CN1345322A - 含有中性、多齿氮杂环配位体的金属化合物,使用它们的催化剂,和用它们进行烯烃聚合的方法 - Google Patents
含有中性、多齿氮杂环配位体的金属化合物,使用它们的催化剂,和用它们进行烯烃聚合的方法 Download PDFInfo
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- CN1345322A CN1345322A CN00805727A CN00805727A CN1345322A CN 1345322 A CN1345322 A CN 1345322A CN 00805727 A CN00805727 A CN 00805727A CN 00805727 A CN00805727 A CN 00805727A CN 1345322 A CN1345322 A CN 1345322A
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- silicon
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- 239000003446 ligand Substances 0.000 title claims abstract description 51
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- 238000000034 method Methods 0.000 title claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 3
- 150000002736 metal compounds Chemical class 0.000 title description 2
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 39
- 150000003624 transition metals Chemical class 0.000 claims abstract description 39
- 125000003226 pyrazolyl group Chemical group 0.000 claims abstract description 22
- 239000012190 activator Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
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- 125000001425 triazolyl group Chemical group 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- ZGYMTXXXQBXQPB-UHFFFAOYSA-N [SiH](C)(C1=NNC=C1)C Chemical compound [SiH](C)(C1=NNC=C1)C ZGYMTXXXQBXQPB-UHFFFAOYSA-N 0.000 description 2
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- KLORKMOYYIOYOT-UHFFFAOYSA-K titanium(3+);triacetate Chemical compound [Ti+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KLORKMOYYIOYOT-UHFFFAOYSA-K 0.000 description 1
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
