JP5555183B2 - ポリエチレン組成物、その生成方法、それから作製される製品、およびその製品の作製方法 - Google Patents
ポリエチレン組成物、その生成方法、それから作製される製品、およびその製品の作製方法 Download PDFInfo
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- JP5555183B2 JP5555183B2 JP2010544433A JP2010544433A JP5555183B2 JP 5555183 B2 JP5555183 B2 JP 5555183B2 JP 2010544433 A JP2010544433 A JP 2010544433A JP 2010544433 A JP2010544433 A JP 2010544433A JP 5555183 B2 JP5555183 B2 JP 5555183B2
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- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- C08L23/08—Copolymers of 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
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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
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
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- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
本出願は、2008年1月29日に出願された、「ポリエチレン組成物、その生成方法、それから作製される製品、およびその製品の作製方法」という名称の米国仮出願第61/024,237号の優先権を主張する通常(non-provisional)出願であり、上記出願の教示は、その全体が以下に記載されていることとして、本明細書において参照として組み込まれる。
本発明は、ポリエチレン組成物、その生成方法、それから作製される製品、およびその製品の作製方法に関する。
射出成形品の製造における直鎖状低密度ポリエチレンおよび/または高密度ポリエチレン等のポリエチレン組成物の使用は、一般的に公知である。気相プロセス、スラリープロセス、溶解プロセス、または高圧プロセス等の任意の従来方法を採用して、このようなポリエチレン組成物を生成することができる。
CpaHfXp (1)
(式中、nは1または2、pは1、2または3、Cpはそれぞれ独立してハフニウムに配位したシクロペンタジエニルリガンド、シクロペンタジエニルにアイソローバルなリガンド、またはそれらの置換バージョンであり;Xは、水素化物、ハロゲン化物、C1〜C10アルキル、およびC2〜C12アルケニルからなる群より選択され;nが2の場合、Cpはそれぞれ、C1〜C5アルキレン、酸素、アルキルアミン、シリル-炭化水素、およびシロキシル-炭化水素からなる群より選択される架橋基Aを介して互いと結合している)。C1〜C5アルキレンの例としては、エチレン(--CH2CH2--)架橋基が挙げられ;アルキルアミン架橋基の例としては、メチルアミド(--(CH3)N--)が挙げられ;シリル-炭化水素架橋基の例としては、ジメチルシリル(--(CH3)2Si--)が挙げられ;シロキシル-炭化水素架橋基の例としては、(--O--(CH3)2Si--O--)が挙げられる。特定の一実施形態では、ハフノセン成分は式(1)(式中、nは2、pは1または2である)で表される。
(CpR5)2HfX2 (2)
(式中、Cpはそれぞれシクロペンタジエニルリガンドであって、それぞれハフニウムに配位しており;Rはそれぞれ独立して、水素化物およびC1〜C10アルキル、最も好ましくは水素化物およびC1〜C5アルキルから選択され;Xは、水素化物、ハロゲン化物、C1〜C10アルキルおよびC2〜C12アルケニルからなる群より選択され、より好ましくはXは、水素化物、C2〜C6アルキレンおよびC1〜C6アルキルからなる群より選択され、最も好ましくはXは、塩化物、フッ化物、C1〜C5アルキルおよびC2〜C6アルキレンからなる群より選択される)。最も好適な実施形態において、ハフノセンは、上記式(2)により表され、式中、少なくとも1つのR基は上記定義したアルキル、好ましくはC1〜C5アルキルであり、その他は水素化物である。最も好適な実施形態では、Cpはそれぞれ独立して、メチル、エチル、プロピル、ブチルおよびそれらの異性体からなる群より選択される1、2、3基で置換される。
以下の実施例は、本発明を例示するものであり、本発明の範囲を限定することを意図したものではない。本発明の実施例は、本発明のポリエチレン組成物が、剛性および加工性は維持したままで、分子量分布が狭く、組成分布が狭く、ならびに低温および室温衝撃耐性が改善されたことを実証する。
触媒成分調製
