JP2022542232A - チーグラー・ナッタ触媒および水素化プロ触媒を使用する溶液中のエチレンの重合プロセス - Google Patents
チーグラー・ナッタ触媒および水素化プロ触媒を使用する溶液中のエチレンの重合プロセス Download PDFInfo
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- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
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- NBEFTNDCBLLNCG-UHFFFAOYSA-N 3-[3-(3,6-ditert-butylcarbazol-9-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]-5-methylbenzonitrile Chemical compound CC1=CC(C#N)=CC(C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 NBEFTNDCBLLNCG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MQHIHSHXASHXLK-UHFFFAOYSA-N OC=1C(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=CC=1C1=CC=CC(Cl)=C1 Chemical compound OC=1C(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=CC=1C1=CC=CC(Cl)=C1 MQHIHSHXASHXLK-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- HAEBMOGKTDSWHJ-UHFFFAOYSA-L [Cl-].[Cl-].CC1(C=CC=C1)[Ti+2]C1(C=CC=C1)C Chemical compound [Cl-].[Cl-].CC1(C=CC=C1)[Ti+2]C1(C=CC=C1)C HAEBMOGKTDSWHJ-UHFFFAOYSA-L 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
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- 238000006758 bulk electrolysis reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CZQIDPLTQBOKMO-UHFFFAOYSA-L butylcyclopentane;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCC[C]1[CH][CH][CH][CH]1.CCCC[C]1[CH][CH][CH][CH]1 CZQIDPLTQBOKMO-UHFFFAOYSA-L 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- 238000012937 correction Methods 0.000 description 1
- 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 1
- YMNCCEXICREQQV-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical group [Cl-].[Cl-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YMNCCEXICREQQV-UHFFFAOYSA-L 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- YQZMEUFOYRWASB-UHFFFAOYSA-L dichlorotitanium;ethylcyclopentane Chemical compound Cl[Ti]Cl.CC[C]1[CH][CH][CH][CH]1.CC[C]1[CH][CH][CH][CH]1 YQZMEUFOYRWASB-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
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Abstract
Description
本出願は、2019年7月31日に出願された米国仮特許出願第62/881,184号に対する優先権を主張するものであり、この開示全体が、参照により本明細書に組み込まれる。
式(I)または式(II)の金属-配位子錯体を含む触媒系は、オレフィン重合反応の金属系触媒を活性化するための当該技術分野で既知の任意の技法によって触媒的に活性にされ得る。例えば、式(I)または式(II)の金属-配位子錯体によるプロ触媒は、錯体を活性化助触媒と接触させるか、または錯体を活性化助触媒と組み合わせることによって触媒的に活性にされ得る。加えて、式(I)または式(II)による金属-配位子錯体は、中性であるプロ触媒形態、およびベンジルまたはフェニルなどのモノアニオン性配位子の損失によって正に帯電され得る触媒形態の両方を含む。本明細書で使用するのに好適な活性化助触媒としては、アルキルアルミニウム;ポリマーまたはオリゴマーのアルモキサン(アルミノキサンとしても既知);中性ルイス酸;および非ポリマー、非配位性、イオン形成性の化合物(酸化条件下でのそのような化合物の使用を含む)が挙げられる。好適な活性化技法は、バルク電気分解である。また、前述の活性化助触媒および技法のうちの1つ以上の組み合わせも企図される。「アルキルアルミニウム」という用語は、モノアルキルアルミニウムジヒドリドもしくはモノアルキルアルミニウムジハライド、ジアルキルアルミニムウヒドリドもしくはジアルキルアルミニウムハライド、またはトリアルキルアルミニウムを意味する。ポリマーまたはオリゴマーのアルモキサンの例としては、メチルアルモキサン、トリイソブチルアルミニウムで修飾されたメチルアルモキサン、およびイソブチルアルモキサンが挙げられる。