本发明公开了中性、多齿氮杂环配位体和它们与第3－10族金属和镧系金属的络合物。该配位体具有通式:Ra－A－(L)b,其中R是氢或烃基,A是硅、锗、锡或铅,每个L是吡唑基、三唑基或四唑基,a=0－2,b=2－4,和a+b=4。在用常用活化剂活化时,所述金属络合物可使烯烃聚合。
Description
发明的技术领域
本发明涉及含中性吡唑基、三唑基和四唑基的配位体(“氮杂环”配位体)和含有上述配位体的过渡金属络合物。该络合物是有机反应，特别是烯烃聚合的有价值的前催化剂(procatalyst)。
发明的背景技术
化学工业中应用多种过渡金属络合物作为有机反应的催化剂。聚烯烃的制备就是一个很好的实例。多年来齐格勒-纳塔催化剂在工业上占有优势，并且出现了高活性的金属茂催化剂或单点催化剂，用它们可得到分子量分布窄、密度低和共聚单体结合好的新聚合物。
用于烯烃聚合的过渡金属络合物通常是由阴离子配位体(例如氯、烷基、环戊二烯基)包围的非零价金属(例如Ti4+，Zr4+，Sc3+)，它们既可满足金属化合价的要求，又可改善催化剂在反应介质中的溶解性。阴离子配位体对催化剂的活性和聚合物的性质有意想不到的影响。
中性、多齿的配位体过去仅在制备过渡金属络合物时用作金属茂或单点聚烯烃催化剂的前体。例如，1，4，7-三甲基-1，4，7-三氮杂环壬烷(tmtacn)用于制备钪、铬和铑的(tmtacn)MCl3络合物(参见Wang等人，J.Am.Chem.Soc.，119(1993)6999)；这些络合物的衍生物可催化烯烃的聚合。其它实例是1，4，7-三硫杂环壬烷(ttcn)，用它已制备了(ttcn)RhCl3(参见S.Timonen等人，J.Mol.Catal.A.，111(1996)267)。由于它们的复杂性、高成本和合成时的竞争。这些配位体没有能够广泛推广。也有更容易被接受的中性配位体(例如1，2-双(二苯膦)乙烷)，一般来说，它们没有给金属茂或单点催化剂带来显著的优点。
对中性、多齿配位体来说，可能具有生命力的一种途径是在碱存在下，使三价的吡唑与氯仿反应，得到三(吡唑基)甲烷。此方法是经济的和有吸引力的，因为通过使乙酰基丙酮类化合物与肼反应可得到多种吡唑。不幸的是，形成碳烯使产物的混合物复杂化，并且会减少目的产物三(吡唑基)化合物的产率。
阴离子三(吡唑基)硼酸盐配位体是已知的。例如，在USP 5,504,049中，VOCl3与三(吡唑基)硼酸钾反应，制备得到一络合物，在活化剂如MAO存在下，用该络合物使乙烯聚合。此外，三(吡唑基)硅烷也是已知的：S.Vepachedu等人(Acta Cryst.C51(1995)423)报道了三(3，5-二甲基吡唑基)甲基甲硅烷的结晶结构。
总之，需要有新的中性、多齿配位体。特别是由容易买到的原料很容易合成的有价值的配位体。优选的是，该配位体可以高产率制备，并且没有诸如形成碳烯的复杂的副反应。理想的是，该配位体能够用来制备新的过渡金属络合物，该络合物可用作烯烃聚合的前催化剂。
发明综述
本发明是一类新的中性、多齿配位体。该配位体具有通式：Ra-A-(L)b，其中R是氢或C1-C30烷基、芳基或芳烷基，A是硅、锡、锗或铅，L各自独立地是取代或未取代的吡唑基、三唑基或四唑基，a＝0-2，b＝2-4，和a+b＝4，条件是当R＝甲基，A是硅，和a＝1时，L不是3，5-二甲基吡唑基。
本发明包括过渡金属络合物，该络合物含有第3-10族过渡金属或镧系金属(M)，一个或多个阴离子或中性配位体，该配位体的数量要满足M的化合价，以及如上文所述的中性、多齿配位体。本发明还包括烯烃聚合催化剂；所述的催化剂含有过渡金属络合物和诸如MAO或硼酸盐的活化剂。最后，本发明还包括应用这些催化剂的烯烃聚合方法。
发明人出人意料地发现，以第14族元素(硅、锡、锗或铅)为基础的中性、多齿配位体和吡唑基、三唑基或四唑基很容易合成和纯化。而且，配位体容易与第3-10族过渡金属和镧系金属反应得到络合物，该络合物对很多有机变换反应，包括烯烃复分解(metathesis)、异构化、齐聚作用等都是很有价值的。特别是，该络合物与常用的活化剂如铝氧烷或硼酸盐反应，得到优良的烯烃聚合单点催化剂。