ハフノセン成分は、当該分野で公知の技術により調製できる。例えば、HfCl4(1.00等量)を、-30℃〜-50℃のエーテルに添加し、攪拌して白色懸濁液を得ることができる。次いで、懸濁液を-30℃〜-50℃まで再冷却した後、リチウムプロピルシクロペンタジエニド(2.00等量)を分けて添加する。リチウムプロピルシクロペンタジエニドの添加の際に、反応液は薄茶色になり、懸濁固形物により粘度が高くなる。その後、反応液をゆっくり室温まで温めて、10〜20時間攪拌する。残った茶色の混合液をろ過すると、茶色の固体と淡黄色の溶液が得られる。次に、固体を、当該分野で公知の通りにエーテルで洗浄し、一緒にしたエーテル溶液を真空下で濃縮して、冷たい白色懸濁液を得る。そして、オフホワイトの固体生成物を、ろ過して単離し、真空下で乾燥させる(収率70〜95%)。
触媒組成物は、以下の一般的な手順を使用して約80:1〜130:1のAl/Hfモル比で調製され、完成した触媒に対するハフニウム充填は約0.6〜0.8重量%Hfである。メチルアルミノキサン(MAO)含有トルエンを、きれいで乾燥した容器に入れ、50〜80 rpmおよび華氏60〜100度にて攪拌する。その後、追加のトルエンを攪拌している間に追加できる。次に、ハフノセンを、トルエンに溶解し、MAOと共に容器に入れられる。そして、メタロセン/MAO混合液を、30分間から2時間攪拌すればよい。次に、適量のシリカ(平均粒径22〜28μm、600℃にて脱水したもの)を添加し、さらに1時間以上攪拌する。そして、液体を静かに移し、窒素流の下で攪拌しながら高温で触媒組成物を乾燥させる。
以下の一般的な手順に従って、エチレン/I-ヘキセンコポリマーを生成した。触媒組成物は、シリカ担持ビス(n-プロピルシクロペンタジエニル)二塩化ハフニウムを、メタルモキサンと共に含んでいた(Al:Hf比は約80:1〜130:1)。触媒組成物は、乾燥した状態で、流動床気相重合化反応器に注入された。より具体的には、重合化は、全圧約2068〜2586kPaにて動作する336.5〜419.3 mm ID径の気相流動床反応器において行われた。反応床の重量は約41〜91 kgであった。流動ガスは、約0.49〜0.762 m/秒の速度で床を通るようにした。床から出た流動ガスは、反応器の上部に配置した樹脂離脱ゾーンに入れた。次に、流動ガスは、再利用ループに入り、循環ガス圧縮機および水冷却熱交換器を通した。シェル側水温度を調整して、反応温度を特定値で維持した。エチレン、水素、1-ヘキセン、および窒素を、所望のガス濃度を維持するのに十分な量で、圧縮機のすぐ上流の循環ガスループに供給した。ガス濃度は、オンライン蒸発率分析器によって測定した。生成物(本発明のポリエチレン粒子)を、反応器からパージ容器にバッチ式に取り出した後に、生成物ビンに移した。樹脂中に残った触媒および活性剤は、生成物ドラムにおいて湿り窒素パージによって失活させた。触媒を、ステンレススチール注入管を介して反応床に、所望のポリマー生成速度を維持するのに十分な速度で供給した。この一般的なプロセスを用いて6つの別々の重合化運転が、それぞれ表Iに明記した異なる条件下で行われた。表II〜IVは、それぞれの運転で得られた本発明のポリエチレン組成物1〜6の特性をまとめている。
以下の比較例を提供する。
テスト方法は、以下を含んでいる:
密度(g/cm3)を、ASTM-D792-03、方法Bに従ってイソプロパノール中で測定した。イソプロパノール浴を測定前に熱平衡状態にするために23℃にて8分間調節した後に、試料を、成形の1時間以内に測定した。ASTM D-4703-00添付Aに従い、約190℃にて5分間の初期加熱期間、および手順Cにつき15℃/分の冷却速度にて、試料を圧縮成形した。試料を、「触って冷たくなる」まで連続冷却して、プレスの中で45℃まで冷却した。
Mポリエチレン=A×(Mポリスチレン)B
(式中、Mは分子量、Aは0.41の値を有し、Bは1.0に等しい)。多重検出器オフセットを決定するための系統的アプローチは、Balke、Moureyら(MoureyおよびBalke、Chromatography Polym. 第12章(1992)、ならびにBalke、Thitiratsakul、Lew、Cheung、Mourey、Chromatography Polym. 第13章(1992))の発表に従い、Dow broad polystyrene 1683からの二重検出器log結果をインハウスソフトウェアを使用した狭標準品較正曲線から得た狭標準カラム較正結果に対して最適化して、行った。オフセット決定のための分子量データは、Zimm(Zimm, B.H., J. Chem. Phys., 16, 1099(1948))およびKratochvil(Kratochvil, P., Classical Light Scattering from Poymer Solutions, Elsevier, Oxford, NY(1987))の発表に従って得た。分子量決定のために使用した総注入濃度は、115,000 g/モル分子量の直鎖状ポリエチレンホモポリマーから得たサンプル屈折率面積および屈折率検出器較正から得た(NISTポリエチレンホモポリマー標準品1475を参照して測定)。クロマトグラフィー濃度は、第2ビリアル係数(分子量に対する濃度影響)に対処しない程度に十分に低いと見なした。分子量計算は、インハウスソフトウェアを用いて行った。数平均分子量、重量平均分子量、およびz平均分子量の計算は、以下の式に従って行った(屈折計シグナルは重量分率に正比例すると見なす)。基準値を差し引いた屈折計シグナルは、以下の式において重量分率にそのまま代入できる。分子量は、光散乱対屈折計の比に基づく従来の較正曲線または絶対分子量から得られることを記しておく。z平均分子量の改善された推定、基準値が差し引かれた光散乱シグナルは、以下の式における重量平均分子量および重量分率の積にそのまま代入できる:
