CN1334817A - 制备三氟芳基铝醚合物的方法 - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- -1 aluminum compound Chemical class 0.000 claims abstract description 6
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- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 10
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 claims description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 229910000085 borane Inorganic materials 0.000 abstract description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 11
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 101710097035 4-hydroxyphenylalkanoate adenylyltransferase Proteins 0.000 description 7
- 101710145976 Long-chain-fatty-acid-AMP ligase FadD26 Proteins 0.000 description 7
- 101710145980 Long-chain-fatty-acid-AMP ligase FadD32 Proteins 0.000 description 7
- 101710097703 Probable long-chain-fatty-acid-AMP ligase FadD30 Proteins 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 150000001983 dialkylethers Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
三(氟芳基)铝化合物的单醚加合物,通过在每摩尔铝0.9-1.0摩尔的C1-6脂族醚存在下使三烃基铝化合物和三(氟芳基)硼烷化合物在烃溶剂中进行交换反应而制备。
Description
本发明涉及制备用于烯烃聚合的催化活化剂或合成这些活化剂的三氟芳基铝醚合物、特别是三(五氟苯基)铝醚合物的方法。本发明特别适用于以改进的分离产率和较低的工艺复杂性制备这些化合物。
在US-A-5,602,269中,公开了一种制备含铝、镓或铟的氟芳基衍生物复合物的非醚合物的方法。该方法涉及在烃溶剂中进行相应的金属三烷基化物与氟芳基硼化合物的交换,以得到无配位醚分子的纯形式复合物。然而,已知这些非配位铝复合物是非常敏感的且难以处理。
制备三芳基铝醚合物的工艺包括使用格氏试剂,如US-A-2,960,516、Australian Journal of Chemistry,卷16,第794-800页(1963)、DE-A 1,057,600、Zeitschrift fur Naturforschung,卷20b,第5页(1965)和Journal of the Chemical Society.(1967),第2185页中描述的。
根椐本发明,现已发现在脂族醚和烃稀释剂存在下对三烃基铝和三(氟芳基)硼烷化合物之间的交换反应可加以控制,以得到三(氟芳基)铝化合物的单醚加合物,或从三烃基铝化合物夺去一个烃基配体基团并在生成的阳离子和阴离子之间形成离子对而形成的硼酸铝盐醚合物。为了得到高产率的三(氟芳基)铝化合物,在反应混合物中存在的醚的总量应为每摩尔铝0.9-1.0摩尔,优选每摩尔铝0.95-1.0摩尔。相反,为了得到高产率的硼酸盐,在反应混合物中存在的醚的总量应为每摩尔铝至少5.0摩尔。当使用的醚的总量为每摩尔铝1.0-5.0摩尔时,形成三(氟芳基)铝醚合物与硼酸铝盐醚合物两者的混合物。若使用的醚的量低于上述量,则可能形成少量的非常敏感的无醚化合物。最优选所用的醚量为每摩尔铝1.0摩尔。更优选,该醚是在每个烷基含有1-6个碳原子的二烷基醚。
为了高产率地制备所需的三(氟芳基)铝醚合物,优选三烃基铝试剂是每个烷基含有4-10个碳原子的三烷基铝化合物,最优选三异丁基铝或三(叔丁基)铝。此外,虽然这些试剂可按任何顺序混合,但当将三(氟芳基)硼化合物最后加入到前面形成的三烃基铝化合物和醚的混合物中时,所需的三(氟芳基)铝醚合物的产率最高。
Q1是含有1-20个碳原子的脂族、芳族或脂环族单官能基团,优选苄基型的、或1-20个碳原子的直链或支链烷基,更优选C4-20烷基,最优选异丁基或叔丁基;
Arf是含6-20个碳原子的氟化芳基,优选全氟芳基、最优选全氟苯基;和
Q2是C1-6烷基。
在5∶1摩尔比或更多的醚存在下,工艺步骤概列于下面的流程(B)中:
与≥5.0摩尔醚/摩尔Al的交换反应
其中Q1、Q2和Arf定义如上。
根据流程(A)或(B)的反应在脂族、脂环族或芳族烃溶剂中通过在所需量的醚存在下混合固体形式或在上述溶剂中的液体溶液形式的各试剂来进行。优选该反应通过如下方式进行:将铝试剂溶解在溶剂、优选甲苯或己烷中,加入所需量的醚,最后在搅拌下向如此获得的溶液中加入固体形式或在烃溶剂中的溶液形式的硼试剂。由于这些试剂和产物对氧气或湿气或此两者非常敏感,因此所有反应阶段和所需产物的后继分离都应在惰性气体下进行。