发明的详细描述
本发明的中性、多齿氮杂环配位体具有通式Ra-A-(L)b，式中A是碳以外的第14族元素。换言之，A可以是硅、锗、锡或铅，硅是优选的。R是氢或C1-C30烷基、芳基或芳烷基。优选的，R是氢或C1-C5烷基基团。每个L各自独立地是吡唑基、三唑基或四唑基；a＝0-2，优选1-2；b＝2-4，优选2-3；和a+b＝4。
所谓“吡唑基”，是指具有下述结构的基团：其中三个环碳上的原子中的任意一个是未取代(即有一个氢)或被R1、R2和/或R3取代的，其中每个R1、R2和/或R3可独立地是烃基、卤化物、烷醇盐、二烷氨基、硝基或类似基团。两个相邻的烃基基团可以结合形成环状结构，如吲唑或四氢吲唑。所述的吡唑基通过1-位氮原子以σ-键与硅、锡、锗或铅原子键合。未取代或烃基取代的吡唑基是优选的。
类似地，三唑基配位体具有下式结构：
其中R1和R2如上文定义。四唑基配位体具有下式结构：
其中R1如上文定义。
适当的中性、多齿配位体包括例如：双(吡唑基)二甲基甲硅烷、双(吡唑基)甲基苯基甲硅烷、双(吡唑基)二苯基甲硅烷、双(吡唑基)双(二甲氨基)甲硅烷、双(吡唑基)硅杂环丁烷、双(吡唑基)硅杂环戊烷、双(3，5-二甲基吡唑基)二甲基甲硅烷、双(吲唑)二甲基甲硅烷、双(4-氯吡唑基)二甲基甲硅烷、双(4-甲基吡唑基)二甲基甲硅烷、双(3，5-三氟甲基吡唑基)二甲基甲硅烷、三(吡唑基)甲基甲硅烷、双(吡唑基)甲基甲硅烷、三(3-甲基吡唑基)甲基甲硅烷、四(吡唑基)甲硅烷、双(三唑基)二甲基甲硅烷、双(苯并三唑基)二甲基甲硅烷、三(苯并三唑基)甲基甲硅烷、双(四唑基)二甲基甲硅烷、三(四唑基)甲基甲硅烷、三(吡唑基)甲基锡、三(3，5-二甲基吡唑基)锗烷、三(吡唑基)甲基锗烷、四(吡唑基)铅、四(3，5-二氯吡唑基)甲硅烷等，和其混合物。特别优选的是二和三(吡唑基)烷基甲硅烷，以及二和三(3，5-二取代的吡唑基)烷基甲硅烷。
中性、多齿配位体很容易制备。氮杂环化合物(例如吡唑、3，5-二甲基吡唑、苯并三唑、四唑等)通常可以买到。在一方便的制备中，使氮杂环与强碱如正丁基锂在惰性溶剂(如醚)中反应进行脱质子化，蒸发溶剂后得到其碱金属盐。然后使2-4当量的这种盐与第14族的化合物反应，优选与具有相当数目的良好离去基团的化合物(例如，三摩尔的氮杂环盐和一摩尔的三氯甲基甲硅烷反应)，得到中性、多齿配位体。精制过程通常由下述步骤组成：将反应产物溶于溶剂(例如烃或卤代烃)，过滤除去碱金属盐，以及使配位体重结晶。下面的实施例1-14说明了如何制备本发明的中性配位体。
本发明包括用中性、多齿配位体制备的过渡金属络合物。除了中性、多齿配位体以外，该过渡金属配位体还包括第3-10族过渡金属或镧系金属M，以及一个或多个阴离子或中性配位体，其数量能够满足M的化合价。
第3-10族的金属包括Sc，Ti，Cr，Mn，Fe，Co，Ni和元素周期表中直接于这些元素以下的元素。适当的镧系金属包括Le，Ce，Pr，Eu，Yb等。优选的是第3-6族过渡金属和镧系金属。最优选的是第4族过渡金属。
阴离子或中性配位体使过渡金属络合物达到平衡。其实例包括未取代的或取代的环戊二烯基、茚、芴、氢化物、卤化物、烷基、芳基、芳烷基、二烷氨基、硅氧基、烷氧基、吡咯基、吲哚基、咔唑基、喹啉基、吡啶基、氮杂borolinyl、硼杂芳基基团等，以及它们的结合。中性配位体的实例是羰基、η6-芳基、η4-丁二烯、η4-环丁二烯、η4-环辛四烯、叔膦等。适当的阴离子或中性配位体的其它实例见USP5,756,611、5,637,659、5,637,660、5,554,775和5,539,124，引用上述文件的教导作为本文的参考。
任何常用的过渡金属源均可使用。例如，络合物可由过渡金属卤化物、烷基化物、烷醇盐、乙酸盐、酰胺等制备。尤其常用的过渡金属源是过渡金属卤化物。例如可用的是氯化钒(III)-四氢呋喃络合物(VCl3(THF)3)、氯化钛(III)THF络合物、氯化铬(III)THF络合物、氯化钴(II)、溴化镍(II)、氯化铂(II)、氯化钯(II)、氯化镧(III)、乙酸钛(III)等。络合物也可以由带有不稳定基团的盐如四(乙腈)铂(II)双(四氟硼酸盐)制备。