、SCBDBを以下の式から計算した:
Claims (18)
1つ以上のαオレフィンコモノマーから誘導された15%重量未満の単位;を含むポリエチレン組成物であって、
密度が0.940〜0.975g/cm 3 、分子量分布(Mw/Mn)が1.70〜3.62であるとともに[(-16.18)(D)]+18.83(Dは前記ポリエチレン組成物の密度である)未満、溶融指数(I2)が2〜1000g/10分、分子量分布(Mz/Mw)が2.5未満、および組成物の骨格に存在する1000炭素原子あたりのビニル不飽和度が0.06ビニル未満である、ポリエチレン組成物。
エチレンと、任意に1つ以上のαオレフィンコモノマーとを、ハフニウム基質メタロセン触媒の存在下で、一段式反応器における気相(共)重合化プロセスにより(共)重合化する工程と;
その結果、密度が0.940g/cm3を上回るが0.975g/cm3以下、分子量分布(Mw/Mn)が1.70〜3.62であるとともに[(-16.18)(D)]+18.83(Dは前記ポリエチレン組成物の密度である)未満、溶融指数(I2)が2〜1000g/10分、分子量分布(Mz/Mw)が2.5未満、および組成物の骨格に存在する1000炭素原子あたりのビニル不飽和度が0.06ビニル未満である前記ポリエチレン組成物を生成する工程と、
を包含する、ポリエチレン組成物の生成プロセス。
密度が0.940g/cm3を上回るが0.975g/cm3以下、分子量分布(Mw/Mn)が1.70〜3.62であるとともに[(-16.18)(D)]+18.83(Dは前記ポリエチレン組成物の密度である)未満、溶融指数(I2)が2〜1000g/10分、分子量分布(Mz/Mw)が2.5未満、および組成物の骨格に存在する1000炭素原子あたりのビニル不飽和度が0.06ビニル未満である、ポリエチレン組成物。
1つ以上のαオレフィンコモノマーから誘導された15%重量未満の単位;を含むポリエチレン組成物であって、
密度が0.940g/cm3を上回るが0.975g/cm3以下、分子量分布(Mw/Mn)が1.70〜3.62であるとともに[(-16.18)(D)]+18.83(Dは前記ポリエチレン組成物の密度である)未満、溶融指数(I2)が2〜1000g/10分、分子量分布(Mz/Mw)が2.5未満、および組成物の骨格に存在する1000炭素原子あたりのビニル不飽和度が0.06ビニル未満であるポリエチレン組成物を含む、射出成形品。
1つ以上のαオレフィンコモノマーから誘導された15%重量未満の単位;を含むポリエチレン組成物であって、
密度が0.940g/cm3を上回るが0.975g/cm3以下、分子量分布(Mw/Mn)が1.70〜3.62であるとともに[(-16.18)(D)]+18.83(Dは前記ポリエチレン組成物の密度である)未満、溶融指数(I2)が2〜1000g/10分、分子量分布(Mz/Mw)が2.5未満、および組成物の骨格に存在する1000炭素原子あたりのビニル不飽和度が0.06ビニル未満であるポリエチレン組成物を選択する工程と;
該ポリエチレン組成物を射出成形する工程と;
その結果、射出成形品を形成する工程;
を包含する、製品の作製プロセス。
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AR070284A1 (es) | 2010-03-25 |
JP2011511107A (ja) | 2011-04-07 |
RU2009146381A (ru) | 2011-06-20 |
CN101778707B (zh) | 2014-05-21 |
MX2009013622A (es) | 2010-01-20 |
RU2487015C2 (ru) | 2013-07-10 |
AU2009209329A1 (en) | 2009-08-06 |
US20100298508A1 (en) | 2010-11-25 |
KR101450936B1 (ko) | 2014-10-14 |
EP2188100B1 (en) | 2012-11-28 |
WO2009097222A1 (en) | 2009-08-06 |
BRPI0903706A2 (pt) | 2020-08-18 |
ES2399313T3 (es) | 2013-03-27 |
AU2009209329B2 (en) | 2013-12-05 |
KR20100115700A (ko) | 2010-10-28 |
TW200942571A (en) | 2009-10-16 |
TWI575009B (zh) | 2017-03-21 |
BRPI0903706B1 (pt) | 2021-09-08 |
EP2188100A1 (en) | 2010-05-26 |
US8481666B2 (en) | 2013-07-09 |
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