Phillips Oxides

The Use of Nuclear Magnetic Resonance in Inorganic Chemistry E. L. Muetterties and W. D. Phillips Oxide Melts J. D. Mackenzie... 

Oxidation of Ethylene. In 1894 F. C. Phillips observed the reaction of ethylene [74-85-17 in an aqueous paHadium(II) chloride solution to form acetaldehyde. 

Second, in the early 1950s, Hogan and Bank at Phillips Petroleum Company, discovered (3,4) that ethylene could be catalyticaHy polymerized into a sohd plastic under more moderate conditions at a pressure of 3—4 MPa (435—580 psi) and temperature of 70—100°C, with a catalyst containing chromium oxide supported on siUca (Phillips catalysts). PE resins prepared with these catalysts are linear, highly crystalline polymers of a much higher density of 0.960—0.970 g/cnr (as opposed to 0.920—0.930 g/cnf for LDPE). These resins, or HDPE, are currentiy produced on a large scale, (see Olefin polymers, HIGH DENSITY POLYETHYLENE). 

HDPE resias are produced ia industry with several classes of catalysts, ie, catalysts based on chromium oxides (Phillips), catalysts utilising organochromium compounds, catalysts based on titanium or vanadium compounds (Ziegler), and metallocene catalysts (33—35). A large number of additional catalysts have been developed by utilising transition metals such as scandium, cobalt, nickel, niobium, molybdenum, tungsten, palladium, rhodium, mthenium, lanthanides, and actinides (33—35) none of these, however, are commercially significant. 

LLDPE resias are produced ia iadustry with three classes of catalysts (11—14) titanium-based catalysts (Ziegler), metallocene-based catalysts (Kaminsky and Dow), and chromium oxide-based catalysts (Phillips). 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

This process has many similarities to the Phillips process and is based on the use of a supported transition metal oxide in combination with a promoter. Reaction temperatures are of the order of 230-270°C and pressures are 40-80 atm. Molybdenum oxide is a catalyst that figures in the literature and promoters include sodium and calcium as either metals or as hydrides. The reaction is carried out in a hydrocarbon solvent. 

The first commercial grades were introduced by Phillips Petroleum in 1968 under the trade name Ryton. These were of two types, a thermoplastic branched polymer of very high viscosity which was processed by PTFE-type processes and an initially linear polymer which could be processed by compression moulding, including laminating with glass fibre, and which was subsequently oxidatively cross-linked. 

Explds violently on contact with Cu oxide and is friction sensitive. Its Hg salt is also an expl Refs 1) Beil 25, 114 2) D.D. Phillips ... 

Olefin metathesis is the transition-metal-catalyzed inter- or intramolecular exchange of alkylidene units of alkenes. The metathesis of propene is the most simple example in the presence of a suitable catalyst, an equilibrium mixture of ethene, 2-butene, and unreacted propene is obtained (Eq. 1). This example illustrates one of the most important features of olefin metathesis its reversibility. The metathesis of propene was the first technical process exploiting the olefin metathesis reaction. It is known as the Phillips triolefin process and was run from 1966 till 1972 for the production of 2-butene (feedstock propene) and from 1985 for the production of propene (feedstock ethene and 2-butene, which is nowadays obtained by dimerization of ethene). Typical catalysts are oxides of tungsten, molybdenum or rhenium supported on silica or alumina [ 1 ]. 

Phillips, J. F. Dissolution of Oxide-Coated Zirconium and Zirconium Alloys, U.S. AEC Report BNWL-600, Pacific Northwest Laboratory, Richland, WA, 1968. 

PHILLIPS ETAL. Supported Iron Oxide Particles... 

Lovley DR, EJP Phillips (1988) Novel mode of microbial energy metabolism organic carbon oxidation coupled to dissimilatory reduction of iron or manganese. Appl Environ Microbiol 54 1472-1480. 

Phillip B, B Schink (1998) Evidence of two oxidative reaction steps initiating anaerobic degradation of resorcinol (1,3-dihydroxybenzene) by the denitrifying bacteiimn Azoarcus anaerobius. J Bacteriol. 180 3644-3649. 

Arata, K. and Hino, M., Proc. 9th Intern. Congr. Catal. ( Oxide Catalysts and Catalyst Development , Phillips, M.J. and Teman, M., eds.). The Chemical Institute of Canada, Ontario (1988) 1727. 

The most important approach was to use poly(methyl methacrylate), PMMA, in formulations, either as a particulate filler or as a coating on zinc oxide particles (Jendresen Phillips, 1969 Jendresen et al., 1969 Civjan et al., 1972). It is claimed that such materials can be used for permanent as well as temporary cementation. 

Jendresen, M. D. Phillips, R. W. (1969). A comparative study of four zinc oxide eugenol formulations as restorative materials. Part II. Journal of Prosthetic Dentistry, 21, 300-9. 

Norman, R. D., Phillips, R. W., Swartz, M. L. Frankiewicz, T. (1964). The effect of particle size on the physical properties of zinc oxide-eugenol mixtures. Journal of Dental Research, 43, 252-62. 

El-Agamey, A, Lowe, GM, McGarvey, DJ, Mortensen, A, Phillip, DM, Truscott, TG, and Young, AJ, 2004b. Carotenoid radical chemistry and antioxidant/pro-oxidant properties. Arch Biochem Biophys 430, 37-48. 

---