过渡金属络合物很容易制备。通常，是把过渡金属源(如卤化物)溶于或悬浮于有机溶剂，小心加入中性、多齿配位体。如果需要，为完成反应进行回流。如果有不溶的副产物，可过滤除去，蒸发溶剂，分离过渡金属络合物，洗涤，和干燥。通常所得到的络合物可直接使用而不需要进一步纯化。
双核络合物(含有一个以上的金属中心)可由二当量的适当金属前体与四(氮杂环)甲硅烷反应来制备。因此，使两当量的NiCl2与(C3H3N2)Si(即(Pz)4Si)反应可得到双核络合物Cl2Ni(Pz)2Si(Pz)2NiCl2。类似地，用树枝状(dendrimeric)的多臂配位体如[(Pz)3SiCH2CH2]Si(由12当量的Li(Pz)和[Cl3SiCH2CH2]4Si制备)可得到多核金属络合物。
预期本发明过渡金属络合物是有价值的催化剂、催化剂前体或各种有机反应的试剂，例如包括烯烃的复分解、异构化和聚合反应。
本发明包括含有上述过渡金属络合物和活化剂的催化剂。一般来说，活化剂使络合物转化成阳离子活性种。所述的催化剂对烯烃聚合是特别有价值的，例如乙烯、丙烯和/或其它α-烯烃如1-丁烯或1-己烯的聚合。
适当的活化剂在本领域是已知的。实例包括铝氧烷(甲基铝氧烷(MAO)、PMAO、乙基铝氧烷、二异丁基铝氧烷)、烷基铝化合物(三乙基铝、二乙基铝氯化物、三甲基铝)等。通常活化剂的使用量是相对于每摩尔过渡金属络合物在大约0.01-大约100,000摩尔，优选大约1-大约10,000摩尔的范围内。
适当的活化剂包括酸盐，其中含有非亲核阴离子。这些化合物通常由连接于硼或铝的大体积配位体构成。实例包括四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)苯铵硼酸盐等。这些活化剂一般用量是相对于每摩尔过渡金属络合物在大约0.01-大约1000摩尔，优选大约1-大约10摩尔的范围内。
适当的活化剂还包括三烷基或三芳基硼化合物，例如三(五氟苯基)硼、三(五溴苯基)硼等。其它适当的活化剂在例如下面所述：USP5,756,611、5,064,802和5,599,761，引用上述文件的教导作为本文参考。
该催化剂任意地与无机固体或有机聚合物载体一起使用。适当的载体包括二氧化硅、氧化铝、二氧化硅-氧化铝、氯化镁、二氧化钛、粘土、沸石等。可以用热或化学方法对载体进行预处理，以改进催化剂的产率或产物的性能。催化剂可以任何需要的方式沉积在载体上。例如，可将催化剂溶于溶剂，与载体结合，和汽提。另外，也可以使用初期湿润技术(incipient-wetness technique)。而且也可以将载体与催化剂分别引入反应器。配位体也可以通过适当的连接基团化学键接于载体。
本发明包括烯烃聚合方法。该方法包括按照本领域已知的方法，在本发明的催化剂存在下使烯烃聚合。适当的技术包括气相、高压液相、浆液、溶液或悬浮相的方法，以及它们的结合。适当的烯烃包括乙烯、丙烯、丁烯、戊烯、己烯、辛烯、苯乙烯、1，3-丁二烯、降冰片烯等，优选的烯烃是乙烯、丙烯和α-烯烃如1-丁烯、1-己烯和1-辛烯。下文的实施例11和12说明了本发明制备聚乙烯的实验室规模的方法。
下面的实施例仅仅是为了说明本发明，本领域熟练技术人员可以理解的是有很多变化都在本发明的精神和权利要求的保护范围之内。
实施例1-4
配位体的制备
实施例1
制备双(吡唑基)二甲基甲硅烷
将吡唑(6.81g)溶于乙醚(125ml)，并加入正丁基锂(40ml的2.5M己烷溶液)。半小时之后，蒸发溶剂，加入戊烷。过滤出白色固体(7.30g)，并干燥。
把上述固体溶于乙醚(100ml)，向其中滴加二氯二甲基甲硅烷(6.36g)的乙醚(10ml)溶液。将雾状的悬浮液搅拌过夜，过滤。蒸发滤液，残余物溶于温热的戊烷，过滤。将滤液冷却至-30℃，沉淀出白色固体(7.26g)。1H NMR(甲苯-d8)：0.64(s，CH3-Si)，6.09(t)，7.28(d)，7.70(d)。
