Introduction to Polymer Solutions

Science and Technology of Polymer Nanofibers. By Anthony L. Andrady Cop5fright 2008 John Wiley Sons, Inc. 

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This book offers a formal introduction to polymer solution theory. It contains many experimental data. 

The introduction of many fugacities is a source of complications which one would like to avoid. Thus, in order to apply field theory and renormalization principles to polymer solutions, des Cloizeaux used a simpler ensemble2 admitting that for long polymers, this ensemble has the same scaling properties as the exact grand canonical ensemble. 

FIGURE 2. Schematic representation of a flexible macroanion in solution. Reproduced by permission from F. A. Bovey and F. H. Winslow. Eds., Macromolecules, An Introduction to Polymer Science, Academic Press, New York, 1979. 

Detailed explanations on theoretical tools are given. Emphasis is on viscoelastic properties. The book contains a few chapters on dilute, semidilute, and concentrated solutions of rodlike molecules. The following is a simphfied version M. Doi, Introduction to Polymer Physics, Oxfor Univ. Press Clarendon, 1996. 

After an introduction to polymers as materials in the first two chapters, the mechanisms of polymerization and their effect on the engineering design of reactors are elucidated. The succeeding chapters consider polymer characterization, polymer thermodynamics, and the behavior of polymers as melts, solutions, and sohds both above and below the glass transition temperature. Also examined are crystallization, diffusion of and through polymers, and polymer processing. Each chapter can, for the most part, be... 

This concludes our discussion of the viscosity of polymer solutions per se, although various aspects of the viscous resistance to particle motion continue to appear in the remainder of the chapter. We began this chapter by discussing the intrinsic viscosity and the friction factor for rigid spheres. Now that we have developed the intrinsic viscosity well beyond that first introduction, we shall do the same (more or less) for the friction factor. We turn to this in the next section, considering the relationship between the friction factor and diffusion. 

Have compared intensity F, measured from the films prepared by introduction of an analyzed material to polymer in a various aggregative stations as a powder, a solution and a mix of a powder with a solution. The weight of an introduced material (in recalculation on superficial density P ) changed from 0,14 up to 0,43 mg/cm. Have established, that in some cases the value I, measured from films with a powder, it is essential ( 40 %) less the value I, measured from films with a solution, containing identical quantity of determined elements. By using of methods of a standard - background and internal standard this decrease is saved. 

A switching valve (low pressure) may be used to divert the eluent from the detector to the fraction collector as soon as the polymer is detected. Another switching valve can be used to select the polymer solution or the solvent for introduction into the pump. 

Teraoka, Iwao. Polymer Solutions An Introduction to Physical Properties. John Wiley Sons, 2002. 

Introduction of the reptation concept by De Gennes [43] led to further essential progress. Proceeding from the notion of a reptile-like motion of the polymer chains within a tube of fixed obstacles, De Gennes [43-45], Doi [46,47] and Edwards [48] were able to confirm Bueche s 3.4-power-law for polymer melts and concentrated polymer solution. This concept has the disadvantage that it is valid only for homogeneous solutions and no statements about flow behaviour at finite shear rates are analysed. 

The mass spectra of mixtures are often too complex to be interpreted unambiguously, thus favouring the separation of the components of mixtures before examination by mass spectrometry. