JP2017508834A - ポリオレフィン生成物の生成 - Google Patents
ポリオレフィン生成物の生成 Download PDFInfo
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- JP2017508834A JP2017508834A JP2016550621A JP2016550621A JP2017508834A JP 2017508834 A JP2017508834 A JP 2017508834A JP 2016550621 A JP2016550621 A JP 2016550621A JP 2016550621 A JP2016550621 A JP 2016550621A JP 2017508834 A JP2017508834 A JP 2017508834A
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- Prior art keywords
- catalyst
- group
- slurry
- polymer
- catalyst system
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 351
- 229920000642 polymer Polymers 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 59
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 55
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- -1 tetrahydroindenyl Chemical group 0.000 claims description 118
- 239000002002 slurry Substances 0.000 claims description 82
- 239000012190 activator Substances 0.000 claims description 52
- 125000004429 atom Chemical group 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
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- 150000004678 hydrides Chemical class 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 4
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- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
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- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- PQWIFOZEPZWISQ-UHFFFAOYSA-N C1=CC=C2C(CC)C([Zr]C=3C(C4=CC=CC=C4C=3)CC)=CC2=C1 Chemical compound C1=CC=C2C(CC)C([Zr]C=3C(C4=CC=CC=C4C=3)CC)=CC2=C1 PQWIFOZEPZWISQ-UHFFFAOYSA-N 0.000 claims 1
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- 150000001875 compounds Chemical class 0.000 description 86
- 239000000243 solution Substances 0.000 description 62
- 239000000203 mixture Substances 0.000 description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 37
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- 125000004122 cyclic group Chemical group 0.000 description 13
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- 239000002904 solvent Substances 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052732 germanium Inorganic materials 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 230000003068 static effect Effects 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
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- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 10