实施例2
制备双(3，5-二甲基吡唑基)二甲基甲硅烷
将3，5-二甲基吡唑(9.61g)溶于乙醚(175ml)，并加入正丁基锂(10ml的10M己烷溶液)。1.5小时之后，蒸发该混合物，加入戊烷。冷却至-30℃，沉淀出白色固体(8.53g)，过滤和干燥。
把上述固体溶于乙醚(100ml)，向其中滴加二氯二甲基甲硅烷(5.40g)的乙醚(10ml)溶液，沉淀出白色固体。混合物回流1.5小时，然后冷却至室温，过滤。蒸发滤液，将得到的白色结晶溶于戊烷，过滤。将滤液冷却至-30℃，沉淀出白色结晶(5.43g)。1H NMR(甲苯-d8)：0.82(s，CH3-Si)，1.79(s)，2.20(s)，5.69(s)。
实施例3
制备三(吡唑基)甲基甲硅烷
将吡唑(6.81g)溶于乙醚(125ml)，并加入正丁基锂(40ml的2.5M己烷溶液)。半小时之后，蒸发溶剂，加入戊烷。过滤出白色固体(7.20g)，干燥。
把上述固体溶于乙醚(150ml)，向其中滴加三氯甲基甲硅烷(4.85g)的乙醚(15ml)溶液。混合物搅拌过夜，过滤。蒸发滤液，残余物溶于温热的戊烷，过滤。将滤液冷却至-30℃，沉淀出白色结晶(5.13g)。1H NMR(甲苯-d8)：1.04(s，CH3-Si)，5.89(t)，7.21(s)，7.52(s)。
实施例4
制备三(3，5-二甲基吡唑基)甲基甲硅烷
将3，5-二甲基吡唑(19.2g)溶于乙醚(150ml)，并加入正丁基锂(20ml的10M己烷溶液)。0.5小时之后，蒸发溶剂，用己烷收集固体，并冷却至-30℃，产率：(14.7g)。
把上述固体溶于乙醚(125ml)，向其中滴加三氯甲基甲硅烷(7.17g)，混合物回流1小时，冷却，过滤。蒸发滤液，将得到的残余物溶于戊烷(200ml)，过滤。将滤液冷却至-30℃，沉淀出白色结晶(9.84g)。1H NMR(甲苯-d8)：1.58(s，3-CH3和CH3-Si)，2.19(s)，5.69(s)。
实施例5-10
制备过渡金属络合物
实施例5
制备MeSi(Me2Pz)3VCl3
将氯化钒(III)-四氢呋喃络合物(VCl3(THF)3，1.86g)溶于2∶1CH2Cl2/THF溶液(40ml)。缓慢加入溶于CH2Cl2(15ml)中的实施例4的产物(1.64g)。15分钟后，形成橄榄绿的沉淀。混合物搅拌过夜，过滤。用CH2Cl2和戊烷洗涤固体，干燥。产率：1.59g。
实施例6
制备MeSi(Me2Pz)3CrCl3
将氯化铬(III)-四氢呋喃络合物(CrCl3(THF)3，1.87g)悬浮于CH2Cl2(30ml)中。缓慢加入溶于CH2Cl2(15ml)中的实施例4产物(1.62g)。紫色的悬浮液变成澄清的和绿色的。30分钟后，过滤溶液，并蒸发滤液。固体用戊烷洗涤，干燥。产率：2.19g。
实施例7
制备MeSi(Me2Pz)3TiCl3
将氯化钛(III)-四氢呋喃络合物(TiCl3(THF)3，2.57g)溶于3∶1CH2Cl2/THF溶液(40ml)。加入溶于CH2Cl2(40ml)中的实施例4产物(1.70g)。1小时后，蒸发溶剂，用戊烷收集固体。产率：2.49g。
实施例8
制备MeSi(Pz)3TiCl3
将氯化钛(III)-四氢呋喃络合物(TiCl3(THF)3，1.85g)溶于CH2Cl2(15ml)。加入溶于CH2Cl2(30ml)的实施例3的产物(1.22g)。几乎是立刻形成海蓝宝石色的沉淀。45分钟后，过滤出固体，用CH2Cl2和戊烷洗涤，干燥。产率：2.00g。
实施例9
制备MeSi(Me2Pz)2CoCl2
将氯化钴(II)(1.00g)和实施例2的产物(1.54g)于THF(50ml)中回流1小时。蒸发溶剂，用戊烷收集固体。产率：2.10g。
实施例10
制备Me2Si(Me2Pz)2NiBr2
