Polymerization thermodynamics reviews

Polymerization thermodynamics has been reviewed by Allen and Patrick,323 lvin,JM [vin and Busfield,325 Sawada326 and Busfield/27 In most radical polymerizations, the propagation steps are facile (kp typically > 102 M 1 s l -Section 4.5.2) and highly exothermic. Heats of polymerization (A//,) for addition polymerizations may be measured by analyzing the equilibrium between monomer and polymer or from calorimetric data using standard thermochemical techniques. Data for polymerization of some common monomers are collected in Table 4.10. Entropy of polymerization ( SP) data are more scarce. The scatter in experimental numbers for AHp obtained by different methods appears quite large and direct comparisons are often complicated by effects of the physical state of the monomei-and polymers (i.e whether for solid, liquid or solution, degree of crystallinity of the polymer). 

Basic to the thermodynamic description is the heat capacity which is defined as the partial differential Cp = (dH/dT)n,p, where H is the enthalpy and T the temperature. The partial differential is taken at constant pressure and composition, as indicated by the subscripts p and n, respectively A close link between microscopic and macroscopic description is possible for this fundamental property. The integral thermodynamic functions include enthalpy H entropy S, and free enthalpy G (Gibbs function). In addition, information on pressure p, volume V, and temperature T is of importance (PVT properties). The transition parameters of pure, one-component systems are seen as first-order and glass transitions. Mesophase transitions, in general, were reviewed (12) and the effect of specific interest to polymers, the conformational disorder, was described in more detail (13). The broad field of multicomponent systems is particularly troubled by nonequilibrium behavior. Polymerization thermodynamics relies on the properties of the monomers and does not have as many problems with nonequilibrium. 

Polymerization thermodynamics has been reviewed by Allen and Patrick, Ivin, " Ivin and Busfield, Sawada, and Busfield. In most radical polymerizations, the propagation... 

The ring-opening polymerization of is controUed by entropy, because thermodynamically all bonds in the monomer and polymer are approximately the same (21). The molar cycHzation equihbrium constants of dimethyl siloxane rings have been predicted by the Jacobson-Stockmayer theory (85). The ring—chain equihbrium for siloxane polymers has been studied in detail and is the subject of several reviews (82,83,86—89). The equihbrium constant of the formation of each cycHc is approximately equal to the equihbrium concentration of this cycHc, [(SiR O) Thus the total... 

Propagation reactions in radical polymerization and copolymerization arc generally highly exothermic and can be assumed to be irreversible. Exceptions to this general rule arc those involving monomers with low ceiling temperatures (Section 4.5.1). The thermodynamics of copolymerization has been reviewed by Sawada.85... 

AH values for various monomers. The AS values fall in a narrower range of values. The methods of evaluating AH and AS have been reviewed [Dainton and Ivin, 1950, 1958], These include direct calorimetric measurements of AH for the polymerization, determination by the difference between the heats of combustion of monomer and polymer, and measurements of the equilibrium constant for the polymerization. The overall thermodynamics of the polymerization of alkenes is quite favorable. The value of AG given by... 

This contribution will provide a review of polylectrolytes as biomaterials, with emphasis on recent developments. The first section will provide an overview of methods of synthesizing polyelectrolytes in the structures that are most commonly employed for biomedical applications linear polymers, crosslinked networks, and polymer grafts. In the remaining sections, the salient features of polyelectrolyte thermodynamics and the applications of polyelectrolytes for dental adhesives and restoratives, controlled release devices, polymeric drugs, prodrugs, or adjuvants, and biocompatibilizers will be discussed. These topics have been reviewed in the past, therefore previous reviews are cited and only the recent developments are considered here. 

The first basic approach to the thermodynamics of addition polymerization was presented in 1948 by Dainton and Ivin (7) and developed in their review paper (2) published ten years later. In their exposition, they stressed the significance of the propagation step in addition polymerization, emphasizing its critical role in the whole process. This is the step whereby the macromolecule is gradually formed by the sequence of reactions... 

