Polymerization spontaneous

Similarly strange tilings happen to other materials. Above 5 GPa, CO spontaneously polymerizes the... 

Viayl fluoride is flammable ia air between the limits of 2.6 and 22% by volume. Minimum ignition temperature for VF and air mixtures is 400°C. A small amount, <0.2%, of terpenes is added to VF to prevent spontaneous polymerization. The U.S. Department of Transportation has classified the inhibited VF as a flammable gas. 

The spontaneous polymerization of styrene was studied in the presence of various acid catalysts (123) to see if the postulated reactive intermediate DH could be intentionally aromatized to form inactive DA. The results showed that the rate of polymerization of styrene is significantly retarded by acids, eg, camphorsulfonic acid, accompanied by increases in the formation of DA. This finding gave further confirmation of the intermediacy of DH because acids would have Httie effect on the cyclobutane dimer intermediate in the Flory mechanism. 

Another economically driven objective is to utilize initiators that increase the rate of styrene polymerization to form PS having the desired molecular weight. The commercial weight average molecular weight M range for general-purpose PS is 200,000—400,000. For spontaneous polymerization, the is inversely proportional to polymerization rate (Fig. 16). 

Other reasons for a wide propagation of polymerization in water include (1) reduction of energy consumed to separate the initial monomer in crystal form (acrylamide is produced and used in the aqueous solution form), which, in addition, is associated with the probability of its spontaneous polymerization, and (2) recovery of the organic solvents, which results in less environmental pollution and the elimination of the stage of solution of polymer reagents used, as a rule, in the form of the aqueous solutions. 

The spontaneous polymerization of furan adsorbed on carbon black with or without SnCl4 vapours35 has been explained by a similar cationic mechanism. Also, the polymerization of gaseous furan on liquid acidic surfaces35 has the same origin, but in these systems the polymers suffer an acid-catalyzed hydrolysis of their tetrahydrofuran rings which produces a considerable proportion of hydroxyl and carbonyl groups. 

The thermal polymerization of S has a long history.310 The process was first reported in 1839, though the involvement of radicals was only proved in the 1930s. Carefully purified S undergoes spontaneous polymerization at a rate of ca 0.1% per hour at 60 C and 2% per hour at 100 °C. At 180 aC, 80% conversion of monomer to polymer occurs in approximately 40 minutes. Polymer production is accompanied by the formation of S dimers and trimers which comprise ca 2% by weight of total products. The dimer fraction consists largely of cis- and trans-1,2-diphenylcyclobutanes (90 and 91) while the stereoisomeric tetrahydronaphthalenes (92 a nd 93) are the main constituents of the trinier fraction.313... 

Various acrylates, methacrylates and related compounds have been reported to undergo spontaneous polymerization. 110 A complication in studying thermal polymerization of MMA is the difficulty in eliminating impurity initiated polymerization. The monomer is extremely difficult to purify or retain in a "pure" state. These problems have led some to question whether there is any true spontaneous initiation.323 It is, in any event, clear that the rate of thermal polymerization of MMA is substantially less than that of S at the same temperature (at least 70-fold less at 90 °C).310324... 

Dimer and trimer byproducts have been isolated from MMA polymerizations and these are suggestive of 1,4-diradical intermediates.323 28 Lingnau and Mcycrhoff523 found that rates of spontaneous polymerization of MMA were substantially higher in the presence of transfer agents (RH). They were able to isolate the compound (98) that might come from trapping of the biradical intermediate (Scheme 3.65). 

Free-radical polymerizations tend to be highly exothermic. The following data are representative of the thermal (i.e., spontaneous) polymerization of styrene ... 

G-actin is present in most if not all cells of the body. With appropriate concentrations of magnesium and potassium chloride, it spontaneously polymerizes to form double helical F-actin filaments like those seen in muscle. There are at least two types of actin in nonmus-... 

Since spontaneous polymerization is only observed in contact with air or in undesiccated benzene used as a reaction medium, it is natural to attribute this phenomenon to the catalytic effect of traces of water on the opening of the oxirane ring involved in the coordination interaction with the tin atom. 