将溴化镍(II)(1.09g)悬浮于THF(30ml)。加入实施例2的产物(1.24g)，棕色的固体变成蓝色。混合物回流1.5小时，过滤。蒸发滤液，用戊烷收集蓝色固体，过滤和干燥。产率：0.29g。
实施例11-12
聚乙烯的制备
实施例11
用MeSi(Me2Pz)3CrCl3聚合
在实施例6的产物(10mg)中加入甲基铝氧烷(10ml的10wt％MAO的甲苯溶液)。将混合物注射到1.7L不锈钢高压釜中，釜中含有干燥脱氧甲苯(850ml)。将高压釜加热到80℃，用乙烯加压(150psi)。1小时后，冷却高压釜，在氮气流下蒸发其中的内容物，聚乙烯产率：12.1g。
实施例12
用MeSi(Me2Pz)3VCl3聚合
在实施例5的产物(8mg)中加入甲基铝氧烷(10ml的10wt％MAO的甲苯溶液)。混合物在实施例11条件下聚合，聚乙烯产率：2.1g。
前述的实施例仅仅是为了说明；下面的权利要求书确定了本发明的保护范围。
Claims (13)
1.一种催化剂，该催化剂包括：
(a)活化剂；和
(b)过渡金属络合物，该络合物含有：
(i)第3-10族过渡金属或镧系金属，M；
(ii)一个或多个阴离子或中性配位体，其数量要满足M的化合价；
(iii)下式的中性、多齿配位体：
Ra-A-(L)b
其中R是氢或C1-C30烷基、芳基或芳烷基，A是硅、锡、锗或铅，每个L独立地是取代或未取代的吡唑基、三唑基或四唑基，a＝0-2，b＝2-4，和a+b＝4。
2.如权利要求1的催化剂，其中所述活化剂选自铝氧烷、烷基铝化合物、烷基硼化合物以及非亲核硼酸盐和铝酸盐。
3.如权利要求1的催化剂，其中所述过渡金属络合物含有第3-6族的过渡金属或镧系金属。
4.如权利要求1的催化剂，其中M是第4族过渡金属和M的氧化态是3+。
5.如权利要求1的催化剂，其中所述中性、多齿配位体具有下式结构：
(H3C)a-Si-(L)b
其中a＝1-2和b＝2-3。
6.一种权利要求1的负载催化剂。
7.一种下式的中性配位体：
Ra-A-(L)b
其中R是氢或C1-C30烷基、芳基或芳烷基，A是硅、锡、锗或铅，每个L独立地是取代或未取代的吡唑基、三唑基或四唑基，a＝0-2，b＝2-4，和a+b＝4，条件是当R＝甲基，A是硅，和a＝1时，L不是3，5-二甲基吡唑基。
8.如权利要求7的配位体，其中R是甲基，A是硅，L是未取代的吡唑基，以及a＝1。
9.一种过渡金属络合物，该络合物含有：
(a)第3-10族过渡金属或镧系金属，M；
(b)一个或多个阴离子或中性配位体，其数量要满足M的化合价；以及
(c)下式的中性、多齿配位体：
Ra-A-(L)b
其中R是氢或C1-C30烷基、芳基或芳烷基，A是硅、锡、锗或铅，每个L独立地是取代或未取代的吡唑基、三唑基或四唑基，a＝0-2，b＝2-4，和a+b＝4，条件是当R＝甲基，A是硅，和a＝1时，L不是3，5-二甲基吡唑基。
10.如权利要求9的过渡金属络合物，该络合物含有第3-6族过渡金属或镧系金属。
11.如权利要求9的过渡金属络合物，其中A是硅。
12.一种包括烯烃聚合在内的方法，在该方法中存在有权利要求1的催化剂。
13.如权利要求12的方法，其中所述烯烃是乙烯，或是乙烯和α-烯烃的混合物。
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| US09/288,093 US6180552B1 (en) | 1999-04-07 | 1999-04-07 | Transition metal complexes containing neutral, multidentate azacyclic ligands |
| US09/288,093 | 1999-04-07 |
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| CN1300150C (zh) * | 2005-09-01 | 2007-02-14 | 南开大学 | 银配位聚合物和制备方法及其应用 |
