INDEX free-radical processes

The polystyrene produced had a polydispersity index (M /M ) of 1.2 to 1.3, which is much lower than that obtained using conventional free-radical processes. 

In the case of polycarbonate and other polymers which possess a broad MMD, MALDI fails to give reliable Mn and Myf values. MALDI underestimates The Mn value falls invariably too close to so that MALDI underestimates the polydispersity index. Generally, MALDI cannot be applied to polymers obtained by free-radical polymerization, since free-radical processes yield polymers which possess a broad MMD. For instance, we recorded [62] the MALDI spectrum of a PMMA sample with a polydispersity index of around 2.5 (the averages were % = 13 kDa and = 33 kDa)... 

A second theoretical index, and one for which there appears to be more justification in its application to free-radical reactions, is the atom localization energy. This index is a measure of the energy required to localize one electron of the 7r-electron system in the aromatic molecule at the point of attack of the radical. The formation of the intermediate adduct in a free-radical aromatic substitution may be regarded as the sum of two processes one, the localization of an electron at the point of attack and the other, the pairing of this... 

Controlled expansion alloys, 13 520-522 Controlled flavor release systems, 11 528, 543-553, 554-555 characteristics of, ll 544t demand for, 11 555 developments in, 11 558 elements of, 11 555-557 extrusion encapsulation for, 11 550 key aspects of, 11 556t morphologies of, 11 545 Controlled free-radical polymerization, block copolymers, 7 646 Controlled humidity drying, ceramics processing, 5 655-656 Controlled indexing, 18 241 Controlled initiation, 14 268-269 Controlled laboratory studies, in... 

Ethylene Polymers. Depending on the polymerization conditions, three major types of polyethylene are manufactured low-density polyethylene (LDPE) by free-radical polymerization, linear low-density polyethylene (LLDPE) by copolymerization of ethylene with terminal olefins, and high-density polyethylene (HDPE) by coordination polymerization. The processes yield polymers with different characteristics (molecular weight, molecular weight distribution, melt index, strength, crystallinity, density, processability). 

The termination process occurs instantaneously via entrant free radicals of (near) zero molecular weight. These radicals do not perturb significantly the distribution of chain lengths in converting growing chains to dead polymer. Indeed, termination in this instance is equivalent to chain transfer, which gives an identical value for the polydispersity index. 

The volume is divided grossly into sections dealing with individual types of free radicals such as carbon-centered radicals, nitrogen-centered radicals, nitroxyl radicals, oxygen-centered radicals and radicals, centered on other heteroatoms. These sections deal mainly with irreversible reactions. In addition, there are sections on reversible electron and proton transfer processes and their equilibria and a chapter on biradicals. An index of radicals formulae will facilitate data retrieval. 

Lewis and Volpert continue the discussion of the isothermal form of frontal polymerization in Chapter 5. Isothermal frontal polymerization is also a localized reaction zone that propagates but because of the autoacceleration of the rate of free-radical polymerization with conversion. A seed of poly(methyl methacrylate) is placed in contact with a solution of a peroxide or nitrile initiator, and a front propagates from the seed. The monomer diffuses into the seed, creating a viscous zone in which the rate of polymerization is faster than in the bulk solution. The result is a front that propagates but not with a constant velocity because the reaction is proceeding in the bulk solution at a slower rate. This process is used to create gradient refractive index materials by adding the appropriate dopant. 

Reed and coworkers developed a strategy for automatic continuous online monitoring of polymerization (ACOMP). The method may be used during the initial development of the polymerization process, its optimization and monitoring of the continuous reaction. ACOMP automatically dilutes samples from the reactor and measures its properties, e.g., refractive index, near infrared (NIR) spectra, LSc, [ ]], etc., from which it computes evolution of MW, MWD, degree of conversion, copolymer composition (in copolymerization) and others. The method has been applied to a variety of the free radical homo- and co-polymerizations, including the reactions in emulsion or suspension. ... 

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