KR940014457A - 올레핀 중합용 촉매 성분 및 촉매 - Google Patents
올레핀 중합용 촉매 성분 및 촉매 Download PDFInfo
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- KR940014457A KR940014457A KR1019930027080A KR930027080A KR940014457A KR 940014457 A KR940014457 A KR 940014457A KR 1019930027080 A KR1019930027080 A KR 1019930027080A KR 930027080 A KR930027080 A KR 930027080A KR 940014457 A KR940014457 A KR 940014457A
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- 239000003054 catalyst Substances 0.000 title claims abstract 27
- 150000001336 alkenes Chemical class 0.000 title claims abstract 12
- 238000006116 polymerization reaction Methods 0.000 title claims abstract 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract 8
- 238000000034 method Methods 0.000 claims abstract 14
- -1 magnesium halide Chemical class 0.000 claims abstract 13
- 239000010936 titanium Substances 0.000 claims abstract 8
- 239000011777 magnesium Substances 0.000 claims abstract 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract 6
- 150000003609 titanium compounds Chemical class 0.000 claims abstract 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 5
- 150000002367 halogens Chemical class 0.000 claims abstract 4
- 239000011148 porous material Substances 0.000 claims abstract 3
- 238000004438 BET method Methods 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims 19
- 125000004432 carbon atom Chemical group C* 0.000 claims 13
- 125000000217 alkyl group Chemical group 0.000 claims 9
- 150000005840 aryl radicals Chemical group 0.000 claims 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims 7
- 238000006243 chemical reaction Methods 0.000 claims 6
- 239000004215 Carbon black (E152) Substances 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 4
- 229930195733 hydrocarbon Natural products 0.000 claims 4
- 229910052739 hydrogen Inorganic materials 0.000 claims 3
- 239000001257 hydrogen Substances 0.000 claims 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical group CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 150000001993 dienes Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000008378 aryl ethers Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 230000000415 inactivating effect Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052753 mercury Inorganic materials 0.000 abstract 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- 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
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- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F10/08—Butenes
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Abstract
본 발명은 1이상의 Ti-할로겐 결합을 함유하여 임의로 Ti 1몰당 0.5몰 미만의 할로겐과는 다른 기를 함유하는, 마그네슘 할라이드 상에 담지된 티타늄 화합물을 포함함을 특징으로 하는, 올레핀 중합용 구형의 고형 촉매 성분에 관한 것이다.
본 발명의 구형의 고형 성분은 BET법으로 측정한 표면적이 70m2/g미만, 수은법으로 측정한 총 다공도가 약 0.5cm3/g보다 크며 기공 반경의 50% 이상의 800A보다 큼을 특징으로 한다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (32)
1이상의 Ti-할로겐 결합 및 임의로 Ti 1몰에 대하여 0.5몰 미만의 양으로 할로겐과는 다른 기를 함유하는, 마그네슘 할라이드 상에 담지된 티타늄 화합물을 함유하며, BET 법으로 측정한 표면적이 70m2/g미만이고, 수은법으로 측정한 총 다공도가 0.5cc/g보다 크며 기공반경의 50% 이상의 800Å보다 큼을 특징으로 하는, 올레핀 CH2=CHR(식중, R은 수소 또는 탄소수 1~12의 탄화수소 라디칼임) 중합용 구형의 촉매 성분.
제 1항에 있어서, 총 다공도가 0.6~1.2cc/g이며 표면적이 30~70m2/g인 구형의 촉매성분.
제 1항 또는 2항에 있어서, 기공의 80% 이상의 반경이 15000Å 이하이고 다공도가 0.6~0.9cc/g인 구형의 촉매 성분.
제 1항 또는 2항에 있어서, 마그네슘 할라이드에 대한 전자 공여 화합물(내부 공여제)의 몰비가 1:2~1:20인 구형의 촉매 성분.
제 1항 또는 2항에 있어서, 마그네슘 할라이드가 MgCl2인 구형의 촉매 성분.
제 1항 또는 2항에 있어서, 티타늄 화합물의 일반식이 Ti(OR)nXy-n(식중, n은 0~0.5이며 Y는 티타늄의 원자가이고 X는 할로겐이며 R은 탄소수 2~8의 알킬, 시클로알킬 또는 아릴 라디칼이거나 COR기이다)인 구형의 촉매 성분.
제 6항에 있어서, y가 4이고 n은 0~0.02인 구형의 촉매 성분.
제 6항에 있어서, y가 3이고 n이 0~0.015인 구형의 촉매 성분.