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- 150000003254 radicals Chemical class 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229920002873 Polyethylenimine Polymers 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 238000012685 gas phase polymerization Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 229910052735 hafnium Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052752 metalloid Inorganic materials 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 description 4
- 229940083916 aluminum distearate Drugs 0.000 description 4
- RDIVANOKKPKCTO-UHFFFAOYSA-K aluminum;octadecanoate;hydroxide Chemical compound [OH-].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RDIVANOKKPKCTO-UHFFFAOYSA-K 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
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- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
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- 125000003710 aryl alkyl group Chemical group 0.000 description 3
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Images
Classifications
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C07F17/00—Metallocenes
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- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
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Abstract
Description
本出願は、次の番号を有する米国仮特許出願、すなわち、2014年2月11日出願のChing−Tai Lue等による第61/938,466号(2014U002.PRV)、2014年2月11日出願のChing−Tai Lue等による第61/938,472号(2014U003.PRV)、2014年4月18日出願のFrancis C.Rix等による第61/981,291号(2014U010.PRV)、2014年4月28日出願のFrancis C.Rix等による第61/985,151号(2014U012.PRV)、2014年8月1日出願のSun−Chueh Kao等による第62/032,383号(2014U018.PRV)、2014年12月5日出願のFrancis C.Rix等による第62/087,905号(2014U035.PRV)、2014年12月5日出願のDaniel P.Zilker,Jr.等による第62/088,196号(2014U036.PRV)、2014年12月5日出願のChing−Tai Lue等による第62/087,911号(2014U037.PRV)、及び2014年12月5日出願のFrancis C.Rix等による第62/087,914号(2014U038.PRV)の利益を主張するものであり、これらの開示は、参照によりそれらの全体が本明細書に組み込まれる。
メタロセン触媒化合物
メタロセン触媒化合物は本明細書の方法に使用され得る。メタロセン触媒化合物は、少なくとも1つの第3族〜第12族の金属原子、及び少なくとも1つの金属原子に結合された1つ以上の脱離基(複数可)に結合された1つ以上のCp配位子(シクロペンタジエニル及びシクロペンタジエニルにイソローバルな配位子)を有する「ハーフサンドイッチ」及び/または「フルサンドイッチ」化合物を含む。本明細書で使用されるとき、元素の周期表及びその族に対する全ての参照は、ローマ数字で注記される以前のIUPAC形態に対して参照がなされない限り(同書に表示される)、または別途記載されない限り、HAWLEY′S CONDENSED CHEMICAL DICTIONARY,Thirteenth Edition,John Wiley & Sons,Inc.(1997)(IUPACの許可によりそこに再現される)に公表されるNEW NOTATIONに対してである。
CpACpBMXn、
CpA(A)CpBMXn。
触媒系は、1つ以上の第15族の金属含有触媒化合物を含み得る。本明細書で使用されるように、非メタロセン触媒化合物と呼ばれるものがある。第15族の金属含有化合物は、一般的に、第3〜14族の金属原子、第3〜7族、または第4〜6族の金属原子を含む。多くの実施形態では、第15族の金属含有化合物は、少なくとも1つの脱離基に結合され、また少なくとも2個の第15族原子にも結合され、そのうちの少なくとも1個が別の基を介して第15または16族原子にも結合される、第4族金属原子を含む。
