KR910018421A - 기체상 올레핀 중합법 - Google Patents
기체상 올레핀 중합법 Download PDFInfo
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- KR910018421A KR910018421A KR1019910005804A KR910005804A KR910018421A KR 910018421 A KR910018421 A KR 910018421A KR 1019910005804 A KR1019910005804 A KR 1019910005804A KR 910005804 A KR910005804 A KR 910005804A KR 910018421 A KR910018421 A KR 910018421A
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- KR
- South Korea
- Prior art keywords
- catalyst
- transition metal
- antistatic agent
- prepolymer
- alpha
- Prior art date
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- 238000006116 polymerization reaction Methods 0.000 title claims 12
- 150000001336 alkenes Chemical class 0.000 title 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims 19
- 150000003624 transition metals Chemical group 0.000 claims 16
- 239000002216 antistatic agent Substances 0.000 claims 13
- 150000002902 organometallic compounds Chemical class 0.000 claims 10
- 239000004711 α-olefin Substances 0.000 claims 10
- 230000000737 periodic effect Effects 0.000 claims 9
- 229920000642 polymer Polymers 0.000 claims 8
- 229910052751 metal Inorganic materials 0.000 claims 7
- 239000002184 metal Substances 0.000 claims 7
- 238000000034 method Methods 0.000 claims 6
- 229910052723 transition metal Inorganic materials 0.000 claims 6
- 150000003839 salts Chemical class 0.000 claims 5
- 239000011651 chromium Substances 0.000 claims 4
- 229930195733 hydrocarbon Natural products 0.000 claims 4
- 150000002430 hydrocarbons Chemical class 0.000 claims 4
- 239000007788 liquid Substances 0.000 claims 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- -1 aromatic carboxylic acids Chemical class 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002736 metal compounds Chemical class 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 150000005215 alkyl ethers Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229940068041 phytic acid Drugs 0.000 claims 1
- 235000002949 phytic acid Nutrition 0.000 claims 1
- 239000000467 phytic acid Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
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
- C08F210/00—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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
-
- 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
- Y10S526/903—Monomer polymerized in presence of transition metal containing catalyst and hydrocarbon additive affecting polymer properties of catalyst activity
-
- 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
- Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
내용 없음
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (14)
- 알파-올레핀 (공)중합에서 촉매적 활성이 있는 하나 또는 그 이상의 C2∼C12알파-올레핀류의 초기중합체에 있어서, 50∼500마이크론 범위의 매쓰-평균 직경(mass-mean diameter)을 가진 입자들로 구성되어 있고, 초기중합체 1g당 원소 주기유표 Ⅳ,Ⅴ또는 Ⅵ족중의 하나에 속하는 적어도 하나의 전이금속 원자0.002∼10㎎,대전 방지제 및 상기 주기율표 Ⅱ 또는 Ⅲ족 금속의 적어도 하나의 유기 금속 화합물을 전이 금속(들)에 대한 유기 금속 화합물(들)의 금속(들)의 원자비가 0.01/10로 함유하는 초기중합체.
- 제1항에 있어서, 초기 중합체 1g당 0.01∼10㎎의 대전 방지제를 함유함을 특징으로 하는 초기중합체.
- 제1항 또는 제2항에 있어서, 대전 방지제가 하기:-금속이 알칼리 금속, 알킬리토금속,Cu,Zn, Cd, Al,Pd, Cr,Mo또는 MN인 C6-C30카르복실산의 금속염, -C10∼C20알킬-또는 알케일 치환 방향족 카르복실산의 Cr염,-N-알킬 또는 N-알켄일-안트라닐산의 Cr염-알킬카복시레이트-치환 술폰산의 알칼리 또는 알칼리토금속염,-알킬화된 피트산 폴리에틸 이민염,-피트산의 4 암모늄염,-에틸렌형 불포화 카르복실산 또는 에틸렌향 불포화 에스테르(i)와 에틸렌형 불포화 유기염(ⅱ)의 공중합체,-술폰산 에스테르염,-지방 카르복실산의 폴리에틸렌 글리콜 에스테르, 및-폴레옥시에틸렌 알킬 에테르 중에서 선택된 적어도 하나의 생성물 또는 화합물을 함유하는 초기중합체.
