Recyclable polymerization catalyst

Three key conditions must be met to design a uniformly reactive, recoverable, and recyclable polymerization catalyst (1) the synthetic protocol used to make the immobilized catalyst must lead to only one type of active site on the surface, (2) the support material must be able to allow sufficient transport of reactants to and polymer from the active site, and (3) at the end of the reaction, the active site must not be irreversibly changed or decomposed [23]. Research in our lab has thus far sought to investigate these points using the atom transfer radical polymerization (ATRP) of methyl methacrylate as a model reaction. 

Nguyen JV, Jones CW (2005) Recyclable polymerization catalysts methyl methacrylate polymerization with sihca-supported CuBr-bipyridine atom transfer radical polymerization catalysts. J Catal 232 276... 

A multi-step asymmetric synthesis of a hydrindane framework was achieved in water via asymmetric allylic alkylation, propargylation and aquacatalytic cycloisomerization of a 1,6-enyne, where all three steps were performed in water with the recyclable polymeric catalysts. The racemic cyclohexenyl ester 27 reacted with diethyl malonate under the conditions mentioned in Table 6.1 to give 90-92% ee of 34b. The polymeric chiral palladium complex 23-Pd was reused four times... 

Spectacular achievements in catalytic asymmetric epoxidation of olefins using chiral Mnm-salen complexes have stimulated a great deal of interest in designing polymeric analogs of these complexes and in their use as recyclable chiral catalysts. Techniques of copolymerization of appropriate functional monomers have been utilized to prepare these polymers, and both organic and inorganic polymers have been used as the carriers to immobilize these metal complexes.103... 

Immobilization of phase-transfer catalysts on polymeric matrices avoids the problem of separating and recycling the catalysts. In this case the chemical stability of the immobilized catalyst becomes very important quaternary salts often decompose under drastic reaction conditions whereas polydentate ligands are always stable. However, the difficult synthesis of cryptands, despite their high catalytic efficiency, can hardly justify their use. Synthesis of crown-ethers is much easier, but catalytic efficiences are often too low. 

Tab. 6.4 Recycling experiments Table 6.3, reaction time = 3 h). and subsequent reuse of the polymeric catalyst (macroligand 3,...

Song et al. [62] reported poly-salen Co(III) complexes 18, 19 as catalyst for HKR (Figure 5) of terminal alkene epoxides. The polymeric catalysts provided product epoxides with excellent conversion (>49%) and high chiral purity (ee s, 98%) and the catalytic system could be recycled once with retention of activity and enantioselectivity. 

Week et al. [65] further reported the Co salen complex supported on norbomene polymers (23, 24) with stable phenylene-acetylene linker (Figure 8). The polymer-supported salen catalysts were investigated for HKR of the racemic terminal epoxides that showed outstanding catalytic activities and comparable selectivities to the original catalysts reported by Jacobsen. However, the polymeric catalyst was recycled only once after its precipitation with diethylether as the catalyst became less soluble and less reactive in subsequent catalytic... 

Kragl 13) pioneered the use of membranes to recycle dendritic catalysts. Initially, he used soluble polymeric catalysts in a CFMR for the enantioselective addition of Et2Zn to benzaldehyde. The ligand a,a-diphenyl-(L)-prolinol was coupled to a copolymer prepared from 2-hydroxyethyl methyl acrylate and octadecyl methyl acrylate (molecular weight 96,000 Da). The polymer was retained with a retention factor > 0.998 when a polyaramide ultrafiltration membrane (Hoechst Nadir UF PA20) was used. The enantioselectivity obtained with the polymer-supported catalyst was lower than that obtained with the monomeric ligand (80% ee vs 97% ee), but the activity of the catalyst was similar to that of the monomeric catalyst. This result is in contrast to observations with catalysts in which the ligand was coupled to an insoluble support, which led to a 20% reduction of the catalytic activity. 

To a plastic producer (i.e. processor), melt index is one property that is needed in order to evaluate whether the same process can be used irrespective of whether it uses virgin or recycled polymers. This will tell if it is possible to process the recycled polymeric materials in the same set-up as usual. Several other properties are needed in order to quality mark the materials. The melt index is related to what final tensile properties a product obtains, this in turn has an impact on the expected life-time. The purity of a recyclate stream with respect to the amount of foreign polymer in the stream has an impact on melt-index, but will also be an important factor for the final mechanical properties. Another very important property is the amount of low molecular weight compounds, which may be of vastly different types. Typically such an analysis will show the presences of additives and their degradation products, degradation products of the polymeric matrices, traces of solvents, initiators, or catalysts, compounds related to the use of the plastics and others. 

The development of polymer-immobilized ligands and catalysts for asymmetric synthesis is a rapidly growing field [1], which has great importance due mainly to the easy separation and recyclability of polymer-supported catalysts. The polymeric catalysts also represent one of the most powerful tools for green sustainable chemistry, in the sense that they can be easily recovered and reused many times. 

Nonracemic Ti-BINOLate (BINOL = l,l -bi-2-naplilli()l) and Ti-TADDOLate (TADDOL = a,a,a, a -tetraaryl-2,2-dimethyl-l,3-dioxolan-4,5-dimethanol) complexes are also effechve chiral catalysts for the asymmetric alkylation of aldehydes [9-11]. Seebach developed polystyrene beads with dendritically embedded BINOL [9] or TADDOL derivatives 11 [10, 11]. As the chiral ligand is located in the core of the dendritic polymer, less steric congeshon around the catalyhc center was achieved after the treatment with Ti(OiPr)4. This polymer-supported TiTADDOLate 14 was then used for the ZnEt2 addition to benzaldehyde. Chiral 1-phenylpropanol was obtained in quantitahve yield with 96% ee (Scheme 3.3), while the polymeric catalyst could be recycled many times. 

Amphiphilic diblock copolymers based on 2-oxazoline derivatives with chiral diphosphine 187 were prepared (Scheme 3.61) and used in the asymmetric hydrogenation of methyl (Z)-(z-acelarnido cinnamate 188 in water to give the (R)-phenylalanine derivative 189 in 85% ee [124]. The polymeric catalyst could be recycled. This result illustrated the advantages of using amphiphihc copolymers for the efficient transformation of a hydrophobic substrate in water. 

Cyclization of the bisurethane 198 to the oxazolidin-2-one 199 was examined by using the polymeric catalyst derived from 197 (Scheme 3.64), which was prepared by using ArgoGel-NH2 as the polymer support. Altliough a somewhat lower enantioselectivity was obtained with the non-supported catalyst than with the supported catalyst, the former could be recycled several times without any significant differences in either yield or enantiomeric excess [127]. 

Potential recycling of the polymeric catalysts is a very important feature of supported systems. According to this, all polymer-bound catalysts prepared were recovered after the initial reaction, washed, dried and reused for the same reaction, under similar conditions. This procedure was repeated for several cycles. Results obtained showed that all resins partially lose... 

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