JP2019529653A - 改質されたチーグラーナッタ(プロ)触媒および系 - Google Patents
改質されたチーグラーナッタ(プロ)触媒および系 Download PDFInfo
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/14—Monomers containing five or more carbon atoms
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- 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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
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- 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
- C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/64168—Tetra- or multi-dentate ligand
- C08F4/64186—Dianionic ligand
- C08F4/64193—OOOO
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- 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
- C08F4/654—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
- C08F4/6545—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium and metals of C08F4/64 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
- 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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
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- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
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Abstract
Description
Claims (15)
- (C)飽和または芳香族炭化水素液中の改質されたチーグラーナッタプロ触媒と活性剤との反応の生成物を含む改質された触媒系を使用してオレフィンを重合する方法であって、反応器中の少なくとも1つの重合性オレフィンを有効条件下で前記改質された触媒系に接触させてポリオレフィン生成物を得ることを含む方法であり、前記改質されたチーグラーナッタプロ触媒は、前記接触工程の前に、前記改質されたチーグラーナッタプロ触媒を得るための100℃未満の改質温度および少なくとも1分間の改質時間を含む改質条件下で、(C)飽和または芳香族炭化水素液中で初期チーグラーナッタプロ触媒および分子(プロ)触媒および場合により活性剤を一緒に混合することにより調製されるものである、重合方法。
- (i)前記初期チーグラーナッタプロ触媒が、(B)ハロゲン化マグネシウム担持チタンプロ触媒であって、前記(B)ハロゲン化マグネシウム担持チタンプロ触媒が、(B)ハロゲン化マグネシウム担持チタンプロ触媒を得るように(C)飽和または芳香族炭化水素液中で(D)本質的にハロゲン化マグネシウムからなる固体微粒子を(E)四塩化チタンと接触させることにより調製されるか、(ii)前記分子(プロ)触媒が、本質的に分子配位子−金属錯体(プロ)触媒からなるか、または(iii)(i)および(ii)の両方である、請求項1に記載の方法。
- 前記改質条件が、(i)0℃〜50℃の改質温度、(ii)3時間〜3ヶ月の改質時間、(iii)不活性ガス雰囲気(例えば、窒素分子、ヘリウム、アルゴン、またはそれらの任意の2つ以上の混合物)、(iv)(i)および(ii)の両方、(v)(i)および(iii)の両方、(vi)(ii)および(iii)の両方、または(vii)(i)、(ii)および(iii)の各々、を含む、請求項1または2に記載の方法。
- 前記改質された触媒系がさらに、(G)有機ホウ酸塩または(H)有機ホウ素を含む、請求項1または2に記載の方法。
- (i)前記少なくとも1つの重合性オレフィンがエチレンであり、かつ前記ポリオレフィン生成物がポリエチレンを含むか、(ii)前記少なくとも1つの重合性オレフィンが、少なくとも1つの(C3−C40)アルファ−オレフィンであり、かつ前記ポリオレフィン生成物が、ポリ((C3−C40)アルファ−オレフィン)を含むか、または(iii)前記少なくとも1つの重合性オレフィンが、エチレンと少なくとも1つの(C3−C40)アルファ−オレフィンとの組み合わせを含み、かつ前記ポリオレフィン生成物が、ポリ(エチレン−コ−(C3−C40)アルファ−オレフィン)コポリマーを含む、請求項1〜4のいずれか1項に記載の方法。