- 제1항 내지 제3항중의 어느 한 항에 있어서, 초기중합체 1G당 2∼10,000㎎의 내화 산화물을 함유함을 특징으로 하는 초기중합체.
- 제1항 내지 제4항중의 어느 한항에 있어서, 0.3∼0.55g/㎤의 벌크 밀도(bulk density)를 갖는 분말형임을 특징으로 하는 초기중합체.
- 원소 주기율표 Ⅳ,Ⅴ 또는 Ⅵ족 중의 하나에 속하는 적어도 하나의 전이 금속을 기재로 하는 촉매(a)를 적어도 하나의 C2∼C12알파-올레핀 및 주기율 표 Ⅱ 또는 Ⅲ족 금속의 적어도 하나의 유기 금속 화합물(b)에 접촉시키는 것으로 구성된 초기중합 이전 및/또는 동안에, 상기 촉매의 전이 금속 원자1g 당 0.1∼200g의 대전 방지제 및 상기 촉매의 전이 금속 원자 1g 당 0.01∼100mole의 상기 유기 금속 화합물의 양으로, 대전 방지제를 상기촉매 및 상기 유기 금속 화합물과 접촉시키고, 상기 촉매의 전이 금속 원자 1㎎당 0.1∼500g의 초기중합체를 수득할 때까지 초기중합 수행함을 특징으로 하는 제1항 내지 제5항중 어느 한 항에 따른 초기중합체의 제조 방법.
- 제6항에 있어서, 불활성 포화 탄화수소이거나 또는 알파-올레핀인 탄화수소 액체의 존재하에서 대전 방지제를 촉매(a) 및 유기 금속 화합물(b)에 접촉시키는 것을 특징으로 하는 방법.
- 원소 주기율표 Ⅳ,Ⅴ또는 Ⅵ족중의 하나에 속하는 적어도 하나의 전이 금속을 기재로 한 촉매를 상기 주기율표 Ⅱ 또는 Ⅲ족 금속의 적어도 하나의 유기 금속 화합물 및적어도 하나의 C2∼12알파-올레핀과 접촉시키는 것을 포함하는 초기중합 이후에 수득되고, 0.002∼10㎎의 상기 촉매의 전이 금속 원자를 함유하며 상기 촉매의 전이 금속에 대한 상기 유기 금속 화합물의 금속의 원자비가 0.01∼100인 초기 중합체 및 초기 중합체내에 포함된 전이 금속 원자 1g당 0.1∼200g의 양으로 초기중합체와 접촉하는 대전 방지제를 접촉하게 함을 특징으로 하는 제1항 내지 제5항중 어느 한항에 따른 초기중합체의 제조 방법.
- 제8항에 있어서, 불활성 포화 탄화수소 또는 알파-올레핀인 탄화수소 액체의 존재하에서 대전 방지제와 초기중합체를 접촉시킴을 특징으로 하는 방법.
- 먼저, 원소 주기율표 Ⅳ,Ⅴ또는 Ⅵ족중의 하나에 속하는 적어도 하나의 전이 금속을 기재로 한 촉매(a)를 적어도 하나의 C2∼C12알파-올레핀 및 상기 주기율표 Ⅱ 또는 Ⅲ쪽 금속의 적어도 하나의 유기 금속 화합물(b)에 접촉시키는 것으로 구성된 초기중합 이전 또는 동안에 상기촉매의 전이 금속 원자 1g당 0.05∼100g의 대전 방지제 및 상기 촉매의 전이 금속 원자 1g당 0.01∼100mole의 상기 유기 금속 화합물의 양으로, 대전 방지제를 상기 촉매 및 상기 유기 금속 화합물과 접촉시키고, 상기 촉매의 전이 금속 원자 1㎎당 0.1∼500g의 초기 중합체를 수득할 때까지 초기 중합을 수행하고(i) 그후, 대전 방지제를 초기 중합체내에 함유된 전이 금속 원자 1g당 0.05∼100g 범위의 양의로 초기 중합 종료후에 수득된 초기중합체와 접촉시킴(ⅱ)을 특징으로 하는 제1항 내지 제5항 중의 어느 한 항에 따른 초기중합체의 제조방법.