Consider now a polymerization which is thermodynamically impossible at normal pressure because the reaction proceeds with a positive A H and a negative A S. However, at higher pressures, A H may become negative and the process would then be feasible. This and similar problems have been reviewed in a recent paper by Ivin (47), [see also the review by Weale (42)]. 

These polymerizations depend upon the ability to oxidize the monomer to a radical cation, whose further reactions lead to polymer. Since the oxidation potentials of the polymers are lower than those of the corresponding monomer, the polymer is simultaneously oxidized into a conducting state so that it is non-passivating. Some of the more important electrochemically-synthesised structures are discussed in more detail below and Chandler and Pletcher U4) have reviewed the electrochemical synthesis of conducting polymers. Detailed discussion in terms of thermodynamic parameters is impossible because the polymerizations are irreversible, so that E0 is undefined for the monomer-polymer equilibrium. 

In this chapter, subsequent to an introduction to devolatilization equipment, we review the thermodynamics of polymer solution equilibrium, which determines the maximum amount of volatiles that can be separated under a given set of processing conditions the phenomena associated with diffusion and diffusivity of small molecules in polymeric melts, which affects the rate of mass transfer the phenomena and mechanisms involving devolatilization and their modeling and the detailed and complex morphologies within the growing bubbles created during devolatilization of melts. 

Many reviews deal with the main mechanistic aspects of the metathesis reaction [10]. There are three basic metathesis reactions (apart from polymerization reactions) the ring-closing metathesis (RCM), the cross-metathesis (CM) and the ringopening metathesis (ROM) [11]. Among the fundamental aspects that govern the reaction course, the thermodynamic versus kinetic issue is particularly important when considering the application of RCM to the construction of macrocydes. 

The viewpoint sketched above has been so far developed and applied mainly in the context of mechanics and thermodynamics of complex fluids (Grmela, 2009 and references cited therein, also Section 3.1.6 of this review). The coupling between macroscopic (hydrodynamic) flow behavior and the behavior of a microstructure (e.g., macromolecules in polymeric fluids or suspended particles or membranes in various types in suspensions) is naturally expressed in the multiscale setting. In this review we shall include in illustrations also... 

In many instances in cationic ring-opening polymerization, all the reaction steps, however, are reversible. The final composition of copolymer (in equilibrium) is governed then by thermodynamics. Thermodynamic approaches have been developed [305] and recently reviewed [306]. Such thermodynamic approach has been used to analyze the copolymerization of pairs of cyclic acetals (1,3-dioxolane with 1,3-dioxepane and... 

Polymeric materials are not costabilizers in the sense that costabihzers cause superswelling. Rather, they slow the onset of Ostwald ripening and preserve the number of monomer droplets, if not their size. However, this review will take a functional, rather than thermodynamic definition of a costabilizer, and include a discussion of the use of polymers as agents to enhance droplet nuclea-tion under the heading of costabihzers. 

This review is concerned primarily with the distribution of cyclic species in polymeric systems where there are thermodynamic equilibria between ring and chain molecules. Such equilibria may be represented as follows... 

Some readers will be interested in the fact that Huang and Wang [75] in 1972 presented a newer theoretical treatment of the reaction kinetics of reversible polymerization in which this classic derivation of Dainton and Ivin is a special case. The thermodynamics of equilibrium polymerizations have recently been reviewed by Sawada [76]. 

Earlier investigations in our laboratory 56) have shown that several chain reaction polymerizations at temperatures below the melting or dissolution temperature of the final polymer lead to a thermodynamically more stable state than crystallization of the identical polymer from the polymer melt. Bawn and Ledwith mentioned in a review on stereoregular addition polymerization 57) that crystallization of the growing polymer chain might influence the polymerization step such that a more stereoregular polymer results. Ham 58—60) has finally pointed out a possible influence of the crystallization on the tacticity of the preceeding poljonerization which should only be possible when both processes are practically simultaneous. 

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