CN110914283A - 三齿亚氨基吡咯基镍配合物以及其作为乙烯聚合为超支化聚乙烯的反应的催化剂的用途 - Google Patents
三齿亚氨基吡咯基镍配合物以及其作为乙烯聚合为超支化聚乙烯的反应的催化剂的用途 Download PDFInfo
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- CN110914283A CN110914283A CN201880041109.6A CN201880041109A CN110914283A CN 110914283 A CN110914283 A CN 110914283A CN 201880041109 A CN201880041109 A CN 201880041109A CN 110914283 A CN110914283 A CN 110914283A
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Classifications
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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Abstract
本发明涉及具有一般分子结构(I)的含有亚氨基吡咯基型配体的新型镍配合物的制备以及其在乙酯聚合反应为超支化聚乙烯过程中作为活性催化剂的用途。配体前体的结构使得其能够在针对金属中心的配位反应中通过C‑H键活化发生环金属化反应,产生C,N,N'‑三齿配合物。
Description
技术领域
本发明涉及含有亚氨基吡咯基型三齿配体的新型有机金属镍化合物的合成,属于有机化学和有机金属化学领域。本发明还涉及这些化合物作为乙烯低聚或聚合为超支化聚乙烯的反应的无铝催化剂的用途,属于均相催化剂和烯烃的低聚或聚合领域。
背景技术
无论是寻找更有效的新催化体系或新材料还是更可持续的反应介质,对乙烯和α-烯烃的均聚和共聚反应的研究一直是科学界和工业界正在关注的主题。特别地,在开发在没有铝助催化剂的情况下具有活性的含有后过渡金属的新型均相催化剂方面已经取得了重要的进展。R.Grubbs和合作者(1998-2003)通过合成具有单负电苯氧基亚胺配体的烷基或芳基镍配合物开始了这一领域的开拓性工作,所述配合物在没有铝助催化剂的情况下作为乙烯与极性单体的均聚和共聚的催化前体进行试验,在温和的反应条件下显示出高活性。其它作者,如M.Brookhart(2003)、Y.-S.Li(2005-2012)或S.Mecking(2004-2009),通过开发类似的镍基催化剂扩展了该研究领域。然而,到目前为止,关于与先前体系可能有关的含有亚氨基吡咯基型配体的镍配合物研究的报道很少。这一事实引起了带有双齿配体2-亚氨基吡咯基衍生物的中性镍配合物的开发,其显示出在乙烯的低聚中具有作为催化剂的活性(R.M.Bellabarba,P.T.Gomes,S.I.Pascu,Dalton Trans.2003,4431)。
考虑到螯合配体的体积影响催化体系对低聚/聚合的活性,以及所获得的低聚物/聚合物的分子量,开发了一个新的带有5-芳基-2-(N-芳基)亚胺甲基吡咯基型的大体积双齿配体的镍(II)配合物家族,并通过使用不同的芳基取代基引入了立体化学和/或电子改性(C.A.Figueira,2013)。该研究还使得通过分子内C-H活化形成C,N,N'-三齿镍(II)配合物。
在文献中,有一些涉及分子内C-H键活化反应导致形成C,N,N'-三齿(或类似的)后过渡金属配合物的报道的实例。通常,配体的结构在苯基或芳基环的邻位碳中具有特定的C-H键,其被迫使接近金属中心,这促进了活化和环金属化产物的形成。报道的实例涵盖N,X铱配合物(其中X=N'、O、S)、N,O锇配合物以及Ν,Ν'铂和钯配合物。有限数量的作者对于镍也描述了这种出乎意料的反应。G.Bazan和合作者(2001)报道了第一个实例,同时研究了在吡啶甲酰胺合镍配合物中取代吡啶配体的作用。在N-(2,6-ipr2C6H3)-6-(SiiPr3)-2-吡啶甲酰胺配体的具体情况中,与Si原子键合的异丙基之一在配位后经历了C-H活化。M.Chetcuti和合作者(2010)研究了带有N-杂环卡宾(NKC)配体的Cp和Cp*镍配合物,并描述了乙腈配体的C-H活化,产生了氰甲基镍配合物。随后,他们还报道了一系列[Ni(NHC)CpX](其中X=Cl、Br、I)型配合物,其中,卡宾环的氮原子之一包含烷基腈链,描述了发生在腈基的C-H键α处的分子内活化反应,产生了金属环状镍物种(2011)。
