KR830007724A - 에틸렌을 중합하기 위한 촉매조성물의 제조방법 - Google Patents

에틸렌을 중합하기 위한 촉매조성물의 제조방법 Download PDF

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KR830007724A
KR830007724A KR1019810005149A KR810005149A KR830007724A KR 830007724 A KR830007724 A KR 830007724A KR 1019810005149 A KR1019810005149 A KR 1019810005149A KR 810005149 A KR810005149 A KR 810005149A KR 830007724 A KR830007724 A KR 830007724A
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aliphatic
precursor composition
carbon atoms
aromatic hydrocarbon
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에릭 와그너 부크하드
레나드 고에케 죠오지
죤 카롤 프레드릭
프란시스 죠오지 케슬린
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에드워드 지 글리어
유니온 카바이드 코포레이션
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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
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst

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  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Pyrane Compounds (AREA)
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Abstract

내용 없음

Description

에틸렌을 종합하기 위한 촉매조성물의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
본 도면은 본 발명에서 사용될 수 있는 유동층 반응계를 나타내는 도.

Claims (11)

  1. 불활성 담체물질로 희석되며 하기 일반식(Ⅱ)의 10몰 내지 400몰의 활성제 화합물로 완전히 활성화 되는 전구체 조성물내에 전자주게(donor)몰당 0.1몰 내지 3몰의 하기 일반식(Ⅲ)의 보론 할라이드 화합물을 함유하는 전구체 조성물을 특징으로하여, 에틸렌 또는 에틸렌과 탄소수 3내지 8의적어도 하나의 알파올레핀의 혼합물을 90°내지 115℃의 온도와 1000psi이하 압력의 가스상 반응 대역내에서 하기 일반식(Ⅰ)의 상기 전구체 조성물을 함유하는 촉매계 입자와 반응시켜 에틸렌 단일중합체 또는 적어도 97몰%의 에틸렌과 거의 3몰%의 하나 또는 그 이상의 탄소수 3내지 8의 알파 올레핀은 함유하는 혼성중합체를 제조하기 위한 연속 촉매계방법(상기 중합체는 0.94g/cm3내지 0.97g/cm3의 밀도를 가지며 용융 유동비는 22내지 32이다).
    MgmTi(OR)nXp [ED]q(Ⅰ) Al(R")dX11 eHf(Ⅱ) BRcX' 3-C (Ⅲ)
    상기 일반식을 설명하면, 일반식(Ⅰ)에서
    R은 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기 또는 COR1(여기서 R1은 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기)이며,
    X는 (Cl,Br, I 및 이들의 혼합물을 구성하는 그룹으로부터 선택되었으며,
    ED는 지방족산 및 방향족 산의 알킬에스테르, 지방족 에테르, 환 에테르 및 방향족 케톤을 구성하는 그룹으로 부터 선택된 유기 전자주게 화합물이며,
    m은 0.5내지 56이며
    n은 0,1 또는 2이며
    p는 2내지 116이며
    q는 2 또는 85이며,
    X11및 Cl은 같거나 다르며, 탄소수 1내지 14의 포화 탄화수소 기이며,
    e은 0내지 1.5이며
    f는 1 또는 0이며
    d+e+f는 3이며
    R은 탄소수 1내지 14의 지방족 또는 방향족 탄화 수소기 또는OR'(여기서 R'은 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기이다)이며,
    X'은 Cl, Br 및 이들의 혼합물을 구성하는 그룹으로부터 선택되었고,
    C은 0 또는 1(여기서 R은 지방족 또는 방향족 탄화수소기) 및 0,1 또는 2(여기서 R은)이다.
  2. 제1항에 있어서, 상기 전구체 조성물을 불활성 담체물질과 기계적으로 혼합시켜 이 혼합물을 10중량%내지 50중량%의 전구체 조성물을 함유하는 상기방법.
