JP4216185B2 - エチレンポリマー組成物 - Google Patents
エチレンポリマー組成物 Download PDFInfo
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- JP4216185B2 JP4216185B2 JP2003506358A JP2003506358A JP4216185B2 JP 4216185 B2 JP4216185 B2 JP 4216185B2 JP 2003506358 A JP2003506358 A JP 2003506358A JP 2003506358 A JP2003506358 A JP 2003506358A JP 4216185 B2 JP4216185 B2 JP 4216185B2
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- ethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Description
−第1反応器ではエチレンは、希釈剤、酸素、遷移金属ベースの触媒、及び共触媒を含む媒体中の懸濁液で重合され、総重量に対して53−63重量%のエチレンポリマー(A)の組成物を形成する、
−さらに、ポリマー(A)を含む前記媒体は前記反応器から取り除かれて膨張にかけられて少なくとも一部の水素をガス抜きする、その後、
−ポリマー(A)といくらかのエチレンを有する少なくとも部分的にガス抜きされた前記媒体と4〜10個の炭素原子を含む少なくとも別のαオレフィンは別の反応器に導入され、そこで懸濁液中での重合が行われ、総重量に対して37−47重量%のエチレンのコポリマー(B)の組成物を形成する。
−遷移金属の10−30重量%、好ましくは15−20重量%と、
−マグネシウムの0.5−20重量%、好ましくは1−10重量%と、
−塩素などのハロゲン20−60重量%、好ましくは30−50重量%と、
−アルミニウムの0.1−10重量%、好ましくは0.5−5重量%とからなる触媒で良い結果が得られた。一般的に残りは炭素、水素、酸素などの製造用に使用される製品から生じる元素からなる。これらの触媒はハロゲン化有機アルミニウム組成物によって少なくとも1つの遷移金属組成物とマグネシウム組成物の共沈により得られることが好ましい。そのような触媒は米国特許3901863号明細書、米国特許42942200号明細書、米国特許4617360号明細書に特に記載されている。触媒は第1重合反応器にのみ導入されることが好ましい。つまり、別の重合反応器へ新鮮な触媒を導入することはない。
−作製基準ISO/DIS16770.2(2001)(80℃、5.0MPaの応力下(Arkopal N110 2%溶液中))に記載される方法によって測定された場合、破裂時間によって示された一般的に100時間より長い良好な遅い亀裂伝播耐性(FNCT)と、
−ISO基準F/DIS13477(1996)に記載された方法S4に従って0℃でパイプの直径110mmと厚さ10mmで測定された場合、一般的に少なくとも10バールに等しい内部圧力で亀裂伝播の停止によって示される良好な急速亀裂伝播耐性(RCP)と、
−基準ISO/TR9080に従ってMRS10評価より高いMRS評価に帰属することを可能にする良好な長期圧力耐性と、
によって特徴付けられる。典型的に、本発明の組成物から製造されるパイプは圧力耐性を有し、基準ISO/TR9080に従って11.2又は12.5のMRS評価に帰属することを可能にする。
Q=コポリマー(B)のコモノマー含量、先に述べたように測定されたモル%で表される。
QT=組成物のコモノマー含量、モル%で表される。この含量はコポリマー(B)のコモノマー含量に対して先に説明されたように測定される。
(a)触媒の調製
マグネシウムジエチレートはチタニウムテトラブチレートとチタニウムとマグネシウムのモル比が2に等しい量で150℃で4時間反応させて生成された。その後、得られた反応生成物は二塩化エチルアルミニウム溶液と90分間45℃で接触してそれを置くことによって沈殿する。こうして得られた触媒は懸濁液から集められ、(重量%で)Ti:17、Cl:41、Al:2、Mg:5を含む。
ヘキサン、エチレン、水素、トリエチルアルミニウムと事項(a)に記載された触媒は重合反応器に導入され、エチレンは90℃で1時間33分重合された。反応器中の水素/エチレンのモル比は0.4であった。
得られたポリマーの特徴は表1に示される。
イソブタン、エチレン、水素、1−ブテン、トリエチルアルミニウムと事項(a)に記載された触媒は重合反応器に導入され、エチレンは75℃で55分間重合された。水素/エチレンと1−ブテン/エチレンのモル比はそれぞれ0.000と1.009であった。
事項(b)に記載されたポリマー(A)600gは事項(c)に記載されたコポリマー(B)400gと押出機で混合された。それによって得られた混合物は粒状化され、その特徴が測定された。それらは表1に示される。
異なる量を含む組成物または実施例1(c)に記載されるコポリマー(B)と異なるコポリマーが製造された。これらの組成物の特徴と特性は表1に示される。
異なる量を含む本発明に合致する組成物または実施例1(c)に記載されるコポリマー(B)と異なるコポリマーが製造された。これらの組成物の特徴と特性は表1に示される。
イソブタンの懸濁液中のエチレンポリマー組成物は直列に連結された2つのループ反応器で製造され、連続的に圧力膨張を行うことを可能にする装置によって分離された。
実施例10を繰り返すが表3に記載された他の組成物を得るために重合条件(表2参照)を変えている。
Claims (11)
- 密度が少なくとも950kg/m3で流動性指数MI5が0.05−2g/10分で4〜10個の炭素原子を含むαオレフィン含量が0.15−1モル%である組成物であって、流動性指数MI2が少なくとも100g/10分で密度が少なくとも969kg/m3で分子量分布Mw/Mnが4より大きく、総重量に基づいて53−63重量%のエチレンホモポリマー(A)と、流動性指数MI5が0.001−0.5g/10分で密度が930kg/m3以下で分子量分布Mw/Mnが4より大きく、エチレンと0.32−2.7モル%の4〜10個の炭素原子を有する少なくとも1個のαオレフィンである1−ブテンまたは1−ヘキセンのいずれかとからなるコポリマー(B)であって総重量に基づいて37−47重量%の前記コポリマー(B)とを含み、ここで前記ホモポリマー(A)の前記MI2と前記コポリマー(B)の前記MI5の比率は25000より大きい組成物。