为方便反应、简化反应和最终产物的纯度,保持流程(A)中所示的试剂的摩尔比为约1∶1。事实上,若用过量的试剂BArf 3,则在反应结束时必须对其部分回收;使得分离纯态的所需产品变得更困难。相反,若使用过量的三烃基铝试剂或其醚合物,则也会危害最终产物的纯度,这是因为在反应结束时,除了所要的产品外,还有许多来自于步骤1和2的混合产品,如流程(A)说明的。
交换反应的温度合适地为-20℃至100℃、优选0-45℃、最优选20-30℃。合适的反应时间为数秒钟至数小时,取决于所用试剂和溶剂的种类。所需的产品可通过过滤并随后在真空中干燥数小时从反应混合物中回收。
三(全氟芳基)铝化合物是可用于多种用途的强路易斯酸。最近发现它们可与铝氧烷进行配体交换形成可作为烯烃聚合催化活化剂的化合物。
应懂得本发明可在无任何尚未具体公开的组分下实施。提供下列实施例以更进一步说明本发明而非限制本发明。除非另有说明,所有份和百分数以重量为基准。本文所述的“室温”是指20-25℃,术语过夜”是指12-18小时。
实施例
从Boulder Scientific Inc.得到固体形式的三(全氟苯基)硼(C6F5)3B(FAB),可将其在不进行进一步纯化下使用。从AldrichChemical Co.购得在甲苯或己烷中的三甲基铝(TMA)、在己烷中的三乙基铝(TEA)和三异丁基铝(TIBA)。如Biagini等人的US 5,602,269报道,通过三(全氟苯基)硼烷与三甲基铝的交换反应来制备三(全氟苯基)铝(FAAL,作为甲苯加合物),由FAAL和TMA以1∶1比率进行交换反应制备双核(C6F5)3Al2Me3(FAAl·TMA)。用Pangborn等人,Organometallics,1996,15,1518-1520中公开的方法纯化所有溶剂。所有化合物、溶液和反应都在惰性气氛(干燥箱)中操作。19F NMR谱的所有化学位移都是相对于在苯-d6或甲苯-d8(在使用前都在Na/K合金上干燥和过滤过)中的固定外标(CFCl3)。1H和13C NMR位移参照内溶剂共振并相对于TMS来记录。
为表征目的,制备数种铝化合物和醚合物衍生物。为此,在手套箱中,将FAAL(0.125g,0.20mmol,甲苯加合物)溶于烧瓶中的20ml(约200mmol)的干燥二乙基醚中并滴加TMA(0.101mL,在甲苯中2.0M,0.20mmol)。将该反应混合物在室温下搅拌2小时,在减压下除去溶剂,得到定量产率的粘性白色固体。产物的1H和19F NMR谱图表明形成五种物质的混合物,包括:
(C6F5)3Al·Et2O,(C6F5)2AlMe·Et2O,(C6F5)AlMe2·Et2O,AlMe3·Et2O,and[AlMe2·2Et2O]+[(C6F5)3AlMe]-.
(C6F5)3Al·Et2O:19F NMR(C7D8,23℃)atδ-122.60(d,6F,o-F),-151.04(t,3F,p-F),-160.69(t,6F,m-F).
(C6F5)2AlMe·Et2O:1H NMR(C7D8,23℃)atδ-0.17ppm;19F NMR(C7D8,23℃)δ-122.28(d,4F,o-F),-153.25(t,2F,p-F),-161.64(t,4F,m-F).
(C6F5)AlMe2·Et2O:1H NMR(C7D8,23℃)atδ-0.37ppm;19F NMR(C7D8,23℃)atδ-122.79(d,2F,o-F),-155.78(t,1F,p-F),-162.43(t,2F,m-F).
[AlMe2·2Et2O]+[(C6F5)3AlMe]-:1H NMR(C7D8,23℃)atδ-0.52,-0.95 ppm;19FNMR(C7D8,23℃)at δ-121.59(d,6F,o-F),-158.93(t,3F,p-F),-164.15(t,6F,m-F).
(C6F5)3Al·Et2O与AlMe3·Et2O在二乙基醚中的反应得到类似的形成下列四种物质的结果:(C6F5)3Al·Et2O、(C6F5)2AlMe·Et2O、(C6F5)AlMe2·Et2O和[AlMe2·2Et2O]+[(C6F5)3AlMe]-。长时间反应后或在高温反应后,物质[AlMe2·2Et2O]+[(C6F5)3AlMe]-从NMR谱图中消失。
同样,(C6F5)3Al2Me3与二乙基醚的反应得到(C6F5)2AlMe·Et2O与(C6F5)AlMe2·Et2O的混合物。
实施例1
由(C6F5)3B和AlMe3制备(C6F5)3Al·Et2O
在手套箱中,将TMA(0.50mL,在己烷中2.0M,1.00mmol)溶于烧瓶中的20ml己烷中并加入二乙基醚(0.102mL,1.00mmol),接着按小部分加入固体FAB(0.512g,1.00mmol)。加入FAB期间反应混合物变浑浊,搅拌数分钟后变清且数滴油沉在烧瓶的底部。在室温下搅拌1小时后开始形成沉淀,并将生成的悬浮液在该温度下再搅拌3小时。过滤后收集的白色固体用己烷洗涤两次,并在真空下干燥得到0.28g、47%产率的所需产物(C6F5)3Al·Et2O。
1H NMR(C6D6,23℃):δ3.45(m),0.48(m)ppm.19F NMR(C6D6,23℃):δ-122.68(d,6F,o-F),-151.06(t,3F,p-F),-160.75(t,6F,m-F).