触媒系は、初期触媒化合物を有し得るスラリー中に触媒または触媒構成成分、及びスラリーに添加される添加溶液触媒構成成分を含み得る。初期触媒構成成分スラリーは触媒を有しない場合がある。この場合、2つ以上の溶液触媒がスラリーに添加されて、各々を担体させることができる。
本明細書で使用されるとき、用語「担体」及び「キャリア」は、互換的に使用され、タルク、無機酸化物、及び無機塩化物などの多孔質担体材料を含む、あらゆる担体材料を指す。スラリーの1つ以上のシングルサイト触媒化合物は、活性化剤と一緒に同一または別個の担体上で担持され得るか、または活性化剤は非担持形態で使用され得るか、またはシングルサイト触媒化合物とは異なる担体上に付着され得るか、またはこれらの任意の組み合わせであってよい。これは、当該技術分野において一般的に使用される任意の技術により実現することができる。当該技術分野において、シングルサイト触媒化合物を担持するための様々な他の方法がある。例えば、シングルサイト触媒化合物は、ポリマー結合配位子を含有することができる。スラリーのシングルサイト触媒化合物は、噴霧乾燥され得る。シングルサイト触媒化合物を用いた担体は官能化され得る、または少なくとも1つの置換基または離脱基が選択される。
本明細書で使用されるとき、用語「活性化剤」は、触媒構成成分のカチオン種を作製するなどによってシングルサイト触媒化合物または構成成分を活性化することができる、担持または非担持された、任意の化合物または化合物の組み合わせを指す場合がある。例えば、これは、シングルサイト触媒化合物/構成成分の金属中心からの少なくとも1つの脱離基(本明細書に記載のシングルサイト触媒化合物中の「X」基)の引抜を含み得る。活性化剤は、「共触媒」とも称される場合がある。
触媒構成成分溶液は、メタセロン等の触媒化合物のみを含むか、または触媒化合物に加えて、活性化剤を含み得る。トリムプロセスにおいて使用される触媒溶液は、触媒化合物及び任意の活性化剤を液体溶媒中に溶解することにより調製され得る。液体溶媒は、C5〜C30アルカンまたはC5〜C10アルカンなどのアルカンであり得る。シクロヘキサンなどの環状アルカン及びトルエンなどの芳香族化合物も使用され得る。加えて、鉱油が溶媒として使用され得る。採用される溶液は、重合の条件下で液体であり、比較的不活性でなくてはならない。一実施形態では、触媒化合物溶液に利用される液体は、触媒構成成分スラリーにおいて使用される希釈剤とは異なる。別の実施形態では、触媒化合物溶液に利用される液体は、触媒構成成分溶液において使用される希釈剤と同じである。
気相ポリエチレン生成プロセスにおいて、反応器中の静電気レベルの調節に役立つ1つ以上の静電気制御剤を使用することが望ましい場合がある。本明細書で使用される静電気制御剤は、流動床反応器内に導入されたとき、流動床の静電荷(負、正、またはゼロ)に影響を及ばす、またはそれを動かすことができる化学組成物である。使用される特定の背電気制御剤は静電荷の性質に依存し得、静電気制御剤の選択は、生成されるポリマー及び使用されるシングルサイト触媒化合物により変動し得る。
−(CH2−CH2−NH)n−、
図2は、気相反応器系200の概略図であり、少なくとも2つの触媒の添加を示し、そのうちの少なくとも1つはトリム触媒として添加される。触媒構成成分スラリー、好ましくは少なくとも1つの担体及び少なくとも1つの活性化剤、少なくとも1つの担持活性化剤、及び任意の触媒化合物を含む鉱油スラリーは、槽または触媒ポット(cat pot)202に設置され得る。一実施形態では、触媒ポット202は、固体濃度を均質に保つように設計された攪拌保持タンクである。好ましくは溶媒と少なくとも1つの触媒化合物及び/または活性化剤とを混合することによって調製された触媒構成成分溶液は、トリムポット204と呼ばれ得る別の槽に設置される。次に、触媒構成成分スラリーは、触媒構成成分溶液とインラインで混合されて最終触媒組成物を形成し得る。シリカ、アルミナ、フュームドシリカ、または任意の他の粒子状物質などの核形成剤206は、インラインでスラリー及び/もしくは溶液に、または槽202もしくは204に添加され得る。同様に、追加の活性化剤または触媒化合物がインラインで添加され得る。例えば、異なる触媒を含む第2の触媒スラリーは、第2の触媒ポットから導入され得る。2つの触媒スラリーは、トリムポットからの溶液触媒を添加して、または添加することなく触媒系として使用され得る。
生成物ポリマーの特性は、上述の溶液、スラリー、及びいずれの任意の添加材料(核形成剤、触媒化合物、活性化剤等)の混合のタイミング、温度、濃度、ならびに順序を調整することにより制御され得る。MWD、メルトインデックス、各触媒によって生成されたポリマーの相対量、及び生成されたポリマーの特性は、プロセスパラメータを操作することによっても変更することができる。重合系中の水素濃度の操作、重合系中の第1の触媒の量の変更、重合系中の第2の触媒の量の変更を含む、任意の数のプロセスパラメータが調整され得る。調整され得る他のプロセスパラメータは、重合プロセスにおける触媒の相対比を変更すること(及び任意に、安定した、または一定のポリマー生成速度を維持するために、それらの個々の供給速度を調整すること)を含む。反応器222中の反応物の濃度は、プロセスから引き抜かれる、もしくはパージされる液体またはガスの量を変更する、重合プロセスに戻される回収した液体及び/もしくは回収したガスの量及び/または組成を変更することにより調整することができ、回収した液体または回収したガスは、重合プロセスから排出されたポリマーから回収され得る。更に、調整され得る濃度パラメータは、重合温度の変更、重合プロセスにおけるエチレン分圧の変更、重合プロセスにおけるエチレンのコモノマーに対する比率の変更、活性化配列における活性化剤の遷移金属に対する比率の変更を含む。スラリーまたは溶液の相対供給速度の変更、インラインでのスラリー及び溶液の混合の混合時間、温度、及びまたは程度の変更、異なる種類の活性化剤化合物の重合プロセスへの添加、ならびに酸素もしくはフルオロベンゼンまたは他の触媒毒の重合プロセスへの添加などの時間依存パラメータが調整され得る。これらの調整の任意の組み合わせは、最終ポリマー生成物の特性を制御するために使用され得る。