ゲル浸透クロマトグラフィー(GPC)法
ゲル浸透クロマトグラフィー(GPC)において、クロマトグラフィー系は、Precision Detectors(現在はAgilent Technologies)二角レーザ光散乱(LS)検出器モデル2040に結合された内部IR5赤外線検出器(IR5)を備えた、PolymerChar GPC-IR(Valencia、Spain)高温GPCクロマトグラフを含む。オートサンプラのオーブンコンパートメントを160℃に設定し、カラムコンパートメントを150℃に設定する。カラムは、4つのAgilent「Mixed A」30cm、20ミクロンの線形混合床カラムである。クロマトグラフィーの溶媒は、1,2,4トリクロロベンゼンであり、200ppmのブチル化ヒドロキシトルエン(BHT)を含有する。溶媒源を窒素でスパージする。注入体積は、200マイクロリットルであり、流量は、1.0ミリリットル/分である。
Mポリエチレン=A×(Mポリスチレン)B (等式1)
式中、Mは、分子量であり、Aは、0.4315の値を有し、Bは、1.0に等しい。
流量(実効)=流量(名目)*(RV(較正済みFM)/RV(FM試料))(等式7)
1000個の総C当たりの短鎖分岐(SCDB/1000TC)を、WO2015/200743(A1)の「分子量コモノマー分布指数(MWCDI)」のセクションに記載の方法に従って測定する。
触媒効率を、重合プロ触媒中の金属1グラム当たりの、重合中に消費されるエチレンの量(gエチレン/g金属)に基づいて計算する。金属のグラム数は、重合プロ触媒中の金属に寄与される金属のグラム数を指し、アルキル化チタノセン水素化プロ触媒中のTiを含まない。
バッチ反応器に、指定された量の1-オクテンおよびIsopar Eを充填し、1-オクテンおよびIsopar Eの総量は、1580gである。反応器の内容物を所望の重合温度に加熱し、次いで、内容物を、指定された量の水素分子(H2)の存在下でエチレンで飽和させる。水素を生成しないポストメタロセンプロ触媒および助触媒の溶液を、助触媒対プロ触媒のモル比1.2:1で混合し、続いて、MMAO-3Aを、MMAO-3A対プロ触媒のモル比50/1で混合物に添加する。アルキル化チタノセン水素化プロ触媒(Cp2TiCl2-TiBAlまたはCp2TiCl2-MMAO-3A)を、混合物に添加する。内容物を、反応器に直ちに注入する。プロ触媒の量は、重合開始時の反応器内の大きな温度スパイクを回避するために、重合中のエチレン消費量を約10~30g以内に維持するように調整する。反応器内の圧力を、エチレン流で3100キロパスカル(kPa、1平方インチ当たり(psi)450ポンドに等しい)に維持して、その重合中のエチレン消費に起因する圧力降下を補償する。10分間の反応時間の後、底部バルブを開き、反応器の内容物をガラス製ケトルに移す。ケトルの内容物を、マイラーで裏打ちされたトレイ上に注ぎ、完全に冷却させ、標準温度および圧力で乾燥させる。乾燥させた内容物を、減圧下でさらに乾燥させて、生成物ポリ(エチレン-コ-1-オクテン)コポリマーを得る。
触媒効率を、重合プロ触媒中の金属1グラム当たりの、重合中に消費されるエチレンの量(gエチレン/g金属)に基づいて計算する。金属のグラム数は、重合プロ触媒中の金属に寄与される金属のグラム数を指し、アルキル化チタノセン水素化プロ触媒中のTiを含まない。
PCAT-1を、WO2017/058981の実施例I4に概ね従って、実施例I4のHfCl4を等モル量のZrCl4に置き換えて合成した。
アルキル化チタノセン水素化プロ触媒Cp2TiCl2-Al(iBu)3。4オンスのボトルに、0.544gのCp2TiCl2、4mLのIsopar E溶媒、および攪拌棒を入れ、混合物を形成した。この混合物に、ヘキサン中の1.0Mのトリイソブチルアルミニウム(Al(iBu)3)の溶液38.0mLを、攪拌しながら10分間にわたってゆっくりと添加した。固体であるCp2TiCl2は可溶性になり、青色の溶液を形成した。Al(iBu)3からのAl対Cp2TiCl2からのTiの溶液中のモル比は、17.4であった。
Claims (13)
- 触媒系であって、
水素を生成しないポストメタロセンプロ触媒と、
助触媒と、
式Cp2TiX2TiCp2またはCp2TiXnを有する水素化プロ触媒と、を含み、
式中、
各Cpが、少なくとも1つの(C1-C10)アルキルで任意選択的に置換されたシクロペンタジエニルであり、
各Xが、独立して、モノアニオン性または中性であり、各Xが、独立して、(C1-C40)炭化水素、(C1-C40)ヘテロ炭化水素、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、またはハロゲン原子であり、
nが、1または2である、触媒系。 - 触媒系であって、
水素を生成しないポストメタロセンプロ触媒と、
アルキルアルミニウム種で処理されたCp2TiX2と、を含み、式中、
各Cpが、少なくとも1つの(C1-C10)アルキルで置換されたシクロペンタジエニルであり、
各Xが、独立して、モノアニオン性または中性であり、各Xが、独立して、(C1-C40)炭化水素、(C1-C40)ヘテロ炭化水素、(C1-C40)炭化水素アニオン、(C1-C40)ヘテロ炭化水素アニオン、またはハロゲン原子であり、