Polymers Polyacrylamide and hydrolyzed polyacrylamide were prepared by the American Cyanamid Company specifically for this project, starting with l C labelled monomer. The radioactivity level of the monomer was kept below 0.20 mC /g in order to avoid significant spontaneous polymerization, utilizing a copper inhibitor. The homopolymer was synthesized by free radical solution polymerization in water at 40°C, using monomer recrystallized from chloroform, an ammonium persulfate-sodium metabisulfite catalyst system, and isopropanol as a chain transfer agent. Sodium... 

The best developed example of a material produced by VDP is poly(p-xylylene) designated as Parylene-N by the Union Carbide Corporation. Poly(/i-xylylene) was discovered by Szwarc12 in 1957 and then commercialized by Gorham at Union Carbide.13,14 (Scheme 1). Gorham has reported that di-p-xylylene is quantitatively cleaved by vacuum vapor-phase pyrolysis at 600°C to form two molecules of the reactive intermediate /i-xylylene, which subsequently polymerizes on the cold substrate. In a system maintained at less than 1 Torr, p-xylylene spontaneously polymerizes on surfaces below 30°C to form... 

Spontaneously twisted nematics, 15 92 Spontaneous polarization, in compound semiconductors, 22 152 Spontaneous polymerization ofVDC, 25 695... 

Mielke and Ringsdorf (197 la,b, 1972) have found that the mechanism for the spontaneous polymerization of 4-vinylpyridinium perchlorate changes... 

EDC and VC are each traded commercially as a 99% pure grade. VC is usually designated as inhibited, indicating the presence of phenol to prevent spontaneous polymerization. 

Due to its aromatic iminodiacetic acid structure, PIDAA is not only more acidic than NPG but is also a more efficient chelator for Ca+. Thus it can effectively serve both as an etchant and as a primer like NPG because of its arylamine structure. To gain further insight into the mechanism of the spontaneous polymerization of acrylics caused by PIDAA, several derivatives of PIDDA with electron-withdrawing or -donating aromatic ring substituents were prepared. The rationale for this study was to ascertain, by... 

A spontaneous polymerization of glucose methacrylate, however, is observed during the monomer preparation without gel formation and a very hydrophilic water soluble polymer with high viscosity is obtained by precipitation in acetone. This procedure requires further improvement. 

Acid-catalyzed dimerization and oligomerization of 1,2,4-trioxolanes will be covered in Section 4.16.5.2.1. In general, ozonides are not prone to spontaneous polymerization. Polymeric products can be obtained from the ozonolysis of alkenes but most likely arise from reaction of the primary ozonide. Bicyclic 1,2,4-trioxolanes such as 2,5-dimethylfuran endoperoxide can dimerize on warming in CCI4 (Section 4.16.5.1.1). 1,2,4-Trithiolane tends to polymerize at room temperature especially if left open to air, whilst more highly substituted ring systems are stable. 

Certain substances which are susceptible to spontaneous polymerization or decomposition are generally placed on the market in a stabilized form. It is in this form that they are listed in Annex I to the Commission Directive 98/98/EC. However, such substances are sometimes sold in a nonstabilized form. In this case, the manufacturer or any person who places such a substance on the market must state on the label the name of the substance followed by the words non-stabilized . 

Spontaneous polymerization of 4-vinyl pyridine in the presence of polyacids was one of the earliest cases of template polymerization studied. Vinyl pyridine polymerizes without an additional initiator in the presence of both low molecular weight acids and polyacids such as poly(acrylic acid), poly(methacrylic acid), polyCvinyl phosphonic acid), or poly(styrene sulfonic acid). The polyacids, in comparison with low molecular weight acids, support much higher initial rates of polymerization and lead to different kinetic equations. The authors suggested that the reaction was initiated by zwitterions. The chain reaction mechanism includes anion addition to activated double bonds of quaternary salt molecules of 4-vinylpyridine, then propagation in the activated center, and termination of the growing center by protonization. The proposed structure of the product, obtained in the case of poly(acrylic acid), used as a template is ... 

A template mechanism was also proposed for spontaneous polymerization of propargyl chloride in the presence of poly(4-vinylpyridine). The reaction consists of partial (6-8%) alkylation of P4VPy by propargyl chloride which leads to stable complex P4VPy with monomer and then to polymerization. The product obtained contains a conjugated bond system formed by opening triple bonds in the monomer according to reaction ... 

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