- 密度が952kg/m3と960kg/m3の間であることを特徴とする請求項1記載の組成物。
- MI5が少なくとも0.1g/10分であって1g/10分を超えないことを特徴とする請求項1記載の組成物。
- 総重量に対して少なくとも55重量%の前記エチレンホモポリマー(A)を含むことを特徴とする請求項1乃至3いずれかに記載の組成物。
- 総重量に対して57−62重量%の前記エチレンホモポリマー(A)と総重量に対して38−43重量%の前記コポリマー(B)とを含むことを特徴とする請求項4記載の組成物。
- 4〜10個の炭素原子を含む前記αオレフィンから派生する少なくとも0.2モル%及び多くて0.7モル%のモノマー単位を含むことを特徴とする請求項1乃至5いずれかに記載の組成物。
- 前記αオレフィンは1−ブテン及び/又は1−ヘキセンであることを特徴とする請求項1乃至6いずれかに記載の組成物。
- 作製基準ISO/DIS16770.2(2001)(80℃、5.0MPaの応力下(Arkopal N110 2%溶液中))に記載される方法で測定されたとおり破裂時間によって示されたFNCTが100時間より長い請求項1乃至7いずれかに記載の組成物。
- 基準ISO/TR9080に従って11.2かそれよりよいMRS評価を有する請求項1乃至8いずれかに記載の組成物。
- パイプ製造用である請求項1乃至9いずれかに定義された組成物の使用法。
- 請求項1乃至9いずれかに記載の組成物の押出しからなるパイプ製造用の方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01202288A EP1266933A1 (fr) | 2001-06-14 | 2001-06-14 | Composition de polymères d'éthylène |
PCT/EP2002/006370 WO2002102891A1 (en) | 2001-06-14 | 2002-06-10 | Ethylene polymer composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004530761A JP2004530761A (ja) | 2004-10-07 |
JP4216185B2 true JP4216185B2 (ja) | 2009-01-28 |
Family
ID=8180477
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003506358A Expired - Fee Related JP4216185B2 (ja) | 2001-06-14 | 2002-06-10 | エチレンポリマー組成物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7232866B2 (ja) |
EP (2) | EP1266933A1 (ja) |
JP (1) | JP4216185B2 (ja) |
KR (1) | KR100849051B1 (ja) |
AT (1) | ATE476473T1 (ja) |
DE (1) | DE60237207D1 (ja) |
ES (1) | ES2350088T3 (ja) |
WO (1) | WO2002102891A1 (ja) |
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EP1359192A1 (en) * | 2002-04-30 | 2003-11-05 | Solvay Polyolefins Europe-Belgium (Société Anonyme) | Polyethylene pipe resins |
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EP1605014A1 (en) | 2004-06-09 | 2005-12-14 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Polyethylene pipe fitting resins |
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US7312279B2 (en) | 2005-02-07 | 2007-12-25 | Univation Technologies, Llc | Polyethylene blend compositions |
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CA2657305A1 (en) * | 2006-07-12 | 2008-01-17 | Ineos Manufacturing Belgium Nv | Ethylene polymer composition |
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EP1909014B2 (en) | 2006-10-04 | 2013-08-14 | Borealis Technology Oy | Polyethylene composition for pressure pipes with enhanced flexibility |
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EP2199331A1 (en) | 2008-12-22 | 2010-06-23 | Borealis AG | Polyolefin composition for water pipes with improved chlorine resistance |
EP2199330A1 (en) | 2008-12-22 | 2010-06-23 | Borealis AG | Polyolefin composition for water pipes with good resistance to chlorine dioxide and low migration |