nが、1または2である、触媒系。 - 前記アルミニウム種が、アルキルアルミノキサン、修飾されたアルキルアルミノキサン、または式AlR3を有するアルキルアルミニウムを含み、式中、各Rが、独立して、(C1-C40)炭化水素、(C1-C40)ヘテロ炭化水素、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、またはハロゲン原子である、請求項2に記載の触媒系。
- 前記アルミニウム種が、AlR3と、水、アルコール、シラノール、またはルイス塩基との反応生成物である、請求項2または請求項3に記載の触媒系。
- 前記ルイス塩基が、ピリジン、または一置換アルキルアミン、二置換アルキルアミン、もしくは三置換アルキルアミンである、請求項4に記載の触媒系。
- 前記アルミニウム種が、ジイソブチルアルミニウムオキシド(DIBAOもしくはDIBAL-O)またはイソブチルアルミノキサン(IBAO)である、請求項2~5のいずれか一項に記載の触媒系。
- 前記触媒系が、不純物捕捉剤をさらに含む、先行請求項のいずれか一項に記載の触媒系。
- 各Xが、置換ベンジルまたは置換ヘテロアリールベンジルである、先行請求項のいずれか一項に記載の触媒系。
- 前記水素を生成しないポストメタロセンプロ触媒が、重合条件下で1ppm以下の水素を生成する、先行請求項のいずれか一項に記載の触媒系。
- 前記水素を生成しないポストメタロセンプロ触媒が担持されておらず、かつ前記水素化触媒が担持されていない、先行請求項のいずれか一項に記載の触媒系。
- 前記水素を生成しないポストメタロセンプロ触媒が、式(I)による金属-配位子錯体であり、
Mが、チタン、ジルコニウム、またはハフニウムから選択される金属であり、前記金属が、+2、+3、または+4の形式酸化状態にあり、
nが、0、1、または2であり、
nが1である場合、Xは、単座配位子または二座配位子であり、
nが2である場合、各Xは、独立して、単座配位子であり、
単座配位子である各X1が、独立して、ハロゲン、非置換(C1-C20)ヒドロカルビル、非置換(C1-C20)ヒドロカルビルC(O)O-、またはRKRLN-であり、RKおよびRLの各々が、独立して、非置換(C1-C20)ヒドロカルビルであり、
Lが、(C1-C40)ヒドロカルビレン、(C1-C40)ヘテロヒドロカルビレン、-Si(RC)2-、-Si(RC)2OSi(RC)2-、-Si(RC)2C(RC)2-、-Si(RC)2Si(RC)2-、-Si(RC)2C(RC)2Si(RC)2-、-C(RC)2Si(RC)2C(RC)2-、-N(RN)C(RC)2-、-N(RN)N(RN)-、-C(RC)2N(RN)C(RC)2-、-Ge(RC)2-、-P(RP)-、-N(RN)-、-O-、-S-、-S(O)-、-S(O)2-、-N=C(RC)-、-C(O)O-、-OC(O)-、-C(O)N(R)-、および-N(RC)C(O)-からなる群から選択される、ジラジカルであり、
各Zが、独立して、-O-、-S-、-N(RN)-、または-P(RP)-から選択され、
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、およびR16が、独立して、-H、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、-Si(RC)3、-Ge(RC)3、-P(RP)2、-N(RN)2、-ORC、-SRC、-NO2、-CN、-CF3、RCS(O)-、RCS(O)2-、-N=C(RC)2、RCC(O)O-、RCOC(O)-、RCC(O)N(R)-、(RC)2NC(O)-、ハロゲン、式(XI)を有するラジカル、式(XII)を有するラジカル、および式(XIII)を有するラジカルからなる群から選択され、
R31~R35、R41~R48、およびR51~R59の各々が、独立して、-H、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、-Si(RC)3、-Ge(RC)3、-P(RP)2、-N(RN)2、-ORC、-SRC、-NO2、-CN、-CF3、RCS(O)-、RCS(O)2-、(RC)2C=N-、RCC(O)O-、RCOC(O)-、RCC(O)N(RN)-、(RC)2NC(O)-、またはハロゲンから選択される、先行請求項のいずれか一項に記載の触媒系。 - 前記水素を生成しないポストメタロセンプロ触媒が、式(II)による金属-配位子錯体であり、
Mが、元素周期表の3~13族のうちのいずれかの金属、ランタニド、およびアクチニドから選択される金属であり、前記金属が、+2、+3、または+4の形式酸化状態にあり、
各RA、RB、RC、およびRDが、-H、(C1-C40)ヒドロカルビル、(C1-C40)ヘテロヒドロカルビル、-Si(RC)3、-Ge(RC)3、-P(RC)2、-N(RC)2、-ORC、-SRC、-NO2、-CN、-CF3、RCS(O)-、RCS(O)2-、-N=(RC)2、RCC(O)O-、RCOC(O)-、RCC(O)N(R)-、(RC)2NC(O)-、またはハロゲンであり、任意選択的に、RA、RB、RC、およびRDのうちのいずれか2つが接続して、非芳香族環または芳香族環を形成し得、各RCが、独立して、(C1-C18)炭化水素または(C5-C18)アリールであり、
Qが、ホウ素、窒素、リン、硫黄、酸素、炭素、シリコン、またはゲルマニウムであり、
各X2が、独立して、単座配位子であり、前記単座配位子が、モノアニオン性またはジアニオン性で、ハロゲン、非置換(C1-C20)ヒドロカルビル、非置換(C1-C20)ヒドロカルビルC(O)O-、またはRKRLN-であり、RKおよびRLの各々が、独立して、非置換(C1-C20)ヒドロカルビルであり、
pが、1、2、または3である、請求項1~7のいずれか一項に記載の触媒系。
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