  3. 제1항에 있어서, 상기 불활성 담체물질을 전구체 조성물로 함유시켜 함유된 담체물질이 3중량%내지 50중량%의 전구체 조성물을 함유하는 상기방법.
  4. 제1항, 제2항, 또는 제3항에 있어서, 불활성 담체물질이 실리카인 상기방법.
  5. 제4항에 있어서, 실리카를 디에틸징크로 개질시키는 상기방법.
  6. 제1항, 제2항, 제3항, 제4항, 제5항에 있어서, X및 X'가 Cl, [ED]가 테트라하이드로푸란, n이 0, m이 1.5내지 5,P가 6내지 14이며 q가 3내지 10인 상기방법.
  7. 제1항, 제2항, 제3항, 제4항, 제5항 또는 제6항에 있어서, 보론 할라이드 화합물이 에틸 보론디 트리클로라이드인 상기방법.
  8. 제1항, 제2항, 제3항, 제4항 또는 제5항 또는 제6항에 있어서, 보론 할라이드 화합물이 에틸 보론디클로라이드인 상기방법.
  9. 전자주게 화합물내에 전구체 조성물의 용액을 형성시키기 위해 적어도 하나의 MgX2구조를 갖는 마그네슘 화합물 및 적어도 하나의 Ti(OR)aXb구조를 갖는 티타니움 화합물을 적어도 하나의 액체 유기전자주게 화합물 내에서 용해하여 하기 일반식(Ⅰ) 전구체 조성물을 형성시키며, 상기 전구체 조성물을 불활성 담체물질로 희석시켜 희석된 전구체 조성물을 하기 일반식(Ⅲ)의 보론할라이드 화합물로 처리시킴을 특징으로하여 1000psi이하의 압력하에서 낮게 수반되는 에틸렌 가수소화 반응으로 고밀도 에틸렌 단일 중합체 및 혼성중합체를 제조할 수 있는 촉매 조성물의 성분으로 합당한 처리된 전구체 조성물을 제조하는 방법.
    MgmTi(OR)nXP [ED]q(Ⅰ) BRc X' 3-C (Ⅲ)
    상기 일반식을 설명하면, 일반식(Ⅰ)에서 R은 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기 도는 COR' (여기서 R'은 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기)이며,
    X는 Cl,Br, I및 이들의 혼합물을 구성하는 그룹으로부터 선택되었으며
    ED는 지방족산 및 방향족산의 알킬에스테르, 지방족에테르, 환식 에테르 및 방향족 케톤을 구성하는 그룹으로부터 선택된 유기 전자주게 화합물이며,
    m은 0.5내지 56이며,
    n은 0,1 또는 2이며,
    p는 2내지 116이며,
    q는 2내지 85이며,
    (상기 마그네슘 화합물, 티타니움 화합물, 전자주게 화합물 m,n,p 및 q값을 만족시킨다).
    a는 0,1 또는 2이며,
    b는 1내지 4이며,
    a+b는 3또는 4이며,
    일반식(Ⅲ)에서 R은 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기 또는 OR'(여기서 R'는 탄소수 1내지 14의 지방족 또는 방향족 탄화수소기이다)이며,
    X'은 Cl,Br 및 이들의 혼합물을 구성하는 그룹으로부터 선택되었고,
    C는 0 또는 1(여기서 R은 지방족 또는 방향족 탄화수소기) 및 0,1 또는 2(여기서 R은)이다.
  10. 제9항에 있어서, 상기 전구체 조성물을 불활성 담체물질과 기계적으로 혼합시켜 10중량%내지 50중량%의 전구체를 함유하는 혼합물을 형성시키는 상기방법.
  11. 제9항에 있어서, 불활성 담체물질을 전구체 조성물로 함유시켜 이 함유된 담체물질이 3내지 50중량%의 전구체 조성물을 함유하는 상기방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019810005149A 1980-12-24 1981-12-23 에틸렌 중합용 촉매 조성물의 제조방법 Expired KR870000215B1 (ko)

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US06/219,877 US4379758A (en) 1980-12-24 1980-12-24 Catalyst composition for polymerizing ethylene
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HU185489B (en) 1985-02-28
EP0055605A2 (en) 1982-07-07
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PL234595A1 (ko) 1982-09-13
IE52619B1 (en) 1988-01-06
DE3169765D1 (en) 1985-05-09
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IL64514A (en) 1984-10-31
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ATE12506T1 (de) 1985-04-15
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NO160084C (no) 1989-03-08
IN155642B (ko) 1985-02-16
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