EP2199327A1 (en) | 2008-12-22 | 2010-06-23 | Borealis AG | Polyolefin composition for water pipes with increased resistance to chlorine dioxide |
EP2410011A1 (en) | 2010-07-23 | 2012-01-25 | INEOS Manufacturing Belgium NV | Polyethylene composition |
EP2511332B1 (en) | 2011-04-15 | 2014-09-17 | Borealis AG | Polyolefin pipe with improved migration behaviour |
EP2543715B1 (en) | 2011-07-05 | 2017-11-01 | Borealis AG | Use of carbon black and antioxidants for reducing taste and/or odour in a polyolefin composition |
EP2551295B1 (en) | 2011-07-25 | 2018-09-12 | Borealis AG | Polyolefin composition for pipes and fittings with increased resistance to chlorine dioxide |
EP2551297B1 (en) | 2011-07-25 | 2014-03-12 | Borealis AG | Polyolefin composition with excellent colour and thermal stability as well as oxidation resistance for pipes |
PL2551294T3 (pl) | 2011-07-25 | 2019-06-28 | Borealis Ag | Zastosowanie kompozycji poliolefinowej do rur i kształtek o ulepszonej odporności na ditlenek chloru |
ES2530869T3 (es) | 2011-12-22 | 2015-03-06 | Borealis Ag | Composición de poliolefina con resistencia incrementada a la degradación causada por el dióxido de cloro |
EP2690115B1 (en) | 2012-07-24 | 2018-02-21 | Borealis AG | Slow partial cross-linking polyolefin composition for improving disinfectant resistance of an article |
EP2725057B2 (en) | 2012-10-24 | 2022-08-24 | Borealis AG | Use of an acid scavenger to increase the resistance of a polyolefin composition against disinfectant containing water |
EP2746324A1 (en) | 2012-12-21 | 2014-06-25 | Borealis AG | Use of pigments and additives for improving pipe stability against desinfectant containing water |
PL2818504T3 (pl) | 2013-06-28 | 2021-03-08 | Borealis Ag | Zastosowanie środków ułatwiających wytłaczanie do produkcji barwionych rur polietylenowych |
ES2752741T3 (es) | 2016-09-12 | 2020-04-06 | Thai Polyethylene Co Ltd | Tubería de polietileno multimodal |
RU2759904C2 (ru) * | 2016-09-12 | 2021-11-18 | Тай Полиэтилен Ко., Лтд. | Бимодальная полиэтиленовая композиция и содержащая ее труба |
HUE047424T2 (hu) | 2016-09-12 | 2020-04-28 | Thai Polyethylene Co Ltd | Multimodális polietilén vékony film |
HUE047204T2 (hu) | 2016-09-12 | 2020-04-28 | Thai Polyethylene Co Ltd | Reaktorrendszer multimodális polietilén polimerizáláshoz |
EP3293211B1 (en) | 2016-09-12 | 2019-06-26 | Thai Polyethylene Co., Ltd. | Multimodal polyethylene screw cap |
PT3293210T (pt) | 2016-09-12 | 2019-06-12 | Scg Chemicals Co Ltd | Película de polietileno multimodal |
ES2755384T3 (es) | 2016-09-12 | 2020-04-22 | Thai Polyethylene Co Ltd | Contenedor de polietileno multimodal |
EP3293214B1 (en) | 2016-09-12 | 2019-12-25 | Thai Polyethylene Co., Ltd. | High performances multimodal ultra high molecular weight polyethylene |
HUE047268T2 (hu) | 2016-09-12 | 2020-04-28 | Thai Polyethylene Co Ltd | Többmódusú polietilén csõ |