关于这类活化的最新研究是结果类似于本发明的唯一的实例:G.Du和合作者(2013)描述了由于苯胺基的一个甲基取代基的环金属化反应获得的多种带有β-二酮亚胺配体的C,N,N'-三齿镍配合物的合成和表征。然而,亚胺部分的改性还导致邻苯基位置处的C-H活化反应。
如前所述,寻找具有创新特性的新型聚合物材料一直是研究的主题。在不同的类型中,呈现三维球形结构的树枝状聚合物的合成已引起人们的关注,因为它们的高度支化结构赋予了独特的特性,如低粘度、良好的溶解性和高表面,从而引入反应活性中心/官能团。树枝状聚合物的种类包括均匀支化的树状聚合物和具有不规则分支的超支化聚合物,但是其优点在于它们模拟第一种并且易于合成。通常通过使用非市售单体引入均匀的分支,这需要特定的多步合成方法,限制了所得产物的规模和应用类型,故重要的是开发使用简单市售单体(如乙烯)的替代性一步催化方法。
A.Sen和合作者(1998-2000)使用Ni和Pd催化剂以及Ta和Ti体系合成了低分子量超支化聚乙烯(PE)。但是,该领域的最大进展出现在Z.Guan和合作者(1999)展示了只要通过改变引入乙烯的压力条件,即可在存在α-二亚胺Pd(II)催化剂(由M.Brookhart和合作者开发)的情况下轻松控制聚乙烯(PE)的微观结构。这归因于沿着聚合物链的异构化的内在机理(“链行走”),这是这些类型的催化剂及其Ni(II)类似物的重要特征。在链增长期间,通过β-氢化物消除、键旋转和随后的1,2-移位氢化物迁移的连续过程,活性中心沿着聚合物链异构化到内部位置。因此,下一个单体单元可以结合在聚合物链的任何位置,而不是仅在末端。通过这种策略,由催化剂而非通过单体产生超支化结构。通过改变实验条件,可以控制“链行走”与链增长过程之间的竞争,从而将聚合物链拓扑结构从线性(高压,例如27atm)调整为超支化(通常为低压,约1atm)。针对这一主题,对二亚胺-Pd型催化剂进行了广泛的研究,并且与类似的镍催化剂相比其通常显示出更高的进行“链行走”的能力。然而,最近报道的结果表明,Ni催化剂产生的聚乙烯的支化度在120-150/1000个碳原子范围内。
考虑到先前的结果,因此有兴趣开发具有更高催化活性并同时产生超支化聚乙烯产物的C,N,N'型的新型潜在的三齿亚氨基吡咯基镍配合物。
发明内容
本发明涉及合成具有一般分子结构(I)的C,N,N'-三齿亚氨基吡咯基镍配合物,其可用作乙烯聚合反应为超支化聚乙烯的催化剂。
这些新的配合物的特殊之处在于,螯合的亚氨基吡咯基配体是潜在的双齿配体,但在合成反应结束时,其作为三齿配体与镍中心键合。实际上,N,N'-双齿镍配合物的合成遵循已申请专利的文献中描述的方法(D.A,Sansleben,S.K.Friedrich,T.R.Younkin,R.H.Grubbs,C.Wang,专利W098/42665,1998)。然而,本发明的配体前体的结构特殊性导致在合成反应结束时通过C-H分子内活化反应形成C,M,N'-三齿镍配合物,从而产生具有Ni-碳键的镍金属环状化合物。在本发明中包含这类镍配合物的一些实例。
本发明还包括使用这些新型镍配合物作为乙烯聚合反应的催化剂,以产生超支化聚乙烯,其具有作为聚合物挤出用润滑剂和/或添加剂的潜在用途。
具体实施方式
本发明涉及合成C,N,N'-三齿亚氨基吡咯基镍配合物,其特征为一般分子式(I):
其中,螯合亚氨基吡咯基配体通过分子内C-H活化经随后的环金属化反应而以三齿方式与镍中心键合,其中:
-Ar表示芳基,如苯基、联苯基、萘基及等同物,或有取代基的芳基,特别是有取代基的苯基,其在芳环的一个或两个邻位取代有C1-C4烷基、无取代基或有取代基的烷氧基或芳基,后者优选在间位具有C1烷基或三氟甲基;
-R1表示氢原子或C1-C4烷基;
-R2表示氢原子,或C1-C4烷基,或有取代基或无取代基的芳基,优选苯基;
-R3始终表示亚甲基;
-R4和R5表示氢原子;
-R6表示氢原子、C1-C11烷基、无取代基或有取代基的芳基或卤素原子,但优选氢原子;
