Polymers benzene-sulfur containing

Thiophenes continue to play a major role in commercial applications as well as basic research. In addition to its aromatic properties that make it a useful replacement for benzene in small molecule syntheses, thiophene is a key element in superconductors, photochemical switches and polymers. The presence of sulfur-containing components (especially thiophene and benzothiophene) in crude petroleum requires development of new catalysts to promote their removal (hydrodesulfurization, HDS) at refineries. Interspersed with these commercial applications, basic research on thiophene has continued to study its role in electrocyclic reactions, newer routes for its formation and substitution and new derivatives of therapeutic potential. New reports of selenophenes and tellurophenes continue to be modest in number. 

Pyrolysis products of chlorinated polyethylene contain molecules similar to those found in polyethylene pyrolysates and, in addition, compounds similar to that obtained from vinyl chloride (significant amount of HCI). Chlorosulfonated polyethylene typically contains only about 1.5% sulfur, but sulfur-containing compounds such as SO2 can be detected among its pyrolysis products. The distribution of chlorine atoms in chlorinated polyethylene has been investigated using Py-GC [55, 56]. The polymer was considered equivalent with a terpoiymer poly[ethylene-co-(vinyl chloride)-co-(1,2-dichloroethylene)]. The level of specific degradation products such as aromatic molecules (benzene + toluene + styrene + naphthalene), chlorobenzene, and dichlorobenzenes correlates well with the carbon/chlorine ratio in the polymer. 

A typical example is total monomers. 100 sodium stearate, 5 potassium persulfate, 0.3 lauryl mercaptan, 0.4 to 0.7 and water, 200 parts. In this formula, 75 parts of 1,3-butadiene and 25 parts of 4-methyl-2-vinylthiazole give 86% conversion to a tacky rubber-like copolymer in 15 hr at 45°C. The polymer contains 62% benzene-insoluble gel. Sulfur analysis indicates that the polymer contains 21 parts of combined 4-methyl-2-vinylthiazole (312). Butadiene alone in the above reaction normally requires 25 hr to achieve the same conversion, thus illustrating the acceleration due to the presence of 4-methyl-2-vinylthiazole. 

Even so, a number of chemical agents, including liquids, chemically attack polymers. Reactions that would ordinarily occur with small molecules also occur in polymers, given the same functional groups and reactive sites. Thus benzene, toluene, etc., are readily sulfonated when exposed to sulfuric acid. Likewise polystyrene (PS) is sulfonated when exposed to liquids and gases containing sulfuric acid ... 

Typically, the oil phase contained 78% monomer/co-monomer, 8% divinyl benzene (cross-linking agent), and 14% non-ionic surfactant Span 80 (Sorbitan monooleate), while the aqueous phase contained 1% potassium persulfate as the initiator. In most cases studied here, monomer is styrene and when elasticity of the polymer is required, 2-ethylhexyl acrylate (2EHA) was used (styrene/2EHA ratio is 1 4). Whenever additives/fillers are placed in the aqueous phase their amounts are stated as weight percent while the phase volume of the aqueous phase remains constant. In some cases, the aqueous phase contains 0.5% hydroxyapatite and 15% phosphoric acid which is used to dissolve the hydroxyapatite, or alternatively, the aqueous phase may contain varying amounts of water-soluble polymer, such as polyethylene glycol or polyethylene oxide. If the styrene-based PHP is to be sulfonated to obtain ionic-hydrophilic foam, the pre-dispersion of sulfuric acid within the pores is useful, if not essential, and in that case, acids (typically 10%) can be used as the internal phaseP . ... 

Another addition to polymers with main-chain unsaturation is the Prins reaction between ethylenic hydrocarbons and compounds containing aldehydic carbonyl groups. Kirchof in 1923, described the reaction of natural rubber in benzene solution with aqueous formaldehyde in the presence of concentrated sulfuric acid. The general reaction of an aldehyde, RCHO, with a polyisoprene in the presence of an inorganic or organic acid or an anhydrous metal salt, is represented by... 

Sulfoxides and sulfones (Figure 9.13) contain both sulfur and oxygen. Dimethylsulfoxide (DMSO) is a liquid used to remove paint and varnish, as a hydraulic fluid, mixed with water as an antifreeze solution, and in pharmaceutical applications as an anti-inflammatory and bacteriostatic agent. Sulfolane dissolves both organic and inorganic solutes and is widely used in BTX processing to selectively extract benzene, toluene, and xylene from aliphatic hycbocarbons as the solvent in the Sulfinol process by which thiols and acidic compounds are removed from natural gas as a solvent for polymerization reactions and as a polymer plasticizer. 

Poly(phenylene sulfide) from Benzene and Sulfur but does not contain any evidence that the polymers are PPS. 

In general, it was found that the thio-monomers were more soluble and reactive than the oxo. They also produced more thermally stable polymers. The cis isomers of the monomers were more soluble than the trans, but the trans were more reactive. The polymers were stable in hot dilute hydrochloric acid and sodium hydroxide solutions. All polymers were soluble in chloroform, dimethylformamide, and sulfuric acid. Polymers which contained sulfur were also soluble in carbon tetrachloride, benzene, xylene and toluene. Brittle films could be cast from solution or melt-pressed. 

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