량이 400,000 미만인 에틸렌 중합체를 제조함을 특징으로 하는 방법.
  10. 제1항 내지 제7항 중 어느 한 항에 있어서, 제1중합반응 단계에서 일정량의 C4-C8알파-올레핀 같은 공단량체를 루으프 반응기에 공급하고, 상기 반응기에서 제조될 생성물의 밀도가 910 내지 950kg/m2임을 특징으로 하는 방법.
  11. 제10항에 있어서, 공단량체가 1-부텐, 1-헥센, 4-메틸-1-펜텐, 1-옥텐 또는 그들의 혼합물로 구성되는 군으로부터 선택됨을 특징으로 하는 방법.
  12. 진술한 항 중 어느 한 항에 있어서, 공단량체로서 C4-C8알파-올레핀을 제3중합반응 단계의 기체상 반응기에 공급함을 특징으로 하는 방법.
  13. 전술한 항 중 어느 한 항에 있어서, 프로판을 액체 또는 기체 또는 둘 다의 형태로 혼합기를 통해 기체상 반응기 내로 공급함을 특징으로 하는 방법.
    ※ 참고사항:최초출원 내용에 의하여 공개하는 것임.
KR1019950050380A 1994-12-16 1995-12-15 폴리에틸렌의제조방법 KR100411381B1 (ko)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI945926 1994-12-16
FI945926A FI96216C (fi) 1994-12-16 1994-12-16 Prosessi polyeteenin valmistamiseksi

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KR960022599A true KR960022599A (ko) 1996-07-18
KR100411381B1 KR100411381B1 (ko) 2004-04-29

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US (1) US5684097A (ko)
EP (1) EP0797599B1 (ko)
JP (1) JP3743847B2 (ko)
KR (1) KR100411381B1 (ko)
CN (1) CN1093863C (ko)
AR (1) AR000359A1 (ko)
AT (1) ATE177437T1 (ko)
AU (1) AU706963B2 (ko)
BR (1) BR9510034A (ko)
CA (1) CA2207910C (ko)
CZ (1) CZ290644B6 (ko)
DE (1) DE69508277T2 (ko)
ES (1) ES2129878T3 (ko)
FI (1) FI96216C (ko)
GR (1) GR3029896T3 (ko)
IL (1) IL116315A (ko)
MY (1) MY112607A (ko)
RU (1) RU2161625C2 (ko)
WO (1) WO1996018662A1 (ko)
ZA (1) ZA9510501B (ko)

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BR9510034A (pt) 1997-10-28
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WO1996018662A1 (en) 1996-06-20
RU2161625C2 (ru) 2001-01-10
ZA9510501B (en) 1996-06-19
ES2129878T3 (es) 1999-06-16
ATE177437T1 (de) 1999-03-15
CN1173187A (zh) 1998-02-11
CN1093863C (zh) 2002-11-06
CZ290644B6 (cs) 2002-09-11
GR3029896T3 (en) 1999-07-30
FI96216B (fi) 1996-02-15
US5684097A (en) 1997-11-04
DE69508277T2 (de) 1999-09-09
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JPH10510570A (ja) 1998-10-13
AU4118396A (en) 1996-07-03
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EP0797599B1 (en) 1999-03-10
AU706963B2 (en) 1999-07-01
CZ184097A3 (en) 1997-11-12
FI96216C (fi) 1996-05-27
AR000359A1 (es) 1997-06-18
EP0797599A1 (en) 1997-10-01
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