-L表示中性配位配体,如三苯基膦、三(C1-C6烷基)膦、三环烷基膦、二苯基烷基膦、二烷基苯基膦、三烷基胺、芳基胺(如吡啶)、腈(如乙腈)或等同物。
另外,本发明还涉及合成亚氨基吡咯基三齿镍配合物,该配合物的特征为一般分子式(I),其中,亚氨基吡咯基螯合配体通过C-H分子内活化经随后的环金属化反应而以三齿方式与镍中心键合,其中:
-Ar表示芳基,如苯基、联苯基、萘基及等同物,或有取代基的芳基,特别是有取代基的苯基,其在芳环的一个或两个邻位取代有无取代基或有取代基的烷氧基或芳基,后者优选在间位具有C1烷基或三氟甲基;
-R1和R2一起表示在相应的C=C键处稠合的芳环,优选苯基,其至少在一个邻位被亚甲基(R3)取代,其可以在其它位置被不同或相同的取代基取代或不取代,所述取代基可以为C1-C4(优选甲基、异丙基或叔丁基)或三氟甲基、甲氧基或卤素;
-R3始终表示亚甲基;
-R4和R5表示氢原子;
-R6表示氢原子、C1-C11烷基、无取代基或有取代基的芳基或卤素,但优选氢原子;
-L表示中性配位配体,如三苯基膦、三(C1-C6烷基)膦、三环烷基膦、二苯基烷基膦、二烷基苯基膦、三烷基胺、芳基胺(如吡啶)、腈(如乙腈)或等同物。
作为本发明目的的C,N,N'-三齿亚氨基吡咯基镍配合物可用作乙烯聚合反应为超支化聚乙烯的无铝催化剂。
本发明还包括这些新型镍配合物作为催化剂用于乙烯聚合产生超支化聚烯烃或聚乙烯的用途,所述超支化聚烯烃或聚乙烯具有聚合物挤出用润滑剂和/或添加剂的潜在用途。
在本发明中,合成了具有5-R-2-(N-芳基)亚胺甲基吡咯基型螯合配体的三齿镍配合物,其具有图1所示的一般分子结构(I),其中R可以是具有至少一个甲基取代基的芳基或乙烯基。
配体前体的合成分三个步骤进行,起始原料通常成本低廉,并且可轻易地获自商业来源。
在第一步中,合成2-R-吡咯(R=乙烯基或芳基),随后通过二甲基甲酰胺与三氯氧磷的反应获得5-R-2-甲酰基-1H-吡咯,在第三步中,在酸性催化条件下,与芳香族伯胺(ArNH2,Ar优选为在2和6位取代有大体积基团的芳基)进行缩合反应,在配体结构中引入大体积的亚胺基,从而获得5-R-2-(N-芳基)亚胺甲基-1H-吡咯配体前体。
在第一个合成步骤中,取决于R基团是乙烯基(II)还是芳基(III)(图2),合成过程不同。
对于5-R芳基取代基,使用的合成方法是交叉偶联反应。通过氯化吡咯基锌(由吡咯钠盐和氯化锌原位生成)与所需的芳基溴之间的反应进行芳基化。尽管使用了可能会增加合成成本的钯催化剂,但其他原料是廉价的并且可商购,并且该方法实现了以高收率制备2-芳基吡咯。
对于5-R乙烯基取代基,相应的2-乙烯基吡咯的合成通过维蒂希反应完成。如此由2-甲酰基吡咯与有取代基的三苯基鏻叶立德(维蒂希试剂)之间的反应获得2-乙烯基吡咯。相应的叶立德通过鏻盐与强碱的反应原位获得。另一方面,通过将三苯基膦与所需的溴化物(在2-乙烯基吡咯中产生不同的取代基)反应合成鏻盐。
在这种具体情况中,使用2-溴丙烷和(1-溴乙基)苯产生所需的2-乙烯基吡咯。
用过量NaH处理任一种5-R-2-(N-芳基)亚胺甲基-1H-吡咯配体前体(II)或(III),产生相应的钠盐[5-R-2-(N-芳基)亚胺甲基吡咯基]Na(IINa)或(IIINa),其随后通过与反式-[Ni(Cl)(Ar*)(PPh3)2](其中Ar*=苯基或2-氯苯基)型配合物的反应而配位到镍金属中心。在配位后,通过分子内C-H活化发生随后的环金属化反应,产生C,N,N'-三齿配合物和氯化钠,同时消除苯或氯苯,如总反应式(1)中所示:
反式-[Ni(Cl)(Ar*)(PPh3)2]+(IINa)或IIINa)→(I)+Ar*H+NaCl(1)
因此,以包含易受C-H活化作用的基团的方式设计了在吡咯环的5位处具有乙烯取代基的配体前体II的合成(图2a)。双键赋予分子一定的刚性,有利于甲基和金属中心之间的接近,同时通过将吡咯基环的电子的n-离域扩展到其5-烯基臂而在热力学上稳定最终的环金属化产物,使得形成近似平面的六元金属环化合物。
