Thermomorphic

A method has been developed for the continuous removal and reuse of a homogeneous rhodium hydroformylation catalyst. This is done using solvent mixtures that become miscible at reaction temperature and phase separate at lower temperatures. Such behavior is referred to as thermomorphic, and it can be used separate the expensive rhodium catalysts from the aldehydes before they are distilled. In this process, the reaction mixture phase separates into an organic phase that contains the aldehyde product and an aqueous phase that contains the rhodium catalyst. The organic phase is separated and sent to purification, and the aqueous rhodium catalyst phase is simply recycled. 

To eliminate the need to recover the product by distillation, researchers are now looking at thermomorphic solvent mixtures. A thermomorphic system is characterized by solvent pairs that reversibly change from being biphasic to monophasic as a function of temperature. Many solvent pairs exhibit varying miscibility as a function of temperature. For example, methanol/cyclohexane and n-butanol/water are immiscible at ambient temperature, but have consolute temperatures (temperatures at which they become miscible) of 125°C and 49°C, respectively (3). 

The use of thermomorphic systems has recently been studied as a way of achieving catalyst separation in homogeneous catalysis. For example, a biphasic hydroformylation catalyst system was developed to take advantage of the unusual solvent characteristics of perfluorocarbons combined with typical organic solvents (4). Fluorous/organic mixtures such as perfiuoromethylcyclohexane... 

Our approach is to use the inexpensive ligands that are already used industrially as well as conventional solvents. The goal of this project is to develop a thermomorphic approach to the rhodium-catalyzed hydroformylation of higher olefins (>Ce) that enhances conversion rates and ease of product recovery while minimizing catalyst degradation and loss. 

Thermomorphic solvent mixtures have been tested for hydroformylation of 1-octene and 1-dodecene to determine the ease of product recovery and catalyst recycling. Using both batch and continuous reactors, we demonstrated the efficacy of a biphasic, thermomorphic, system that had the following advantages ... 

Batch Experiments with Thermomorphic Systems. As a reference, we tested the hydroformylation of 1-octene in a completely homogeneous system using the same rhodium triphenylphosphine catalyst that is used for hydroformylation of lower aldehydes. This is sample R39 in Table 28.1, and gives us a baseline to compare the performance of our systems in terms of conversion and selectivity. To maintain consistency, we performed all the reactions at 100°C using the same amounts of reactants, catalysts and solvents. Under these conditions we only detected aldehyde products no alcohol or alkene isomers were formed. 

The rhodium loss to the hydrocarbon phase was analyzed by atomic absorption. We found that for a thermomorphic catalyst solution that was cycled three times that the rhodium loss was below the 0.1 ppm detection limit of their instrument. 

In summary, what we have found is that the combination of a thermomorphic system and a surfactant is very effective for the hydroformylation of 1-octene and 1-dodecene. We believe that although a 90 10 ethanol/water and heptane system becomes miscible at 70°C, the additional water in a 50 50 ethanol/water and heptane system raises the miscibility temperature to >100°C. When a surfactant is added, the miscibility temperature is lowered and the biphasic solution becomes monophasic below the reaction temperature, resulting in good reaction rates. In addition, the presence of the surfactant also enhances the selectivity compared to the completely homogeneous system from 1.8 to 5.3 L/B... 

Continuous Experiments with Thermomorphic Systems. For the continuous experiments, we used the best solvent system we identified in the batch reactions, which was 50 50 1,4-dioxane/water. Heptane was the nonpolar solvent and CTAB the surfactant. We chose this system over the 50 50 ethanol/water system because it gave us better selectivity and there is no chance that unwanted acetal side products will be formed by the reaction of ethanol with the aldehyde. We initially used 1-octene as the olefin and after we worked out the process conditions for 1-octene, we tested the higher olefin 1-dodecene. 

The 1-octene conversions averaged 50% at the current flow rate (residence time 30 minutes). We believe the scatter in the data is due to the drift in the pump flow rate, which alters the residence time, and not to a change in the catalyst itself. In all cases the linear to branch aldehyde selectivity was very high in the range of 5 1 linear to branch aldehyde. The reaction was ran under thermomorphic conditions for over 400 hours and we found that we maintained good conversion and good selectivity. 

Economics. Comparison of the material and energy balance for our process and the cobalt-based BASF higher olefin process (8), we foimd that our process reduced the capital investment required by over 50% due to the fact that we require far fewer unit operations, and because the operating pressure is much lower. In sutmnary, the thermomorphic solution developed by TDA allows easy catalyst recycle, which, when coupled with the lower pressure operation possible with Rh catalysts (compared to the cobalt-based process) lowers both capital and operating costs for current oxidation (oxo) plants of similar capacity. 