实施例2
由(C6F5)3B和AlMe3制备(C6F5)3Al·Et2O
在手套箱中,将FAB(0.512g,1.00mmol)溶于烧瓶中的20ml无水己烷中并加入二乙基醚(0.102mL,1.00mmol),接着加入TMA(0.50mL,在己烷中2.0M,1.00mmol)。加入TMA期间反应混合物变浑浊,搅拌数分钟后变清且数滴油沉在烧瓶的底部。在室温下搅拌1小时后开始形成沉淀,并将生成的悬浮液在该温度下再搅拌3小时。过滤后收集的白色固体用己烷洗涤两次,并在真空下干燥得到类似产率的所需产物FAAL·Et2O。
但与1.5当量的二乙基醚的相同反应得到油状的产物混合物,包括形成[AlMe2·2Et2O]+[(C6F5)3BMe]-。当将5当量的二丁基醚用于相同反应时,仅生成产物[AlMe2·2Bu2O]+[(C6F5)3BMe]-。
1H NMR(C6D6,23℃):对于配位Bu2O,δ为3.61(m),1.34(m),1.01(m)和0.77(m),对于Al-Me和B-Me,δ分别为0.90和-0.75ppm。19F NMR(C6D6,23℃):δ-132.24(d,6F,o-F),-164.99(t,3F,p-F),-167.60(t,6F,m-F)。
实施例3
由(C6F5)3B和AlEt3制备(C6F5)3Al·Et2O
在手套箱中,将FAB(0.256g,0.50mmol)溶于烧瓶中的15ml干己烷中并加入二乙基醚(0.051mL,0.50mmol),接着加入TEA(0.50mL,在己烷中1.0M,0.50mmol)。加入TEA期间反应混合物变浑浊,搅拌数分钟后变清且数滴油沉在烧瓶的底部。生成的混合物在回流下加热并在该温度下搅拌6小时。然后将溶液冷却至室温并将生成的悬浮液在该温度下搅拌过夜。过滤后收集的白色固体用己烷洗涤两次,并在真空下干燥得到0.22g、75%产率的所需产物FAAL·Et2O。
实施例4
由(C6F5)3B和Al(i-Bu)3制备(C6F5)3Al·Et2O
在手套箱中,将TIBA(0.126mL,0.50mmol)溶于烧瓶中的20ml无水己烷中并加入二乙基醚(0.051mL,0.50mmol),接着按小部分加入固体FAB(0.256g,0.50mmol)。加入FAB期间反应混合物变浑浊,搅拌数分钟后变清且数滴油沉在烧瓶的底部。在室温下搅拌1.5小时后开始形成沉淀,并将生成的悬浮液在该温度下搅拌过夜。过滤后收集的白色固体用己烷洗涤两次,并在真空下干燥得到0.255g所需产物FAAL·Et2O。产率:85%。
实施例5
由(C6F5)3B和Al(i-Bu)3制备(C6F5)3Al·Et2O
在手套箱中,将FAB(0.256g,0.50mmol)溶于烧瓶中的20ml无水己烷中并加入二乙基醚(0.051mL,0.50mmol),接着加入TIBA(0.126mL,0.50mmol)。加入TIBA期间反应混合物变浑浊,搅拌数分钟后变清且数滴油沉在烧瓶的底部。在室温下搅拌1.5小时后开始形成沉淀,并将生成的悬浮液在该温度下搅拌过夜。过滤后收集的白色固体用己烷洗涤两次,并在真空下干燥得到0.202g(产率67%)所需产物FAAL·Et2O。在不超过1当量的二乙基醚存在下的相同反应得到不能分离出产物的乳白色溶液。
Claims (5)
1.一种在包括烃和非必要的C1-6脂族醚的稀释剂存在下通过三烃基铝化合物或其C1-6脂族醚合物衍生物与三(氟芳基)硼烷化合物或其C1-6脂族醚合物衍生物之间的交换反应而制备三(氟芳基)铝化合物的单醚加合物的方法,所述方法包括在使反应混合物中存在的C1-6脂族醚总量为每摩尔铝0.9-1.0摩尔的条件下进行交换反应。
2.权利要求1的方法,其中三烃基铝试剂是每个烷基上含有4-10个碳原子的三烷基铝。
3.权利要求2的方法,其中三烷基铝试剂是三异丁基铝或三(叔丁基)铝。
4.权利要求1的方法,其中将三(氟芳基)硼化合物加入到预先形成的三烃基铝化合物与C1-6脂族醚的混合物中。
5.权利要求1-4中任一项的方法,其中三烃基铝试剂是三异丁基铝,三(氟芳基)硼化合物是三(五氟苯基)硼。
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US6262200B1 (en) * | 1996-08-19 | 2001-07-17 | Northwestern University | (Polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of enhanced utility, uses thereof, and products based thereon |
US6696379B1 (en) * | 1997-09-19 | 2004-02-24 | The Dow Chemical Company | Supported modified alumoxane catalyst activator |
CN1954005B (zh) | 2004-03-17 | 2012-10-10 | 陶氏环球技术有限责任公司 | 用于形成高级烯烃多嵌段共聚物的包含梭移剂的催化剂组合物 |
TW200604224A (en) | 2004-03-17 | 2006-02-01 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
CA2558251A1 (en) | 2004-03-17 | 2005-09-29 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
CN103102442B (zh) | 2004-06-16 | 2016-01-20 | 陶氏环球技术有限责任公司 | 选择聚合改性剂的方法 |
WO2006020624A1 (en) * | 2004-08-09 | 2006-02-23 | Dow Global Technologies Inc. | Supported bis(hydroxyarylaryloxy) catalysts for manufacture of polymers |
US8981028B2 (en) | 2005-03-17 | 2015-03-17 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