在实施例1中,配体前体II(R'=Me;R”=ipr)在四氢呋喃(THF)中用NaH原位去质子后,将所得溶液添加至配合物反式-[NiCl(2-ClC6H4)(PPh3)2]。在蒸发溶剂后,将该混合物用甲苯萃取,重结晶后,以60%的收率得到对应于配合物I.1的微晶红色固体。通过1H(图3)、13C{1H}和31P{1H}NMR表征该化合物,其分子量通过X射线衍射确定(图6a)。在通过1H和31P{1H}NMR谱法(图4)监测实施例1的反应进展的同时,观察到首先形成N,N'-双齿亚氨基吡咯基镍配合物,其随后通过分子内C-H活化反应转化成C,N,N'-三齿亚氨基吡咯基镍配合物,同时消除苯或2-氯苯。
在实施例2中,进行相似的反应,但使用配体前体II(R'=Ph;R”=ipr),以55%的产率得到与前述化合物类似的化合物I.2,通过1H(图5)、13C{1H}和31P{1H}NMR表征,并且其分子结构通过X射线衍射确定(图6b)。1H(图5)和31p{1H}NMR的类似研究证明,反应模式与先前的情况相似,首先形成双齿配合物,然后演变为C,N,N'-三齿物种。
当前的C,N,N'-三齿Ni(II)配合物中新形成的Ni-C键(伴随氯苯的消除)现占据了通常由三苯基膦配体占据的配位位置,与吡咯基环氮成反式。配合物显示出具有四面体变形(主要由与金属键合的亚甲基所引起)的四方平面几何形状。
在本发明中,基于先前获得的结果(C.A.Figueira,2013),配体前体5-(2,6-Me2C6H3)-2-(N-芳基亚胺甲基)-1H-吡咯III(R'=Me;R”=3,5-(CF3)2C6H3)(图2b)的亚氨基位置的结构也通过引入极其大体积的胺2,6-二[3,5-二(三氟甲基)苯基]苯胺进行了改性。除了由这种胺在配体上以及随后在配合物中施加的高空间体积外,该基团还具有CF3取代基。如此合成配体前体5-(2,6-Me2C6H3)-2-(N-(2,6-二(3,5-(CF3)2C6H3]C6H3)亚胺甲基)-1H-吡咯,并通过与NaH的反应原位获得相应的钠盐,与配合物反式-[NiCl(Ph)(PPh3)2]反应,如实施例3中所述。在纯化后,以61%的产率获得相应的C,N,N'-三齿配合物I.3。通过1H、13C{1Η}、31p{1H}和19F{1H}NMR谱法表征该化合物,其分子结构通过X射线衍射确定(图7),与先前关于金属中心周围配位环境的情况相同。
本发明还确认,通过先前获得的结果(C.A.Figueira,2013)与当前的结果的组合,可以得出关于形成此类C,N,N'-三齿镍配合物的一些必要的要求的结论。另一方面,具有高位阻的配体的存在可导致C-H键活化,正如在配体5-(2,6-二甲基苯基)-2-(N-芳基亚胺甲基)吡咯基的情况中所观察到的那样,其中5-芳基取代基与三苯基膦配体成顺式,有利于CH活化反应。实际上,为了发生环金属化反应,C-H键必须易于接近并指向金属中心,因此,大体积取代基的存在在满足这些要求方面起着重要作用。然而,本发明提出的结果证明了中间体的几何形状是环金属化反应的决定性因素,因为该反应经历了初始形成N,N'-双齿配合物,其中取代基相对于金属中心的位置以及与吡咯基环共轭的不饱和键的存在是形成三齿配合物的重要因素。
尽管C-H键的活化在室温下发生,但使用较高的反应温度也有利于反应,导致双齿配合物完全转化为相应的三齿配合物。
值得注意的是,镍起始配合物反式-[NiCl(Ph)(PPh3)2]或反式-[NiCl(2-ClC6H4)(PPh3)2]的使用不会影响活化,导致类似的反应活性和结果,这是因为Cl取代基的电负性更高,可以看到消除氯苯比消除苯的可能性更大。
实施例1、2和3中提出的配合物I.1、I.2和I.3分别用作将乙烯聚合反应为超支化聚乙烯的催化剂。通常,使用10-2mmol的催化剂,在不同的压力和温度条件下并在助催化剂[Ni(COD)2](膦清除剂)的存在下进行试验。所得产物通过GPC/SEC以及1H和13C{1H}NMR谱法表征。
在本发明的另一个实施方式中,乙烯到超支化聚乙烯的聚合反应在无助催化剂的情况下进行。
用于获得超支化聚乙烯的乙烯催化聚合试验中所用的溶剂选自以下的一种:甲苯、二甲苯、氯苯、邻二氯苯、戊烷、己烷、庚烷。
在本发明的优选实施方式中,所用溶剂是甲苯。
表1中列出了用于获得超支化聚乙烯的乙烯催化聚合试验中所得的结果。可以观察到,尽管具有最高分子量的聚乙烯是在25℃获得的,但在9巴的乙烯压力和50℃下在助催化剂存在下获得了最佳的催化活性值。在15巴下进行的催化测试显示出催化剂活性的普遍降低,但是所得产物的特性没有显著变化。