We have developed a thermomorphic catalyst system for the hydroformylation of higher alkenes. We have built a bench-scale continuous reactor and have used it to determine the long-term performance of the thermomorphic catalyst system. Longterm results (>400 h) using 1-octene and 1-dodecene show that the catalyst has high selectivity and no measurable loss in activity. 

While cobaloximes are the most active CCT catalysts known, they are sensitive to air and moisture, so the more robust porphyrins were considered a better choice for a recoverable catalyst. To better understand how to design an optimal thermomorphic catalyst we initiated an investigation to learn how polyethylene length, number, and the covalent linker influence the catalyst activity and the final color of the methaciylate resin. A series of polyethylene-supported CCT catalysts were thus prepared for study (Scheme 36.2). 

Although porphyrin-derived thermomorphic complexes were demonstrated to be robust and recyclable CCT catalysts, barriers to implementation still existed. One obstacle to scaling the process was the cost of the tetrakis(4-hydroxyphenyl)porphyrin starting material porphyrins are expensive dne to their... 

We have demonstrated a new class of effective, recoverable thermormorphic CCT catalysts capable of producing colorless methacrylate oligomers with narrow polydispersity and low molecular weight. For controlled radical polymerization of simple alkyl methacrylates, the use of multiple polyethylene tails of moderate molecular weight (700 Da) gave the best balance of color control and catalyst activity. Porphyrin-derived thermomorphic catalysts met the criteria of easy separation from product resin and low catalyst loss per batch, but were too expensive for commercial implementation. However, the polyethylene-supported cobalt phthalocyanine complex is more economically viable due to its greater ease of synthesis. 

The idea to use solvent systems enabling homogeneous reaction conditions at elevated temperatures and liquid/liquid phase separation at lower— preferably room—temperature seems to be obvious. Nevertheless, it is only recently that thermomorphic solvent systems gain attention [30-33] for product separation or multiphase catalysis [34,35]. The main reasons for the delayed engagement is that an efficient choice of a useful solvent system is not easy to achieve. There is also a lack of experience with thermomorphic systems in general. Reactions are optimized to be carried out in solvents having certain distinct solubility and polarity characteristics. A thermomorphic solvent system of choice will have to fulfill these requirements and to show the thermomorphic effect in addition. 

On the other hand thermomorphic solvent systems can be used for industrial applications within existing equipment. In principal, it is also possible to use unmodified ligands and catalyst complexes for homogeneously catalyzed reactions. Therefore, the economic hurdles to use the system in industrial practice are not very high. 

Thermomorphic solvents show promise for upcoming use in chemical industry. This is also the case for polymeric thermomorphic solvents [36]. But there are also limitations and items for further investigations ... 

Often reactions only work satisfactory in special solvents. It is not very likely, that thermomorphic solvents or solvent mixtures will extend these options. 

Thermomorphic solvent systems are at a relatively yoimg stage of development. Compared to ionic liquids or supercritical CO2 there is much less experience available. Large-scale applications are unknown at present. There are a lot of options for the future but these will depend on further research in the area. 

Another approach to isolate the catalyst from the products is the application of perfluorinated catalytic systems, dissolved in fluorinated media [63], which are not non-miscible with the products and some commonly used solvents for catalysis like THE or toluene at ambient temperature. Typical fluorinated media include perfluorinated alkanes, trialkylamines and dialkylethers. These systems are able to switch their solubility properties for organic and organometallic compounds based on changes of the solvation ability of the solvent by moving to higher temperatures. This behavior is similar to the above-mentioned thermomorphic multiphasic PEG-modified systems [65-67]. 

This development towards an ecologically and-from an industrial point of view—economically less critical catalytic system based on thermomorphic liuorous catalysts broadens the toolbox of the industrial research chemist and should be taken into consideration in future developments of chemical... 

IMS system temperature dependent or thermomorphic multi-component solvent system... 

From our cooperation partners. Profs. Gladysz and Dinjus, we received ligands with perfluorinated chains ( ponytails ), which show a thermomorphic solubility in organic solvents (P(et-Rf8)2(m-me-bz)) or maybe extracted with fluorous solvents (P(et-Rfs)3). P(et-Rf6)(z-pr)2 with only one perfluorinated... 

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