触媒系は、1つ以上のオレフィンを重合して、そこから1つ以上のポリマー生成物をもたらすために使用され得る。高圧、溶液、スラリー、及び/または気相重合プロセスを含むが、これらに限定されない、任意の好適な重合プロセス使用され得る。気相重合以外の他の技術を使用する実施形態では、図2に関して論じられるものと類似する触媒添加系の修正物が使用され得る。例えば、トリム系は、ポリエチレンコポリマーを生成するためのループスラリー反応器に触媒を供給するために使用され得る。
全ての手順は、空気及び水分を除いて、窒素下で行われた。共担持混合メタロセン触媒の全ての組み合わせHf及びZr充填量は触媒の約30μmol(Zr+Hf)/gであり、アルミニウム充填量は触媒の約4.5mmol Al/gであった。これらの共担持混合メタロセン触媒に関して、触媒調製に使用されたHfP/EtInd比は、以下に示されるように、モル分率に基づく85:15、60:40、及び50:50を含む。メチルアルミノキサン(MAO、Albemarle 10重量%)及びメタロセンを最初に反応器に添加し、室温で30分間混合した。次に、シリカ(ES757、PQ Corp.875℃で焼成)をMAO/メタロセン溶液に直接添加し、室温で更に1時間混合した。次に、内部温度が〜70℃で一定になるまで、2.5時間、触媒を真空下で乾燥させた。実施例1で使用された単一構成成分触媒は、混合メタロセン触媒について上述されるものと類似する方法で調製された。この触媒のHf充填量は触媒の約0.045mmol Hf/gであり、この触媒のアルミニウム充填量は触媒の約4.5mmol Al/gであった。各場合において、触媒スラリーは、乾燥固体触媒をHydrobrite 380鉱油に添加して18重量%のスラリーを形成することにより作製された。
Claims (18)
- オレフィンを重合する方法であって、
エチレン及び少なくとも1つのコモノマーを触媒系と接触させて、多峯性のポリオレフィンポリマーを生成することを含み、前記触媒系が、前記エチレンの、前記ポリオレフィンポリマーの低分子量(LMW)部分への重合を促進する第1の触媒と、前記エチレンの、前記ポリオレフィンポリマーの高分子量(HMW)部分への重合を促進する第2の触媒と、を含み、
前記第1の触媒、及び前記第2の触媒の少なくとも一部が、共担持されて共通担持触媒系を形成し、
前記第2の触媒の少なくとも一部が、触媒トリム供給として前記触媒系に添加される、前記方法。 - 前記共通担持触媒系が、次の構造、
CpACpBMXn
を有する少なくとも1つの触媒を含み、式中、CpA及びCpBが各々独立して、置換または非置換シクロペンタジエニル、インデニル、テトラヒドロインデニル、及びフルオレニル化合物からなる群から選択され、
Mが、CpA及びCpBに化学結合され、第4、5、及び6族原子からなる群から選択され、
各Xが、Mに化学結合され、独立して、ハロゲンイオン、水素化物、C1〜C12アルキル、C2〜C12アルケニル、C6〜C12アリール、C7〜C20アルキルアリール、C1〜C12アルコキシ、C6〜C16アリールオキシ、C7〜C8アルキルアリールオキシ、C1〜C12フルオロアルキル、C6〜C12フルオロアリール、及びC1〜C12ヘテロ原子含有炭化水素からなる群から選択され、
nが、0または1〜4の整数である、請求項1に記載の前記方法。 - 前記共通担持触媒系が、クロム系触媒、チーグラー・ナッタ触媒、または第15族含有触媒である少なくとも1つの触媒を含む、請求項1に記載の前記方法。
- 前記触媒トリム供給が、前記第1の触媒を含むスラリーに添加される、請求項1に記載の前記方法。
- 前記触媒トリム供給が、溶液トリム供給である、請求項1に記載の前記方法。
- 前記乾燥共通担持触媒系1グラム当たりの、前記触媒トリム供給を介して添加される前記触媒のモル量が、1.8μmol〜150μmolの範囲である、請求項1に記載の前記方法。
- 前記乾燥共通担持触媒系1グラム当たりの、前記触媒トリム供給を介して添加される前記触媒のモル量が、12.4μmol〜75μmolの範囲である、請求項1に記載の前記方法。
- 前記ポリオレフィンポリマーが、二峰性である、請求項1に記載の前記方法。
- 前記共通担持触媒系が、活性化剤を含む、請求項1に記載の前記方法。
- 前記活性化剤が、メチルアルミノキサン(MAO)及びシリカメチルアルミノキサン(SMAO)のうちの少なくとも1つを含む、請求項12に記載の前記方法。
- 前記共通担持触媒系における前記第2の触媒対前記第1の触媒のモル分率に基づく初期の共沈着が、約0.7:0.3〜約0.3:0.7の範囲である、請求項1に記載の前記方法。
- 前記共通担持触媒系における前記第2の触媒対前記第1の触媒のモル分率に基づく初期の共沈着が、約0.6:0.4〜約0.4:0.6の範囲である、請求項1に記載の前記方法。
- 前記コモノマーが、4〜20個の炭素原子を有するαオレフィンを含む、請求項1に記載の前記方法。
- 前記コモノマーが、ブテンまたはヘキセンを含む、請求項1に記載の前記方法。
- 請求項1〜17のいずれか一項に記載の方法により作製されたポリマー。
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