Polymerization, history

Mechanical Interlocking of Components. In some instances the polymers in a blend may be prevented from demixing because of numerous mutual entanglements produced by mechanical processing or the polymerization history of the blend. 

Fawcett and Gibson See polymerization history, feather edge See fin. 

Ziegler-Natta catalyst See catalyst, Ziegler-Natta. Ziegler process A process for the low-pressure linear polymerization of ethylene and stereospecific polymerization of polypropylene. The product is a high-density plastic or elastomer. It is named for Karl Ziegler, the German scientist who was corecipient (with Giullo Natta, Italy) of the Noble Prize in 1963. See catalyst polymerization polymerization history. 

With respect to the above it is noteworthy that Kent et al. [107] performed their study using narrow polydispersity probe and matrix polymers. The insensitivity of Rg versus polymer concentration below C only occurs if the molar mass of the probe and background polymer are similar. If the matrix polymer is of much lower molar mass, it can freely penetrate the probe polystyrene molecules and act as a poor viscous solvent inside the probe coils. In that case a decrease in Rg can also be observed at polymer concentration below C [107], In real free-radical polymerizations, polymer molecules with a wide variety of molar masses will be present simultaneously and it can thus be expected that all macroradicals will experience coil contraction to some extent in dilute solutions (except for the very smallest macroradicals). The magnitude of this effect will thus be dependent upon the molecular weight distribution (MWD) of the polymer and thus also upon the systems polymerization history. 

Our mechanistic knowledge of these reactions has also progressed accordingly, and we begin to understand many of the basic factors by which they are governed. However the numerous informations provided by a refined structural analysis of the polymerization history, has revealed an increasingly oorplex picture of these catalysts bdiaviour. 

Our purpose in this introduction is not to trace the history of polymer chemistry beyond the sketchy version above, instead, the objective is to introduce the concept of polymer chains which is the cornerstone of all polymer chemistry. In the next few sections we shall introduce some of the categories of chains, some of the reactions that produce them, and some aspects of isomerism which multiply their possibilities. A common feature of all of the synthetic polymerization reactions is the random nature of the polymerization steps. Likewise, the twists and turns the molecule can undergo along the backbone of the chain produce shapes which are only describable as averages. As a consequence of these considerations, another important part of this chapter is an introduction to some of the statistical concepts which also play a central role in polymer chemistry. 

The soap of modified rosin has a long history as an emulsifier for the polymerization of styrene—butadiene mbber. The rosin soap remains in the mbber after polymerization and increases the tack between the pHes of mbber required in the manufacture of tires. 

PS Foams. The eady history of foamed PS is available (244), as are discussions of the theory of plastic foams (245). Foamable PS beads were developed in the 1950s by BASF under the trademark of STYROPOR (246—248). These beads, made by suspension polymerization in the presence of blowing agents such as pentane or hexane, or by post-pressurization with the same blowing agents, have had an almost explosive growth, with 200,000 metric tons used in 1980. Some typical physical properties of PS foams are Hsted in Table 10 (see Foamed plastics). 

The idea of using polyunsaturated monomers is rooted in the eady history of acryUc elastomers. The first monomers used were butadiene [106-99-0] (35), isoprene [78-79-5] (36), and aHyl maleate [999-21-3] (37), but they did not find commercial success because during polymerization large portions of polymer were cross-linked. Other monomers have been proposed more recentiy tetrahydrobenzyl acrylate (38), dicyclopentenyl acrylate [2542-30-2] (39), and 5-ethyhdene-2-norbomene [16219-75-3] (40). The market potential, at least for the more recent ones, is stiU to be determined. 

The early history of redox initiation has been described by Bacon.23 The subject has also been reviewed by Misra and Bajpai,207 Bamford298 and Sarac.2,0 The mechanism of redox initiation is usually bimolecular and involves a single electron transfer as the essential feature of the mechanism that distinguishes it from other initiation processes. Redox initiation systems are in common use when initiation is required at or below ambient temperature and drey are frequently used for initiation of emulsion polymerization. 

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... 

The history of iodine transfer polymerization may be traced back to telomerization experiments carried out in the 1940fs.26"3" Iodine-transfer... 

History. The first attempts to desensitize RDX were reported by Frankel and Carle ton (Refs 1 thru 5) who made use of polymeric materials such as polyurethanes to coat expl crysts by means of emulsion or soln techniques. The first true PB-RDX was developed in 1952 at the Univ of Califs Los Alamos Lab and consisted of RDX coated with polystyrene plasticized with DOP (Refs 6 21). Since then the Lawrence Livermore Lab has evolved a series of PBX formulations, many of which are listed in Tables 3,4 5. These compns are described in Ref 77... 

The history of polyurethanes begins with Otto Bayer3 at Germany s I. G. Farben-industrie (tire predecessor company of Bayer AG4) in 1937, tire year of tire first disclosure of diisocyanate addition polymerization to form polyurethanes and polyureas. The main impetus for this work was tire success of Wallace Caro titers... 

Polylactides, 18 Poly lactones, 18, 43 Poly(L-lactic acid) (PLLA), 22, 41, 42 preparation of, 99-100 Polymer age, 1 Polymer architecture, 6-9 Polymer chains, nonmesogenic units in, 52 Polymer Chemistry (Stevens), 5 Polymeric chiral catalysts, 473-474 Polymeric materials, history of, 1-2 Polymeric MDI (PMDI), 201, 210, 238 Polymerizations. See also Copolymerization Depolymerization Polyesterification Polymers Prepolymerization Repolymerization Ring-opening polymerization Solid-state polymerization Solution polymerization Solvent-free polymerization Step-grown polymerization processes Vapor-phase deposition polymerization acid chloride, 155-157 ADMET, 4, 10, 431-461 anionic, 149, 174, 177-178 batch, 167 bulk, 166, 331 chain-growth, 4 continuous, 167, 548 coupling, 467 Friedel-Crafts, 332-334 Hoechst, 548 hydrolytic, 150-153 influence of water content on, 151-152, 154... 

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