表1:乙烯聚合为超支化PE的催化试验a和所得PE的特性。
a实验条件:[Ni]=10-2mmol;溶剂:甲苯,50mL;b催化剂:配合物I.X(X=1-3)或I.X*=配合物I.X+2当量[Ni(COD)2](助催化剂);c活性,单位是kg PE/mol Ni.h.bar;d通过GPC/SEC(PS标准)测定;eN=分支/1000C原子,通过1H NMR测定。
对于催化剂I.1和I.2,关于分子量和支化度,结果非常相似,但是第一种显示出更高的催化活性。这些催化剂在结构上相似,仅在吡咯基配体的5-乙烯基臂的取代基甲基或苯基上不同。催化剂I.3不仅显示出最高的催化活性,而且所得聚乙烯具有更高的分子量(Mn=10500-20200g/mol)。三苯基亚胺取代基,尤其是在空间上受阻并带有氟原子的,通过消除β-氢化物而减少链转移反应,从而促进聚合物生长。支化度也显著更低(9.6%)。
通过13C{1H}NMR表征聚合物在沿主链的分支类型和分布方面给出了关于聚乙烯微结构的信息。已经对聚乙烯的表征进行了若干研究,可以比较这些产物的高且复杂的数量的分支的分布。由图8和9可见,通常,产物显示出从甲基到丁基的短链分支、长链分支(n≥6)、小比例的分支上的分支以及主链中的不饱和基团(内部和末端)。然而,最高百分比对应于可以是分离或成对的甲基分支(1,4和1,6)。短链分支(乙基、丙基、丁基)的数量少于长链分支。用催化剂体系I.3得到的聚乙烯在与长链分支和分支上的分支相对应的峰的相对强度上显示出显著降低,相应的微观结构主要由分离或成对的甲基分支组成。
在这种情况下,由于聚合物的高分子量,不饱和键的存在并不明显。
这些催化剂体系具有与文献中描述的相当的体系可比的活性。与报道的体系的主要区别在于用本发明的化合物获得的聚乙烯的两个主要特征的组合:低分子量和高支化度(10-17%),支化度的值甚至高于对于用镍催化剂获得的超支化聚乙烯报道过的支化度(约15%)。
这组性质非常重要,因为低分子量超支化聚乙烯可用作聚合物挤出加工中的共混添加剂,用作润滑剂剪切稳定粘度添加剂以及用于合成单官能超支化乙烯低聚物(其可能作为润滑剂或表面改性剂使用)。具有低粘度的低分子量超支化聚乙烯也具有作为配制合成高性能润滑剂的基础的潜在应用。
附图说明
图1示出了本发明的镍配合物的一般分子结构(I)。
图2分别示出了用于合成配合物I.1、I.2和I.3的配体前体II(a)和III(b)的分子结构。
图3示出了CD2Cl2中配合物I.1的1H NMR谱,以及不同共振的归属和相应的积分值。
图4示出了通过31P{1H}NMR谱法监测的形成配合物I.1的反应(相应的钠盐IINa(R'=Me)与反式-[NiCl(2-ClC6H4)(PPh3)2]配合物的反应)随温度升高的变化。
图5示出了钠盐IINa(R'=Ph)与配合物反式-[NiCl(2-ClC6H4)(PPh3)2]的反应的1HVT-NMR谱的变化。
图6示出了通过X射线衍射获得的配合物I.1(a)和I.2(b)的分子结构。
图7示出了通过X射线衍射获得的配合物I.3的分子结构。
图8示出了在9巴和25℃下通过催化剂体系I.1/[Ni(COD)2]获得的聚乙烯的13C{1H}NMR谱。
图9示出了在9巴和25℃下通过催化剂体系I.3/[Ni(COD)2]获得的聚乙烯的13C{1H}NMR谱。
实施例
实施例中描述的合成C,N,N'-三齿亚氨基吡咯基镍配合物的一般程序
将配体前体悬浮于THF(10mL)中,并在搅拌下缓慢加入装有预先称重的NaH粉末的Schlenk管中。添加完成后,将混合物回流2小时。冷却至室温后,将溶液过滤,除去溶剂,并将粉末在真空下干燥,然后溶解在甲苯(10mL)中。将配合物反式-[NiCl(Ar*)(PPh3)2](Ar*=Ph或2-ClC6H4)悬浮在甲苯(30mL)中,并在-20℃滴加相应的钠盐溶液。将反应混合物逐渐加热至65℃并在惰性气氛下搅拌约12小时,得到深红色溶液。将溶液过滤并蒸发至干,并将残余物在低温(-10℃至0℃)下用正戊烷或正己烷洗涤。随后,用适当的溶剂萃取该化合物,将溶液浓缩并储存在-20℃,得到纯配合物。
实施例1:
[Ni{κ3C,N,N'-5-[(CH2)C(CH3)=C(H)]-NC4H2-2-C(H)=N-2,6-iPr2C6H3}(PPh3)]
