KR100620358B1 - 강성, 내충격성, 내열성이 우수한 올레핀의 중합방법 - Google Patents
강성, 내충격성, 내열성이 우수한 올레핀의 중합방법 Download PDFInfo
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- KR100620358B1 KR100620358B1 KR1020010058251A KR20010058251A KR100620358B1 KR 100620358 B1 KR100620358 B1 KR 100620358B1 KR 1020010058251 A KR1020010058251 A KR 1020010058251A KR 20010058251 A KR20010058251 A KR 20010058251A KR 100620358 B1 KR100620358 B1 KR 100620358B1
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- compound
- catalyst
- olefin polymerization
- silane
- olefin
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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
- 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
- C08F4/656—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
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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
- 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
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
Abstract
Description
실시예 | 비교예 | ||||
1 | 2 | 3 | 1 | ||
물성 | 용융지수(g/10 min) | 4 | 3 | 4 | 3 |
굴곡강도 (kgf/cm2) | 560 | 555 | 495 | 500 | |
굴곡탄성율(kgf/cm2) | 18,500 | 18,500 | 16,300 | 16,500 | |
아이조드 충격강도(kg cm/cm) | 5.8 | 5.0 | 4.8 | 3 | |
열변형온도(℃) | 122 | 119 | 118 | 110 | |
경도(R-scale) | 99 | 100 | 97 | 95 |
Claims (10)
- 다음의 단계를 포함하여 이루어지는 방법에 의하여 제조된, 촉매주위에 고분자량단량체가 캡슐화된 전중합 촉매를 이용하여 중합을 행하는 것을 특징으로 하는 올레핀 중합방법.(i) 올레핀 중합용 고체 티타늄촉매를 두 개 이상의 비닐기를 가지는 실란화합물로 표면처리하는 단계;(ii) 상기 표면처리된 고체 티타늄촉매로 올레핀 단량체와 1,3-부타디엔, 1,5-헥사디엔, 1,7-옥타디엔, 1,9-데카디엔, 또는 1,13-테트라데카디엔 중에서 선택되는 1이상의 디엔화합물을 전중합반응시키는 단계.
- 제1항에 있어서, 상기 고체 티타늄촉매는 다음의 단계를 포함하여 이루어지는 방법에 의하여 제조되는 것임을 특징으로 하는 올레핀 중합방법:(a) 환원성이 없는 마그네슘 화합물을 전자공여체에 용해하여 마그네슘 화합물 용액을 제조하는 단계;(b) 상기 마그네슘 화합물 용액을 전이금속 화합물, 실리콘 화합물, 주석화합물 또는 이들의 혼합물과 반응시켜 고형의 입자를 침전시키는 단계; 및(c) 상기 침전된 고형의 입자와 티타늄 화합물 및 전자공여체를 반응시키는 단계.
- 제1항에 있어서, 상기 두 개 이상의 비닐기를 가지는 실란화합물은 디비닐디메틸실란, 디비닐디페닐실란, 디비닐디에틸실란, 디비닐디이소부틸실란 또는 디비닐디히드라이드실란인 것을 특징으로 하는 올레핀 중합방법.
- 제1항에 있어서, 상기 두 개 이상의 비닐기를 가지는 실란화합물의 사용량은 마그네슘 화합물 1몰당 2몰 내지 200몰인 것을 특징으로 하는 올레핀 중합방법.
- 제1항에 있어서, 전중합단계에서 사용되는 올레핀 단량체는 에틸렌, 프로필렌, 부텐, 1-헥센 또는 1-옥텐 중에서 선택되는 1종 이상인 것을 특징으로 하는 올레핀 중합방법.
- 제1항에 있어서, 상기 촉매 주위에 캡슐화한 고분자량단량체는 중량평균분자량이 500 내지 100,000의 범위이며, 올레핀이 1∼99중량%, 디엔이 0.01∼10중량%, 실란계 물질이 0.001∼1중량%로 이루어진 것을 특징으로 하는 올레핀 중합방법.
- 제1항 내지 제6항 중 어느 한항에 있어서, 상기 전중합 촉매(A)와 함께 다음의 성분들을 사용하는 것을 특징으로 하는 올레핀 중합방법:(B) 주기율표의 제I족 또는 제Ⅲ족 금속의 유기금속 화합물 및(C) 외부전자공여체.
- 제7항에 있어서, 상기 (B)성분의 유기금속화합물은 트리알킬알루미늄인 것을 특징으로 하는 올레핀 중합방법.
- 제7항에 있어서, 상기 (C)성분의 외부전자공여체는 알콕시실란 화합물인 것을 특징으로 하는 올레핀 중합방법.
- 제7항의 방법에 의하여 중합되어, 용융지수가 0.1∼50g/10분이고, 겔투과크로마토그래피법(GPC)으로 측정한 분자량분포가 3∼20이며, 폴리프로필렌 수지 100중량부에 대하여 전중합물 함량이 0.001∼30 중량부로 이루어진 것을 특징으로 하는 폴리프로필렌 수지.
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KR1020010058251A KR100620358B1 (ko) | 2001-09-20 | 2001-09-20 | 강성, 내충격성, 내열성이 우수한 올레핀의 중합방법 |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03119004A (ja) * | 1989-09-21 | 1991-05-21 | Amoco Corp | 広い分子量分布の生成物を製造するためのシラン変性支持ポリオレフィン触媒 |
JPH04293910A (ja) * | 1991-03-22 | 1992-10-19 | Mitsubishi Petrochem Co Ltd | オレフィン重合体の製造 |
JPH072923A (ja) * | 1993-06-15 | 1995-01-06 | Mitsubishi Chem Corp | オレフィンの重合法 |
JPH0725927A (ja) * | 1993-07-15 | 1995-01-27 | Mitsubishi Chem Corp | オレフィンの重合法 |
KR20010113221A (ko) * | 2000-06-17 | 2001-12-28 | 유현식 | 올레핀 중합용 촉매 및 중합방법 |
KR20020034817A (ko) * | 2000-10-30 | 2002-05-09 | 유현식 | 올레핀 중합방법 및 고용융장력의 수지조성물 |
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2001
- 2001-09-20 KR KR1020010058251A patent/KR100620358B1/ko active IP Right Grant
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03119004A (ja) * | 1989-09-21 | 1991-05-21 | Amoco Corp | 広い分子量分布の生成物を製造するためのシラン変性支持ポリオレフィン触媒 |
JPH04293910A (ja) * | 1991-03-22 | 1992-10-19 | Mitsubishi Petrochem Co Ltd | オレフィン重合体の製造 |
JPH072923A (ja) * | 1993-06-15 | 1995-01-06 | Mitsubishi Chem Corp | オレフィンの重合法 |
JPH0725927A (ja) * | 1993-07-15 | 1995-01-27 | Mitsubishi Chem Corp | オレフィンの重合法 |
KR20010113221A (ko) * | 2000-06-17 | 2001-12-28 | 유현식 | 올레핀 중합용 촉매 및 중합방법 |
KR20020034817A (ko) * | 2000-10-30 | 2002-05-09 | 유현식 | 올레핀 중합방법 및 고용융장력의 수지조성물 |
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