Polystyrene formation

SAXSAVAXS/RAMAN is especially useful when dealing with chemically induced phase transitions. The example shown in Figure 2(e) is the polymerisation of solvent styrene into polystyrene in which polyethylene is in solution. Polyethylene is soluble in styrene but insoluble in polystyrene. RAMAN allows the determination of the reaction kinetics of polystyrene formation and monitors the crystallisation of the polyethylene. The SAXS monitors the liquid-liquid phase separation followed by the liquid-solid phase transition, whilst the WAXS also observes the liquid solid phase by monitoring the appearance of peaks due to the crystallisation of polyethylene. These are very valuable parameters when trying to define any new manufacturing process. ... 

Polymerisation. To 0 5 ml. of styrene add i drop of cone. HjSOj. Note the formation of a solid glassy mass of polystyrene. 

Carbanions stabilized by phosphorus and acyl substituents have also been frequently used in sophisticated cyclization reactions under mild reaction conditions. Perhaps the most spectacular case is the formation of an ylide from the >S-lactam given below using polymeric Hflnig base (diisopropylaminomethylated polystyrene) for removal of protons. The phosphorus ylide in hot toluene then underwent an intramolecular Wlttig reaction with an acetyl-thio group to yield the extremely acid-sensitive penicillin analogue (a penem I. Ernest, 1979). 

Up until 1986 the major use for 2-j -butylphenol was in the production of the herbicide, 2-j -butyl-4,6-dinitrophenol [88-85-7] which was used as a pre- and postemergent herbicide and as a defoHant for potatoes (30). The EPA banned its use in October 1986 based on a European study which showed that workers who came in contact with 2-j -butyl-4,6-dinitrophenol experienced an abnormally high rate of reproduction problems. Erance and the Netherlands followed with a ban in 1991. A significant volume of 2-j -butyl-4,6-dinitrophenol is used worldwide as a polymerization inhibitor in the production of styrene where it is added to the reboiler of the styrene distillation tower to prevent the formation of polystyrene (31). OSBP is used in the Par East as the carbamate derivative, 2-j -butylphenyl-Ai-methylcarbamate [3766-81-2] (BPMC) (32). BPMC is an insecticide used against leaf hoppers which affect the rice fields. 

Rhodacarborane catalysts have been immobilized by attachment to polystyrene beads with appreciable retention of catalytic activity (227). A 13-vertex /oj iJ-hydridorhodacarborane has also been synthesized and demonstrated to possess catalytic activity similar to that of the icosahedral species (228). Ak-oxidation of closo- >(2- P((Z [) 2 - i- > l[l-Bih(Z, results in a brilliant purple dimer. This compound contains two formal Rh " centers linked by a sigma bond and a pak of Rh—H—B bridge bonds. A number of similar dimer complexes have been characterized and the mechanism of dimer formation in these rhodacarborane clusters have been studied in detail (229). 

The Q-e Scheme. The magnitude of and T2 can frequentiy be correlated with stmctural effects, such as polar and resonance factors. For example, in the free-radical polymerization of vinyl acetate with styrene, both styrene and vinyl acetate radicals preferentially add styrene because of the formation of the resonance stabilized polystyrene radical. 

Formic anhydride is not stable. However, formate esters of alcohols and phenoHcs can be prepared using formic—acetic anhydride (69,70). Anhydrides can also be incorporated into polystyrene backbones which can then be treated with alcohols to afford the corresponding esters and carboxypolystyrene for recycle (71). 

The intramolecular condensation reaction of diesters, the Dieckmann condensation, works best for the formation of 5- to 7-membered rings larger rings are formed with low yields, and the acyloin condensation may then be a faster competitive reaction. With non-symmetric diesters two different products can be formed. The desired product may be obtained regioselectively by a modified procedure using a solid support—e.g with a polystyrene 10 ... 

The formation of the polyalloy results in improvement in the performance of the blends. This system is similar to the production of high-impact polystyrene (HIPS) where a rubber is dissolved in styrene monomer and then polymerized in the usual way. Even though the impact strength of the compatibilized PS-PE blend was higher than that of PS, it was much less than that of HIPS. In another study. Van Ballegooie and [55] have confirmed... 

Macromonomers always lead to the formation of graft copolymers. For example, the vinyl-terminated polystyrene can be copolymerized with ethylene to produce a graft copolymer of polyethylene, whereby the vinyl moiety of polystyrene is integrally polymerized into the linear polyethylene backbone ... 

The formation of these polar groups contributes increased adhesion. Observation of disappearing vinyl groups in the silane coupling agent and of the formation of polystyrene in the silica by FTIR analysis (Fig. 15) have confirmed the occurrence of a reaction between the polymer and the silane coupling agent [77]. 

Q A Boc-protected amino acid is covalently linked to the polystyrene polymer by formation of an ester bond (Sn2 reaction). 

These ideas might be used to explain the interesting results obtained recently by Williams et al.53 These workers observed formation of crystalline polystyrene when the reaction was initiated by triphenyl methyl potassium (or some other potassium metallo-organic compounds) in a hexane solution, but an amorphous polymer was formed in benzene. They point out that the catalyst is soluble in benzene but insoluble in hexane, and suggest that the heterogeneity of the catalyst is responsible for the results. Although this might be the case, an alternative explanation could be advanced.42 1... 

Formation of block polymers is not limited to hydrocarbon monomers only. For example, living polystyrene initiates polymerization of methyl methacrylate and a block polymer of polystyrene and of polymethyl methacrylate results.34 However, methyl methacrylate represents a class of monomers which may be named a suicide monomer. Its polymerization can be initiated by carbanions or by an electron transfer process, the propagation reaction is rapid but eventually termination takes place. Presumably, the reactive carbanion interacts with the methyl group of the ester according to the following reaction... 

Platinum-cobalt alloy, enthalpy of formation, 144 Polarizability, of carbon, 75 of hydrogen molecule, 65, 75 and ionization potential data, 70 Polyamide, 181 Poly butadiene, 170, 181 Polydispersed systems, 183 Polyfunctional polymer, 178 Polymerization, of butadiene, 163 of solid acetaldehyde, 163 of vinyl monomers, 154 Polymers, star-shaped, 183 Polymethyl methacrylate, 180 Polystyrene, 172 Polystyril carbanions, 154 Potential barriers of internal rotation, 368, 374... 

The kinetics of polymerization and conductometric studies of barium polystyrene with one active end-group per chain were reported by De Groof et al. 79,80). Formation of an unconventional anionic species, Ba2 +, (CH(Ph)CH2—)j, had to be postulated to account for the results. The existence of such a species is supported by the recent study of the kinetics of polymerization of lithium polystyrene performed in the presence of barium polystyrene endowed with two active endgroups 78). The polymerization of the lithium salt is retarded by the presence of the barium salt, and the retardation is accounted for by the formation of the inert aggregated anions,... 

The correct explanation of the peculiar behaviour of the butadiene-styrene system was provided by O Driscoll and Kuntz 144). As stated previously, under conditions of these experiments butadiene is indeed more reactive than styrene, whether towards lithium polystyrene or polybutadiene, contrary to a naive expectation. This was verified by Ells and Morton 1451 and by Worsfold 146,147) who determined the respective cross-propagation rate constants. It is germane to stress here that the coordination of the monomers with Li4, assumed to be the cause for this gradation of reactivities, takes place in the transition state of the addition and should be distinguished from the formation of an intermediate complex. The formation of a complex ... 

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