| CN101889029B (zh) * | 2007-12-05 | 2012-09-19 | Lg化学株式会社 | 用于烯烃聚合的含有四唑基团的非茂金属型催化剂和使用该催化剂的烯烃聚合方法 |
| CN113856764A (zh) * | 2021-10-29 | 2021-12-31 | 华中科技大学 | 一种过渡金属催化剂及其制备方法和应用 |
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| US6391988B1 (en) * | 2001-04-18 | 2002-05-21 | Equistar Chemicals L.P. | Tris(pyrazoyl) based anions |
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- 2000-02-25 EP EP00911957A patent/EP1165568A4/en not_active Withdrawn
- 2000-02-25 AU AU33766/00A patent/AU3376600A/en not_active Abandoned
- 2000-02-25 WO PCT/US2000/004757 patent/WO2000059914A1/en not_active Application Discontinuation
- 2000-02-25 CA CA002364502A patent/CA2364502A1/en not_active Abandoned
- 2000-02-25 KR KR1020017012712A patent/KR20010112403A/ko not_active Application Discontinuation
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| CN1300150C (zh) * | 2005-09-01 | 2007-02-14 | 南开大学 | 银配位聚合物和制备方法及其应用 |
| CN101889029B (zh) * | 2007-12-05 | 2012-09-19 | Lg化学株式会社 | 用于烯烃聚合的含有四唑基团的非茂金属型催化剂和使用该催化剂的烯烃聚合方法 |
| US8431660B2 (en) | 2007-12-05 | 2013-04-30 | Lg Chem, Ltd. | Non-metallocene catalysts having tetrazol group for olefin polymerization and polymerizing method of olefin using the same |
| CN113856764A (zh) * | 2021-10-29 | 2021-12-31 | 华中科技大学 | 一种过渡金属催化剂及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US6180552B1 (en) | 2001-01-30 |
| US6384229B1 (en) | 2002-05-07 |
| EP1165568A1 (en) | 2002-01-02 |
| JP2002541152A (ja) | 2002-12-03 |
| CA2364502A1 (en) | 2000-10-12 |
| AU3376600A (en) | 2000-10-23 |
| EP1165568A4 (en) | 2002-10-16 |
| WO2000059914A1 (en) | 2000-10-12 |
| KR20010112403A (ko) | 2001-12-20 |
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