제 4항에 있어서, 전자 공여 화합물이 알킬, 시클로알킬, 아릴 에테르 및 폴리카르복실산의 에스테르로부터 선택되는 구형의 촉매 성분.
제 4항에 있어서, 전자 공여 화합물이 하기 일반식의 1,3-디에테르로부터 선택되는 구형의 촉매 성분.
(상기 식에서, RI및 RII는 서로 동일하거나 상이하며 탄소수 1~18의 알킬, 시클로알킬, 아릴 라디칼이며, RIII및 RIV는 서로 동일하거나 상이하며 탄소수 1~4의 알킬라디칼이다.)
제1항에 따른 촉매 성분과 A1-알킬 화합물과의 반응 생성물을 함유함을 특징으로 하는 올레핀 중합용 촉매.
제 11항에 있어서, A1-알킬 화합물이 A1-트리알킬인 촉매.
제 4항에 따른 촉매 성분과 A1-알킬 화합물과의 반응 생성물을 함유함을 특징으로 하는 올레핀 중합용 촉매.
제 4항에 따른 촉매 성분, A1-알킬 화합물 및 전자 공여 화합물(외부 공여제)과의 반응 생성물을 함유함을 특징으로 하는 올레핀 중합용 촉매.
제 14항에 있어서, 외부 전자 공여 화합물이 하기 일반식의 1,3-디에테르로 부터 선택되는 촉매:
(상기 식에서, RI및 RII는 서로 동일하거나 상이하며 탄소수 1~18의 알킬, 시클로알킬, 아릴 라디칼이며, RIII및 RIV는 서로 동일하거나 상이하며 탄소수 1~4의 알킬 라디칼이다.)
제 9항에 따른 촉매 성분, A1-알킬 화합물 및 일반식 R1 4-nSi(ORIII)n(식주, RI은 탄소수 1~18의 알킬, 시클로알킬, 아릴 라디칼이고 RIII는 탄소수 1~4의 알킬 라디칼이며 n은 1~3의 수이다.)의 실란으로부터 선택된 전자 공여 화합물(외부 공여제)의 반응 생성물을 함유함을 특징으로 하는 올레핀 중합용 촉매.
-(a) 화합물 MgCl2·mROH(식중, 0≤m≤0.5이며 R은 탄소수 1~12의 알킬, 시클로알킬 또는 아릴 라디칼이다), R은 탄소수 2~8의 알킬 라디칼 또는 COR기이다)간의 반응으로 구성되어 있으며, 화합물 (a)는 부가물 MgCl2·mROH(식중, 0≤m≤0.5이며 R은 탄소수 1~12의 알킬, 시클로알킬 또는 아릴라디칼이다), 및 -(b) 티타늄 화합물 Ti(OR)nXy-n(식중, n은 0~0.5이며 y는 티타늄의 원자가이고 X는 할로겐이며, R은 탄소수 2~8의 알킬 라디칼 또는 COR기이다)간의 반응으로 구성되어 있으며, 화합물 (a)는 부가물 MgCl2·qROH(식중, 2.5≤q≤3.5)의 열적 탈알콜후, 부가물 MgCl2·pROH(식중, 0.1≤p≤2)의 화학적 탈알콜에 의해 제조됨을 특징으로 하는 올레핀 CHl2=CHR(식중, R은 수소 또는 탄소수 1~12의 탄화수소 라디칼임)의 중화용 구형의 촉매 성분의 제조방법.
제17항에 있어서, 화합물(b)와 화합물(a)와의 반응에서 Ti/Mg비가 0.05~3인 제조방법.
제17항에 있어서, 화합물(b)와 화합물(a)와의 반응에서 Ti/Mg비가 3보다 큰 제조방법.
제17항에 있어서, 마그네슘 할라이드에 대한 몰비가 1:2~1:20인 전자 공여 화합물(내부 공여제)의 존재하에 반응을 수행하는 제조방법.
제17항에 있어서, 티타늄 화합물이 TiCl4인 제조방법.
제21항에 있어서, 반응에 액체 TiCl4또는 탄화수소 용액 중에서 수행되는 제조방법.
제17항에 있어서, 부가물 MgCl2·pROH의 탈알콜이 A1-알킬 화합물을 사용하여 수행되는 제조방법.
제23항에 있어서, 화합물(b)와의 반응 전에, 화합물(a)를 A1-알킬 화합물을 불활성화시키는 시약으로 처리하는 제조방법.
제24항에 있어서, 불활성화제가 산소인 제조방법.
제17항에 있어서, 환원 화합물을 사용하는 제조방법.