如一般程序中所述,用0.05g(2.2mmol)的NaH将0.52g(1.7mmol)的配体前体5-(2-CH3C3H4)-2-[N-(2,6-iPr2C6H3)亚胺甲基]-1H-吡咯去质子,将相应的钠盐添加至1.09g(1.5mmol)的配合物反式-[NiCl(2-ClC6H4)(PPh3)2]。用正己烷洗涤后,将得到的红色固体溶于少量甲苯中,并在搅拌下用正己烷分为双层,导致析出微晶红色固体。产率:0.56g(60%)。在-20℃下从甲苯溶液获得适合于单晶X射线衍射的晶体。通过NMR谱法和元素分析表征该化合物。
1H NMR(300MHz,CD2Cl2):δΗ7.40-7.28(m,10H,CHN,PPh3-H对e H邻),7.21-7.15(m,6H,PPh3-H间),6.93(t,1H,3JHH=7.7Hz,N-Ph-H对),6.80(d,1H,3JHH=3.6Hz,H3),6.74(d,2H,3JHH=7.7Hz,N-Ph-H间),6.58(s,1H,CH=C(CH3)(CH2)),6.28(d,1H,3JHH=3.6Hz,H4),3.63(hept,2H,3JHH=6.8Hz,CH(CH3)2),1.89(d,2H,3JHP=11.5Hz,CH=C(CH3)(CH2)),1.39(s,3H,CH=C(CH3)(CH2)),1.05(d,6H,3JHH=6.8Hz,CH(CH3)2),0.86(d,6H,3JHH=6.8Hz,CH(CH3)2)。13C NMR{1H}(75MHz,CD2Cl2):δc160.0(d,3JCP=2.6Hz,CHN),149.4(N-Ph-C本位),147.7(d,3JCP=2.3Hz,CH=C(CH3)(CH2)),146.5(d,3JCP=1.6Hz,C5)141.8(N-Ph-C邻),140.7(d,3JCP=1.4Hz,C2),134.5(d,2JCP=11.3Hz,PPh3-C邻),132.8(d,1JCP=41.0Hz,PPh3-C本位),129.8(d,4JCP=2.1Hz,PPh3-C对),128.5(d,3JCP=9.5Hz,PPh3-C间),125.9(N-Ph-C对),123.3(N-Ph-C间),118.5(d,4JCP=1.5Hz,C3),117.6(CH=C(CH3)(CH2)),109.5(d,=3.6Hz,C4),28.4(CH(CH3)2),25.8(CH(CH3)2),25.3(CH3),25.2(d,2JCP=21.3Hz,Ni-CH2),22.1(CH(CH3)2)。31P{1H}NMR(121MHz,CD2Cl2):δP 32.1。分析。对于C39H41N2NiP的计算值(%):C,74.66;H,6.59;N,4.46。实验值:C,74.94;H,6.69;N,4.28。
实施例2:
[Ni{κ3C,N,N'-5-[(CH2)C(C6H5)=C(H)]-NC4H2-2-C(H)=N-2,6-iPr2C6H3}(PPh3)]
如一般程序中所述,用0.05g(2.0mmol)的NaH将0.56g(1.5mmol)的配体前体5-(2-PhC3H4)-2-[N-(2,6-iPr2C6H3)亚胺甲基]-1H-吡咯去质子,将相应的钠盐添加至0.88g(1.2mmol)的配合物反式-[NiCl(2-ClC6H4)(PPh3)2]。用正己烷洗涤并将剩余的红色固体用乙醚萃取后,将所得溶液进一步浓缩并储存在-20℃,得到适合于单晶X射线衍射的红色晶体。产率:0.46g(55%)。通过NMR谱法和元素分析表征该化合物。
1H NMR(300MHz,CD2Cl2):δH 7.41(s,1H,CHN),7.35-7.29(m,6H,PPh3-H邻),7.24-7.19(m,3H,PPh3-H对),7.10-7.05(m,7H,PPh3-H间e CH=C(CH2)(Ph)),7.01-6.99(m,3H,Ph-H邻和Ph-H对),6.94-6.86(m,4H,Ph-H间,N-Ph-H对e H3),6.73(d,2H,3JHH=7.7Hz,N-Ph-H间),6.49(d,1H,3JHH=2.3Hz,H4),3.62(hept,2H,3JHH=7.0Hz,CH(CH3)2),2.28(d,2H,3JHP=11.2Hz,CH=C(Ph)(CH2)),1.06(d,6H,3JHH=6.7Hz,CH(CH3)2),0.89(d,6K,3JHH=6.7Hz,CH(CH3)2)。