MX2007011340A (es) | 2005-03-17 | 2007-10-03 | Dow Global Technologies Inc | Composicion de catalizador que comprende un agente de transporte para la formacion de copolimero de bloques multiples regio-irregular. |
TW200722441A (en) | 2005-09-15 | 2007-06-16 | Dow Global Technologies Inc | Catalytic olefin block copolymers via polymerizable shuttling agent |
EP1940897B1 (en) | 2005-09-15 | 2014-05-07 | Dow Global Technologies LLC | Control of polymer architecture and molecular weight distribution via multi-centered shuttling agent |
US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
WO2007136494A2 (en) | 2006-05-17 | 2007-11-29 | Dow Global Technologies Inc. | Ethylene/ alpha-olefin/ diene solution polymerization process |
ITMI20070877A1 (it) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | Processo per la produzione di copolimeri a blocchi multipli con l'utilizzo di solventi polari |
ITMI20070878A1 (it) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | Processo per la polimerizzazine di polimeri tattici con l'uso di catalizzatori chirali |
ES2435568T3 (es) * | 2007-11-19 | 2013-12-20 | Dow Global Technologies Llc | Copolímeros de propileno-alfa-olefina con ramificación de cadena larga |
EP2757113A2 (en) | 2009-03-06 | 2014-07-23 | Dow Global Technologies LLC | Catalysts, processes for making catalysts, processes for making polyolefin compositions and polyolefin compositions |
EP2459598B1 (en) | 2009-07-29 | 2017-10-18 | Dow Global Technologies LLC | Dual- or multi-headed chain shuttling agents and their use for the preparation of block copolymers |
WO2011016992A2 (en) | 2009-07-29 | 2011-02-10 | Dow Global Technologies Inc. | Polymeric chain transfer/shuttling agents |
KR102606500B1 (ko) | 2015-09-30 | 2023-11-28 | 다우 글로벌 테크놀로지스 엘엘씨 | 사슬 왕복에 유용한 다중-헤드 또는 이중-헤드 조성물 및 이를 제조하는 방법 |
EP3519474A1 (en) | 2016-09-30 | 2019-08-07 | Dow Global Technologies LLC | Process for preparing multi- or dual-headed compositions useful for chain shuttling |
EP3519456A1 (en) | 2016-09-30 | 2019-08-07 | Dow Global Technologies Llc | Capped multi- or dual-headed compositions useful for chain shuttling and process to prepare the same |
TW201840572A (zh) | 2016-09-30 | 2018-11-16 | 美商陶氏全球科技有限責任公司 | 適用於鏈梭移之多頭或雙頭組合物及其製備方法 |
SG11202107067RA (en) | 2018-12-28 | 2021-07-29 | Dow Global Technologies Llc | Organometallic chain transfer agents |
CN113498414A (zh) | 2018-12-28 | 2021-10-12 | 陶氏环球技术有限责任公司 | 包括遥爪聚烯烃的可固化组合物 |
US20220073540A1 (en) | 2018-12-28 | 2022-03-10 | Dow Global Technologies Llc | Curable compositions comprising unsaturated polyolefins |
KR20210121027A (ko) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 불포화 폴리올레핀을 포함하는 경화성 조성물 |
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