US11214669B2 (en) * | 2018-03-21 | 2022-01-04 | Lg Chem, Ltd. | Polyolefin resin composition and stretch film using the same |
CN112368501B (zh) | 2018-05-18 | 2023-01-31 | 阿布扎比聚合物有限责任公司(博禄) | 改善热塑性聚烯烃组合物的流变性能 |
WO2020157285A1 (en) | 2019-01-31 | 2020-08-06 | Borealis Ag | Polyethylene composition comprising carbonaceous structures and having improved mechanical properties |
EP3988587A1 (en) | 2020-10-26 | 2022-04-27 | Borealis AG | Polyolefin pipe resin with very good sagging and slow crack growth resistance |
EP4092079A1 (en) | 2021-05-21 | 2022-11-23 | Borealis AG | Process for producing polyethylene pipes with high pressure resistance and polyethylene pipes obtained thereby |
EP4201969A1 (en) | 2021-12-23 | 2023-06-28 | Borealis AG | Polyethylene composition for pipes having very good impact properties and slow crack growth resistance |
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KR930006091A (ko) * | 1991-09-18 | 1993-04-20 | 제이 이이 휘립프스 | 폴리에틸렌 블렌드 및 그로부터 제조된 필름, 병 또는 파이프 |
BE1006439A3 (fr) | 1992-12-21 | 1994-08-30 | Solvay Societe Annonyme | Procede de preparation d'une composition de polymeres d'ethylene, composition de polymeres d'ethylene et son utilisation. |
BE1011333A3 (fr) | 1997-08-20 | 1999-07-06 | Solvay | Procede de fabrication d'une composition de polymeres d'ethylene. |
DE19929812A1 (de) * | 1999-06-30 | 2001-01-04 | Elenac Gmbh | Polyethylen Formmasse und daraus hergestelltes Rohr mit verbesserten mechanischen Eigenschaften |
EP1199161A1 (en) | 2000-10-20 | 2002-04-24 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Polyethylene pipe |
-
2001
- 2001-06-14 EP EP01202288A patent/EP1266933A1/fr not_active Withdrawn
-
2002
- 2002-06-10 ES ES02727611T patent/ES2350088T3/es not_active Expired - Lifetime
- 2002-06-10 WO PCT/EP2002/006370 patent/WO2002102891A1/en active Application Filing
- 2002-06-10 KR KR1020037016364A patent/KR100849051B1/ko active IP Right Grant
- 2002-06-10 US US10/480,548 patent/US7232866B2/en not_active Expired - Lifetime
- 2002-06-10 AT AT02727611T patent/ATE476473T1/de not_active IP Right Cessation
- 2002-06-10 EP EP02727611A patent/EP1406967B1/en not_active Expired - Lifetime
- 2002-06-10 JP JP2003506358A patent/JP4216185B2/ja not_active Expired - Fee Related
- 2002-06-10 DE DE60237207T patent/DE60237207D1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
WO2002102891A1 (en) | 2002-12-27 |
ES2350088T3 (es) | 2011-01-18 |
US7232866B2 (en) | 2007-06-19 |
EP1406967A1 (en) | 2004-04-14 |
ATE476473T1 (de) | 2010-08-15 |
KR20040012932A (ko) | 2004-02-11 |
DE60237207D1 (de) | 2010-09-16 |
JP2004530761A (ja) | 2004-10-07 |
US20040204542A1 (en) | 2004-10-14 |
EP1406967B1 (en) | 2010-08-04 |
EP1266933A1 (fr) | 2002-12-18 |
KR100849051B1 (ko) | 2008-07-30 |
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