13C{1H}NMR(75MHz,CD2Cl2):δC160.3(d,3JCP=2.6Hz,CHN),149.2(N-Ph-C本位),148.2(d,3JCP=2.1Hz,CH=C(Ph)(CH2)),146.4(d,3JCP=1.5Hz,C5),144.6(Ph-C本位),141.7(N-Ph-C邻),141.2(d,3JCP=1.2Hz,C2),134.4(d,2JCP=11.2Hz,PPh3-C邻),132.3(d,1JCP=41.1Hz,PPh3-C本位),129.8(d,4JCP=2.0Hz,PPh3-C对),128.4(d,3JCP=9.5Hz,PPh3-C间),127.9(Ph-C邻),126.9(Ph-C间),126.2(Ph-C对),126.1(N-Ph-C对),123.3(N-Ph-C间),118.9(CH=C(Ph)(CH2)),118.6(d,4JCP=1.4Hz,C3),111.6(d,4JCP=3.5Hz,C4),28.5(CH(CH3)2),25.8(CH(CH3)2),22.3(d,2JCP=20.0Hz,Ni-CH2),22.0(CH(CH3)z)。31P{1H}NMR(121MHz,CD2Cl2):δP 32.4。分析。对于C44H43N2NiP的计算值(%):C,76.65;H,6.29;N,4.06。实验值:C,76.19;H,6.01;N,3.78。
实施例3:
[Ni{κ3C,N,N'-5-[2'-CH2-6'-CH3-C6H3]-NC4H2-2-C(H)=N-2,6-[3,5-(CF3)2C6H3]2C6H3}(PPh3)]
如一般程序中所述,用0.05g(2.0mmol)的NaH将1.05g(1.5mmol)的配体前体5-[2',6'-(CH3)2C6H3]-2-{N-[2,6-[3,5-(CF3)2C6H3]2C6H3]亚胺甲基}-1H-吡咯去质子,将相应的钠盐添加至0.83g(1.2mmol)的配合物反式-[NiCl(Ph)(PPh3)2]。用正戊烷洗涤后,将剩余的橙色固体在真空下干燥。由于配合物可部分溶于正戊烷,因此将洗涤产生的溶液浓缩并储存在-20℃,得到适合单晶X射线衍射的晶体。产率:0.74g(61%)。通过NMR谱法和元素分析表征该化合物。
1H NMR(300MHz,CD2CI2):δH 8.06(s,4H,邻-Ph-H邻),7.89(s,2H,邻-Ph-H对),7.32-7.04(m,19H,CHN,N-Ph-H间,N-Ph-H对e PPh3),6.99(d,1H,3JHH=7.3Hz,5-Ph-H间CH3),6.87-6.83(m,2H,H3 e H4),6.54(t,1H,3JHH=7.4Hz,5-Ph-H对),6.01(d,1H,3JHH=7.4Hz,5-Ph-H间CH2),2.61(s,3H,CH3),2.13(d,2H,3JHP=11.1Hz,CH2)。13C{1H}NMR(75MHz,CD2Cl2):δc 162.4(d,3JCP=2.6Hz,CHN),148.9(N-Ph-C本位),147.8(C5),145.0(d,3JCP=1.6Hz,5-Ph-C邻CH2),141.6(C2),141.3(N-Ph-C邻),135.9(5-Ph-C邻CH3),134.3(d,2JCP=11.4Hz,PPh3-C邻),133.6(5-Ph-C本位),133.5(邻-Ph-C本位),131.9(PPh3-C对),131.7(quart,2JCF=33.0Hz,邻-Ph-C间),131.3(d,3JCF=2.7Hz,邻-Ph-C邻),130.2(br,N-Ph-C间和N-Ph-C对),128.6(d,3JCP=10.4Hz,PPh3-C间),127.7(5-Ph-C间CH3),126.7(d,4JCP=7.7Hz,5-Ph-C间CH2),125.2(5-Ph-C对),123.9(quart,1JCF=271.3Hz,CF3),121.0(sept,3JCF=3.6Hz,邻-Ph-C对),120.2(C3),115.3(C4),24.8(d,2JCP=20.9Hz,Ni-CH2),23.7(CH3)。31P{1H}NMR(121MHz,CD2Cl2):δp 33.1。19F{1H}NMR(282MHz,CD2Cl2):δF-63.0。分析。对于C35H35F12N2NiP的计算值(%):C,62.56;H,3.47;N,2.75。实验值:C,62.78;H,3.20;N,2.67。