- (i)前記初期ハロゲン化マグネシウム担持チタンプロ触媒が、Alを含まない(Al/Mg=0のモル比)か、(ii)前記初期ハロゲン化マグネシウム担持チタンプロ触媒が、>0〜<0.05のAl/Mgのモル比を有するか、(iii)前記初期ハロゲン化マグネシウム担持チタンプロ触媒の前記ハロゲン化マグネシウムが、塩化マグネシウムであるか、(iv)前記初期ハロゲン化マグネシウム担持チタンプロ触媒の前記ハロゲン化マグネシウムが、臭化マグネシウムであるか、(v)(i)および(iii)の両方か、(vi)(i)および(iv)の両方か、(vii)(ii)および(iii)の両方か、(viii)(ii)および(iv)の両方である、請求項1〜5のいずれか1項に記載の方法。
- (i)前記(D)本質的にハロゲン化マグネシウムからなる固体微粒子が、Brunauer、Emmett、Teller(BET)表面積法により測定された場合に1グラムあたり≧200平方メートル(m2/g)のBrunauer、Emmett、Teller(BET)表面積を有するか、または(ii)前記(D)本質的にハロゲン化マグネシウムからなる固体微粒子が、前記(C)飽和または芳香族炭化水素液中に溶解した(F)ジアルキルマグネシウム化合物の溶液を1.95〜2.05モル当量のハロゲン化水素と接触させて、前記(C)飽和または芳香族炭化水素液中の前記(D)本質的にハロゲン化マグネシウムからなる固体微粒子の懸濁液を得ることにより調製されたか、または(iii)(i)および(ii)の両方である、請求項1〜6のいずれか1項に記載の方法。
- 前記改質されたチーグラーナッタプロ触媒と共に使用される前記活性剤が、(A)ヒドロカルビルアルミノキサンを含む、請求項1〜7のいずれか1項に記載の方法。
- 前記分子配位子−金属(プロ)触媒が、(i)シクロペンタジエニル配位子−金属錯体(プロ)触媒、(ii)シクロペンタジエニルを含まない配位子−金属錯体(プロ)触媒、または(iii)(i)および(ii)の両方、を含む、請求項1〜8のいずれか1項に記載の方法。
- 前記接触が、(i)前記少なくとも1つの重合性オレフィンを収容する前記反応器中に前記改質された触媒系を添加すること、(ii)前記改質された触媒系を収容する前記反応器中に前記少なくとも1つの重合性オレフィンを添加すること、または(iii)前記改質された触媒系の第1供給物を前記反応器中に添加し、かつ前記少なくとも1つの重合性オレフィンの第2供給物を前記反応器中に添加すること、を含む、請求項1〜9のいずれか1項に記載の方法。
- 改質されたチーグラーナッタプロ触媒と活性剤との反応の生成物である改質された触媒系を使用してオレフィンを重合する液相重合プロセスであって、有効条件下で前記反応器中の少なくとも1つの重合性オレフィンを前記改質された触媒系と接触させてポリオレフィン生成物を得ることを含むプロセスであり、前記改質されたチーグラーナッタプロ触媒は、前記接触工程の前に、100℃未満の改質温度および少なくとも1分間の改質時間を含む改質条件下で初期チーグラーナッタプロ触媒および分子配位子−金属錯体(プロ)触媒および場合により活性剤を一緒に混合し、前記改質されたチーグラーナッタプロ触媒を得ることにより調製される、重合プロセス。
- 請求項1〜11のいずれか1項に記載の重合方法によって製造された、ポリオレフィン生成物。
- 請求項1〜12のいずれか1項に記載の、改質されたチーグラーナッタプロ触媒。
- (i)(A)ヒドロカルビルアルミノキサンをさらに含むか、(ii)有機ホウ酸塩または有機ホウ素をさらに含むか、(iii)トリアルキルアルミニウムをさらに含むか、(iv)トリアルキルアルミニウムを含まないか、(v)(i)および(ii)の両方であるか、(vi)(i)および(iii)の両方であるか、(vii)(i)および(iv)の両方であるか、(viii)(i)、(ii)および(iv)の各々である、請求項13に記載の改質されたチーグラーナッタプロ触媒。
- 請求項13または14に記載の改質されたチーグラーナッタプロ触媒と活性剤との反応の生成物を含む、改質された触媒系。
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US201662401328P | 2016-09-29 | 2016-09-29 | |
US62/401,328 | 2016-09-29 | ||
PCT/US2017/052601 WO2018063898A1 (en) | 2016-09-29 | 2017-09-21 | Modified ziegler-natta (pro)catalyst and system |
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EP (1) | EP3519452B1 (ja) |
JP (1) | JP7050055B2 (ja) |
KR (1) | KR102449456B1 (ja) |
CN (1) | CN109715677B (ja) |
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BR112019005532B1 (pt) | 2023-04-11 |
CN109715677A (zh) | 2019-05-03 |
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US20210332170A1 (en) | 2021-10-28 |
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KR102449456B1 (ko) | 2022-10-11 |
US20220098341A1 (en) | 2022-03-31 |
BR112019005532A2 (pt) | 2019-06-18 |
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US11649307B2 (en) | 2023-05-16 |
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