- 제10항에 있어서, 초기중합 이전 또는 동안에 대전 방지제를 촉매(a) 및 유기금속 화합물(b)과 접촉시키고 초기 중합 종료후 대전 방지제와 초기중합체 와의 접촉이 불활성 포화 탄화 수소 또는 알파-올레핀인 액체 탄화수소의 존재하에서 수행됨을 특징으로 하는 제조방법.
- 제6항 내지 제11항중의 어느 한 항에 있어서, 촉매가 티타늄,바나듐, 하프늄, 지르코늄 및 크롬 및 경우에 따라서는 내화 산화물 지지체중에서 선택된 적어도 하나의 전이 금속을 함유하는 찌글러-나타형 촉매이거나 내화 산화물 상에 지지되고 비환원성 대기하에 열처리에 의해 활성화된 촉매임을 특징으로하는 방법.
- 제1항 내지 제5항중 어느 한 항에 따른 초기중합체를 기체상(공)중합 매질로 주입시키는 것에 의해 수행함을 특징으로 하는 하나 또는 그 이상 알파-올레핀류의 기체상 (공)중합 방법.
- 제13항에 있어서, 초기 중합체가 불활성 포화 탄화수소 이거나 알파-올레핀인 탄화수소 액체내의 슬러리형, 또는 건조 분말형으로 기체상 (공)중합매질에 주입함을 특징으로 하는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9004926 | 1990-04-11 | ||
FR9004916A FR2660926B1 (fr) | 1990-04-11 | 1990-04-11 | Prepolymere d'alpha-olefine contenant un metal de transition et procede de polymerisation d'alpha-olefine en phase gazeuse mettant en óoeuvre le prepolymere. |
Publications (2)
Publication Number | Publication Date |
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KR910018421A true KR910018421A (ko) | 1991-11-30 |
KR100199686B1 KR100199686B1 (ko) | 1999-06-15 |
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Family Applications (1)
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KR1019910005804A KR100199686B1 (ko) | 1990-04-11 | 1991-04-11 | 기체상 올레핀 중합법 |
Country Status (27)
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US (1) | US5283278A (ko) |
EP (1) | EP0453116B1 (ko) |
JP (1) | JPH04225004A (ko) |
KR (1) | KR100199686B1 (ko) |
CN (1) | CN1070502C (ko) |
AT (1) | ATE121426T1 (ko) |
AU (1) | AU631306B2 (ko) |
BG (1) | BG94227A (ko) |
BR (1) | BR9101479A (ko) |
CA (1) | CA2039627C (ko) |
CS (1) | CS100791A2 (ko) |
DE (1) | DE69108975T2 (ko) |
ES (1) | ES2072543T3 (ko) |
FI (1) | FI99226C (ko) |
FR (1) | FR2660926B1 (ko) |
HU (1) | HU208983B (ko) |
MX (1) | MX25306A (ko) |
MY (1) | MY109721A (ko) |
NO (1) | NO177718C (ko) |
NZ (1) | NZ237744A (ko) |
PL (1) | PL289849A1 (ko) |
PT (1) | PT97323B (ko) |
RO (1) | RO109544B1 (ko) |
RU (1) | RU2099358C1 (ko) |
TW (1) | TW209226B (ko) |
YU (1) | YU64791A (ko) |
ZA (1) | ZA912549B (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100721746B1 (ko) * | 2000-03-06 | 2007-05-25 | 이네오스 유럽 리미티드 | 올레핀 중합 동안 시팅 및 응집체를 감소시키는 방법 |
Families Citing this family (152)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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- 1991-04-05 ZA ZA912549A patent/ZA912549B/xx unknown
- 1991-04-08 US US07/681,884 patent/US5283278A/en not_active Expired - Lifetime
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- 1991-04-11 CN CN91102402A patent/CN1070502C/zh not_active Expired - Fee Related
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100721746B1 (ko) * | 2000-03-06 | 2007-05-25 | 이네오스 유럽 리미티드 | 올레핀 중합 동안 시팅 및 응집체를 감소시키는 방법 |
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