乙烯催化聚合为超支化聚乙烯的一般程序
在具有玻璃容器(至多9巴)或不锈钢(至多15巴)容器的300mL Miniclave DriveBüchi压力反应器中进行乙烯的催化聚合反应以获得超支化聚乙烯。将反应器预先在140℃的烘箱中干燥并脱气,并在1.3巴的氮气压力下加入干燥的蒸馏甲苯(50mL)。将反应器温热至所需温度(25℃至50℃),并使其平衡10分钟。再一次脱气后,将反应器用乙烯加压,并加入催化剂的甲苯溶液(10-2mmol,1mL),然后在适当的时候加入[Ni(COD)2]在甲苯(2mL)中的溶液。将乙烯压力升高至所需值(3至15巴),并且在反应时间(2至6小时)内使进气阀保持持续开放。在催化试验结束时,关闭乙烯供应,将反应器减压,并在搅拌下用甲醇淬灭反应介质。在几乎所有试验中均观察到油相的形成,并通过减压蒸发挥发物而将其分离。将分离出的产物干燥至恒重,得到具有不同密度和粘度的无色油。
通过GPC/SSC以及1H和13C{1H}NMR谱法表征所有产物。将NMR样品溶解在0.8mL的1,2,4-三氯苯和C6D6(75:25v/v)的混合物中,并在90℃记录谱图。通过1Η谱图分析可以确定聚合物的支化度N,即每1000个碳原子的分支总数。13C{1H}谱图分析表明了那些分支的类型和分布。
进行空白测试以分析[Ni(COD)2]清除剂在不同温度和压力条件下的催化活性,发现其在所有使用条件下均无活性。
Claims (6)
1.三齿亚氨基吡咯基镍配合物,其特征为一般分子式(I),其中,螯合亚氨基吡咯基配体通过分子内C-H活化经随后的环金属化反应而以三齿方式与镍中心键合,其中:
a)Ar表示芳基,例如苯基、联苯基、萘基及等同物,或有取代基的芳基,特别是有取代基的苯基,其在芳环的一个或两个邻位取代有C1-C4烷基、无取代基或有取代基的烷氧基或芳基,后者优选在间位具有C1烷基或三氟甲基;
b)R1表示氢原子或C1-C4烷基;
c)R2表示氢原子,或C1-C4烷基,或有取代基或无取代基的芳基,优选苯基;
d)R3始终表示亚甲基;
e)R4和R5表示氢原子;
f)R6表示氢原子、C1-C11烷基、无取代基或有取代基的芳基或卤素,但优选氢原子;
g)L表示中性配位配体,例如三苯基膦、三(C1-C6烷基)膦、三环烷基膦、二苯基烷基膦、二烷基苯基膦、三烷基胺、如吡啶等芳基胺、如乙腈等腈或等同物。
2.三齿镍配合物,其特征为一般分子式(I),其中,亚氨基吡咯基螯合配体通过C-H分子内活化经随后的环金属化反应而以三齿方式与镍中心键合,其中:
a)Ar表示芳基,例如苯基、联苯基、萘基及等同物,或有取代基的芳基,特别是有取代基的苯基,其在芳环的一个或两个邻位取代有无取代基或有取代基的烷氧基或芳基,后者优选在间位具有C1烷基或三氟甲基;
b)R1和R2一起表示在相应的C=C键处稠合的芳环,优选苯基,其至少在一个邻位被亚甲基(R3)取代,但其可以在其它位置被不同或相同的取代基取代或不取代,所述取代基可以为C1-C4(优选甲基、异丙基或叔丁基)或三氟甲基、甲氧基或卤素;
c)R3始终表示亚甲基;
d)R4和R5表示氢原子;
e)R6表示氢原子、C1-C11烷基、无取代基或有取代基的芳基或卤素,但优选氢原子;
f)L表示中性配位配体,例如三苯基膦、三(C1-C6烷基)膦、三环烷基膦、二苯基烷基膦、二烷基苯基膦、三烷基胺、如吡啶等芳基胺、如乙腈等腈或等同物。
3.将乙烯聚合反应为超支化聚乙烯的方法,所述方法从权利要求1或2所述的配合物之一和助催化剂二者混合在溶剂中的溶液出发,在25℃至50℃的温度下,在2至6小时的时间内通过3至15巴的压力的单体乙烯进行连续加压,所述配合物的特征在于其用作催化剂。
4.如权利要求3所述的方法,其特征在于,所述助催化剂是[Ni(COD)2]。
5.如权利要求4所述的方法,其特征在于,作为另选,所述方法不添加助催化剂。
6.如权利要求3所述的方法,其特征在于,所用的溶剂选自二甲苯、甲苯、氯苯、邻二氯苯、戊烷、己烷、庚烷。
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