Polymer based catalysts

Oxidation of a phenol to the corresponding ju-qninone nsing a copper catalyst takes place at room temperatnre nnder similar conditions as those nsed for alcohol oxidation, with O2 as oxidant. Likewise, hydroqninones (22) can be transformed to 3-alkoxy-/7-qninones (23) when reacted in the presence of an alcohol. In the case of 4-substituted phenols (24), polymer-based catalysts composed of ligands (e.g. PVBPy) that chelate copper have been used at elevated temperatures to selectively oxidize a benzylic carbon to yield 4-hydroxybenzaldehydes (25) in good yields. ... 

Organic polymer-based catalysts can also be prepared but are generally inferior to those based on inorganic materials. 

Applications of thin plasma-polymerized films in microelectronics, gas separation, and catalysis, such as new types of immobilized polymer-based catalysts, have been already... 

Pt-based catalysts are two necessary approaches at the current technology stage. It is believed that non-noble metal electrocatalysts is probably the sustainable solution for PEM fuel cell commercialization. In the past several decades, various nonnoble metal catalysts for ORR have been explored, including non-pyrolyzed and pyrolyzed transition metal nitrogen-containing complexes, transition metal chalcogenides, conductive polymer-based catalysts, metal oxides/carbides/nitrides/ oxynitrides/carbonitrides, and enzymatic compoimds. The major effort in non-noble metal electrocatalysts for ORR is to increase both the catalytic activity and stability. 

W. Striiver and R. Wagner, Polymer-based Catalysts and New Catalyst Resins and their Application, Bayer A.G., D-5090, Leverkusen. 

The use of the binaphthyl-based chiral polymers in catalysis has been explored. We have demonstrated that incorporation of aluminum metal centers into the rigid binaphthyl polymer backbones leads to greatly enhanced catalytic activity over the monomeric aluminum complex. The catalytic activity of the polymeric aluminum and titanium complexes in the Mukaiyam aldol reaction has been studied. These polymeric metal complexes represent a new generation of polymer-based catalysts... 

Fritsch, D., Kuhr, K., Mackenzie, K., and Kopinke, F. D. (2003). Hydrodechlorination of chloro-organic compounds in ground water by palladium catalysts. Part 1. Development of polymer-based catalysts and membrane reactor tests. Catal. Today 82, 105-118. 

We developed a novel O/W emulsion catalytic system formed by the assembly of amphiphilic polymer-based catalyst Ir-PtsEN at the water-oil interface. This catalyst... 

Another type of synthetic polymer-based chiral stationary phase is formed when chiral catalyst are used to initiate the polymerisation. In the case of poly(methyl methacrylate) polymers, introduced by Okamoto, the chiraUty of the polymer arises from the heUcity of the polymer and not from any inherent chirahty of the individual monomeric subunits (109). Columns of this type (eg, Chiralpak OT) are available from Chiral Technologies, Inc., or J. T. Baker Inc. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

Dicyclopentadiene is also polymerized with tungsten-based catalysts. Because the polymerization reaction produces heavily cross-Unked resins, the polymers are manufactured in a reaction injection mol ding (RIM) process, in which all catalyst components and resin modifiers are slurried in two batches of the monomer. The first batch contains the catalyst (a mixture of WCl and WOCl, nonylphenol, acetylacetone, additives, and fillers the second batch contains the co-catalyst (a combination of an alkyl aluminum compound and a Lewis base such as ether), antioxidants, and elastomeric fillers (qv) for better moldabihty (50). Mixing two Uquids in a mold results in a rapid polymerization reaction. Its rate is controlled by the ratio between the co-catalyst and the Lewis base. Depending on the catalyst composition, solidification time of the reaction mixture can vary from two seconds to an hour. Similar catalyst systems are used for polymerization of norbomene and for norbomene copolymerization with ethyhdenenorbomene. 

An important aspect of this is the splitting of the polymer chain with thiol (eq. 5) or mercaptide ion (thiol + base catalyst). In fact, sodium sulfide or organic monothiols, eg, mercaptoethanol or decyhnercaptan, are utilized to lower the molecular weight of polysulftdes or to limit the extent of curing reactions. 

Few aHyl monomers have been polymerized to useful, weH-characterized products of high molecular weight by ionic methods, eg, by Lewis acid or base catalysts. Polymerization of the 1-alkenes by Ziegler catalysts is an exception. However, addition of acidic substances, at room temperature or upon heating, often gives viscous liquid low mol wt polymers, frequently along with by-products of uncertain stmcture. 

Extensive efforts have been made to develop catalyst systems to control the stereochemistry, addition site, and other properties of the final polymers. Among the most prominant ones are transition metal-based catalysts including Ziegler or Ziegler-Natta type catalysts. The metals most frequentiy studied are Ti (203,204), Mo (205), Co (206-208), Cr (206-208), Ni (209,210), V (205), Nd (211-215), and other lanthanides (216). Of these, Ti, Co, and Ni complexes have been used commercially. It has long been recognized that by varying the catalyst compositions, the trans/cis ratio for 1,4-additions can be controlled quite selectively (204). Catalysts have also been developed to control the ratio of 1,4- to 1,2-additions within the polymers (203). 

The polymer-supported catalysts are thus important conceptually in linking catalysis in solutions and catalysis on supports. The acid—base chemistry is fundamentally the same whether the catalytic groups are present in a solution or anchored to the support. The polymer-supported catalysts have replaced acid solutions in numerous processes because they minimise the corrosion, separation, and disposal problems posed by mineral acids. 

Cocatalysts, such as diethylzinc and triethylboron, can be used to alter the molecular-weight distribution of the polymer (89). The same effect can also be had by varying the transition metal in the catalyst chromium-based catalyst systems produce polyethylenes with intermediate or broad molecular-weight distributions, but titanium catalysts tend to give rather narrow molecular-weight distributions. 

Acid anhydrides have been employed with, and without the use of a base catalyst. For example, acetates, propionates, butyrates, and their mixed esters, DS of 1 to ca. 3, have been obtained by reaction of activated cellulose with the corresponding anhydride, or two anhydrides, starting with the one with the smaller volume. In all cases, the distribution of both ester groups was almost statistic. Activation has been carried out by partial solvent distillation, and later by heat activation, under reduced pressure, of the native cellulose (bagasse, sisal), or the mercerized one (cotton linters). No catalyst has been employed the anhydride/AGU ratio was stoichiometric for microcrystalhne cellulose. Alternatively, 50% excess of anhydride (relative to targeted DS) has been employed for fibrous celluloses. In all cases, polymer degradation was minimum, and functionalization occurs preferentially at Ce ( C NMR spectroscopic analysis [52,56,57]). 

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