제26항에 있어서, 환원 화합물이 Al-트리알킬 또는 A1-알킬 할라이드인 제조방법.
제27항에 있어서, 환원 화합물이 A12Et3Cl3인 제조방법.
제11항에 따른 촉매를 사용함을 특징으로 하는, 올레핀 CH2=CHR(식중, R은 수소 또는 탄소수 1~12의 탄화수소 라디칼이다)의 중합 방법.
제11항 내지 13항에 따른 촉매를 사용함을 특징으로 하는, 임의로 소량의 디엔 존재하에서의 에틸렌 및 그의 혼합물과 올레핀 CH2=CHRv(식중, Rv는 탄소수 1~12의 알킬, 시크로알킬 또는 아릴 라디칼이다)과의 중합 방법.
제30항에 있어서, 올레핀 CH2=CHRv가 1-부텐, 1-펜텐, 1-헥센, 4-메틸-펜텐-1, 1-옥텐으로 부터 선택된 중합 방법.
제14항 내지 16항에 따른 촉매를 사용함을 특징으로 하는, 임의로 소량의 디엔 존재하에서의 프로필렌 및 그의 혼합물과 올레핀 CH2=CHR과의 중합 방법.
※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI922822A IT1256648B (it) | 1992-12-11 | 1992-12-11 | Componenti e catalizzatori per la polimerizzazione delle olefine |
| ITMI92A002822 | 1992-12-11 |
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| Publication Number | Publication Date |
|---|---|
| KR940014457A true KR940014457A (ko) | 1994-07-18 |
| KR100289267B1 KR100289267B1 (ko) | 2001-05-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019930027080A KR100289267B1 (ko) | 1992-12-11 | 1993-12-09 | 올레핀 중합용 촉매 성분 및 촉매 |
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|---|---|
| US (1) | US6388028B2 (ko) |
| EP (1) | EP0601525B1 (ko) |
| JP (1) | JP4023833B2 (ko) |
| KR (1) | KR100289267B1 (ko) |
| CN (2) | CN1034580C (ko) |
| AT (1) | ATE176676T1 (ko) |
| AU (1) | AU673551B2 (ko) |
| BR (1) | BR9305019A (ko) |
| CA (1) | CA2111308A1 (ko) |
| DE (1) | DE69323478T2 (ko) |
| ES (1) | ES2129063T3 (ko) |
| FI (1) | FI112240B (ko) |
| IL (1) | IL107958A (ko) |
| IT (1) | IT1256648B (ko) |
| MX (1) | MX9307843A (ko) |
| NO (1) | NO302825B1 (ko) |
| RU (1) | RU2126420C1 (ko) |
| ZA (1) | ZA939210B (ko) |
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Also Published As
| Publication number | Publication date |
|---|---|
| IL107958A0 (en) | 1994-04-12 |
| FI935550A (fi) | 1994-06-12 |
| FI935550A0 (fi) | 1993-12-10 |
| JPH07300507A (ja) | 1995-11-14 |
| ZA939210B (en) | 1994-08-08 |
| FI112240B (fi) | 2003-11-14 |
| EP0601525A1 (en) | 1994-06-15 |
| CN1089622A (zh) | 1994-07-20 |
| NO302825B1 (no) | 1998-04-27 |
| ES2129063T3 (es) | 1999-06-01 |
| MX9307843A (es) | 1994-07-29 |
| IT1256648B (it) | 1995-12-12 |
| ITMI922822A1 (it) | 1994-06-11 |
| AU5229593A (en) | 1994-06-23 |
| JP4023833B2 (ja) | 2007-12-19 |
| ATE176676T1 (de) | 1999-02-15 |
| KR100289267B1 (ko) | 2001-05-02 |
| CA2111308A1 (en) | 1994-06-12 |
| CN1041525C (zh) | 1999-01-06 |
| DE69323478D1 (de) | 1999-03-25 |
| US6388028B2 (en) | 2002-05-14 |
| CN1034580C (zh) | 1997-04-16 |
| DE69323478T2 (de) | 1999-08-19 |
| US20010011060A1 (en) | 2001-08-02 |
| NO934496L (no) | 1994-06-13 |
| AU673551B2 (en) | 1996-11-14 |
| BR9305019A (pt) | 1994-07-05 |
| CN1127262A (zh) | 1996-07-24 |
| NO934496D0 (no) | 1993-12-09 |
| EP0601525B1 (en) | 1999-02-10 |
| RU2126420C1 (ru) | 1999-02-20 |
| ITMI922822A0 (it) | 1992-12-11 |
| IL107958A (en) | 1998-09-24 |
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