Poly-branched hydrocarbons

We discovered another synthetic technique that involves the conversion by direct fluorination of hydrocarbon polyesters to perfluoropolyesters followed by treatment with sulfur tetrafluoride to produce new perfluoropolyethers.42 The first paper in this area ofreasearch reported that conversion of poly(2,2-dimethyl-1,3-propylene succinate) and poly( 1,4-butylene adipate) by using the direct fluorination to produce novel branched and linear perfluoropolyethers, respectively. The structures are shown in Figure 14.6. The second paper concerns the application of the direct fluorination technology base directed toward oligomers, diacids, diesters, and surfactants.43... 

Branched substituents on the nucleus of PS impede the rotation but do not decrease the Tt to any great extent. The solubility parameter decreases as the size of the substituent alkyl groups increases. Thus although PS is not soluble in aliphatic hydrocarbon liquids, poly / cydohexylstyrene is soluble and serves as a viscosity index improver for lubricating oils. 

Polymerized olefins include poly-a-olefins (PAOs), linear a-olefins (LAOs), and internal olefins (IOs) [24]. Hydrocarbon chain length and branching are selected to optimize the drilling properties and minimize the environmental toxicity [20]. 

In ionic polymerization a hydride (H-) transfer or a proton transfer are the analogues of the hydrogen atom transfer in radical polymerization. A hydride (H-) ion transfer is observed in many isomerizations and dimerizations of hydrocarbons which proceed via carbonium-ion mechanism. A similar process is responsible for chain transfer ip some carbonium-ion polymerizations. The transfer of negative ions like Cl- is also common, e.g. triphenyl methyl chloride is an efficient transfer agent in such a polymerization. Transfer of a proton is, on the other hand, a very common mode of termination of anionic polymerization. Indeed, this mode of termination was discussed previously in connection with branching reactions, and it was postulated in the earliest studies of anionic poly-... 

It should also be noted that the viscometric technique can detect the presence of star-shaped aggregates, having the ionic active centers. The addition of ethylene oxide to hydrocarbon solutions of poly(isoprenyl)lithium leads to a nearly two-fold increase in viscosity144). Conversely, this results in an approximately twenty-fold decrease in solution viscosity, after termination by the addition of trimethylchloro-silane. This change in solution viscosity is reflected in the gelation which occurs when difunctional chains are converted to the ionic alkoxy active centers 140,145,146). Branched structures have also been detected 147> by viscometry for the thiolate-lithium active center of polypropylene sulfide) in tetrahydrofuran. 

These polymers are typically prepared by reaction of sodium polysulfide with a formal. Bis(2-chloroelhy(formal) is commonly used, but some tn functional chlorinated hydrocarbon with its associated higher functionality is typically also added to promote branching. The sodium poly sulfide is usually made by the direct reaction of sodium hydroxide with sulfur at temperatures near 120 °C, as shown in reaction (9) 62... 

Crude petroleum contains complex mixtures of hydrocarbons as well as relatively small amounts of nitrogen-, sulfur-, and oxygen-containing organic compounds, asphaltenes, and various trace metals (uncomplexed and complexed forms). The hydrocarbons can be divided into two classes related to their chemical structure the alkanes (normal, branched, and cyclo) and aromatic compounds (mono-, di-, and poly-, i.e., PAH). 

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