Metathesis under Biphasic Conditions Using Monolithic-Supported Ionic Liquids

使用整体支撑离子液体在双相条件下进行复分解

• 批准号: 136355964
• 负责人: Professor Dr. Michael R. Buchmeiser
• 金额: --
• 依托单位: Lehrstuhl für Makromolekulare Stoffe und Faserchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2013-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/136355964?language=en
• 关键词: Metathesis; under; Biphasic; Conditions; Using

Polymeric monolithic supports shall be prepared either via ring-opening metathesis polymerization (ROMP) or via electron beam (EB) triggered free radical polymerization. The resulting porous monolithic structures shall serve as support materials for Ionic liquids (ILs) in which a series of novel metathesis catalysts bearing ionic moieties shall be dissolved. Metathesis reactions shall be run under biphasic conditions using a second organic phase immiscible with the IL. For these purposes, novel persistent, IL-soluble Schrock and Grubbs-Hoveyda-type catalysts with pendant ionic groups are to be synthesized. The monoliths shall be subject to in situ surface functionalization using ionic monomers based on quaternary ammonium, imidazolium and phosphonium salts as well as with 2-propoxystyryl ethers. In the case of ROMP-derived monoliths, this is to be accomplished by the use of the corresponding norborn-2-ene or cyclooctene derivatives. In the case of EB-triggered free radical polymerization-derived monoliths, acrylates containing quaternary ammonium, imidazolium and phosphonium salts as well as 2-propoxystyryl ethers are to be surface-grafted via post-synthesis, EB-triggered free radical polymerization. Alternatively, a ROMP-based protocol using the above-mentioned norborn-2-ene or cyclooctene derivatives shall be applied. The thus prepared surface-functionalized monoliths shall then be treated with appropriate amounts of ionic liquids (ILs) based on a similar structural motif as used for surface grafting (i.e. for the corresponding quaternaized N- and P-based monomers). Special care shall be devoted to compatibility issues, which are mainly related to both the nature of the grafted molecules and the ILs and to the grafting density as well as of the degree of polymerization of the graft polymers based on the quaternary ammonium, imidazolium and phosphonium salts, respectively. In all cases, the final functionalized monoliths shall be characterized by micro- and mesopores. Apart from ionic interactions between the graft polymers and the ILs, these pores allow for retaining the ionic liquids (ILs) at the surface by capillary forces. In addition, sufficient interconnected pores in the μm-range shall be present and guarantee for a fast flow-through. An optimization in terms of grafting density, chain length of the graft polymers, nature of the functional monomer and IL as well as optimum layer thickness of the IL shall be carried out, thus offering optimum catalytic performance while resulting in a minimum leaching. The ultimate goal is the realization of novel ionic metathesis catalysts, their immobilization within monolith-supported ILs, and the use of the thus prepared supported catalysts in continuous metathesis reactions including ring-closing metathesis (RCM), ring-opening cross metathesis (ROC), cross-metathesis and ene-yne cross metathesis reactions under biphasic conditions. The thus created immobilized systems shall provide further insight into the reactivity of both Schrock- and Grubbs-Hoveyda-type catalysts in metathesis reactions within ILs. Even more important, the supported catalysts to be developed here shall help to solve the problems of support-regeneration and recharging, metal contamination of products and catalyst longevity.

聚合物整体载体应通过开环的分解聚合（ROMP）或通过触发自由基聚合的电子束（EB）来制备。所得的多孔整体结构应用作离子液体（ILS）的支撑材料，其中应溶解一系列具有离子基部分的新型元理解催化剂。元理性反应应在双相条件下使用第二有机相与IL不混溶。为了这些目的，应合成新型的持久性，IL可溶性schrock和Grubbs-hoveyda型催化剂，并具有吊坠离子基团的催化剂。基于基于Quaternary铵，咪唑和磷酸盐以及2-丙氧甲状腺霉苯甲酸酯的离子单体以及2-丙氧甲状腺乙烯乙烯剂，该整体应受到原位表面功能化的作用。对于romp衍生的巨石，这是通过使用相应的Norborn-2-烯或环烯烯衍生物来实现的。在EB触发的自由基聚合衍生的整体中，含有第四纪铵，咪唑和磷酸盐的丙烯酸酯以及2-丙氧化苯甲酰苯丙烯乙烯酯，应通过后同伴进行表面播种，EB触发的自由基聚合物。或者，应采用上述诺本-2-Ene或环辛衍生物的基于ROMP的方案。然后，应根据与表面嫁接的类似结构基序（即，对于相应的Quaternized N-基于N-和P的单体），应使用适当量的离子液体（ILS）处理这样制备的表面功能化的整体。应特别注意兼容问题，这些问题主要与移植分子和IL的性质以及基于Quaternary ammhonium，Imidazolium和磷酸盐的嫁接密度以及嫁接密度以及移植密度以及嫁接密度以及聚合程度有关。在所有情况下，最终功能化的整体均应以微孔和中孔为特征。除了移植聚合物与IL之间的离子相互作用外，这些孔还可以通过毛细管将离子液体（IL）保留在表面上。此外，应存在μm范围内足够的相互连接的孔，并保证快速流通。应进行对移植密度，移植聚合物的链长，功能单体和IL的性质以及IL的最佳层厚度的优化，从而提供最佳的催化性能，同时最小行走。 The ultimate goal is the realization of novel ionic metathesis catalysts, their immobilization within monolith-supported ILs, and the use of the thus prepared supported catalysts in continuous metathesis reactions including ring-closing metathesis (RCM), ring-opening cross metathesis (ROC), cross-metathesis and ene-yne ​​cross metathesis reactions under biphasic conditions.这样创建的固定系统应提供进一步的了解，以了解ILS内的分解反应中Schrock和Grubbs-Hoveyda型催化剂的反应性。更重要的是，这里要开发的受支持的催化剂应有助于解决支持再生和充电，产品的金属污染和催化剂寿命的问题。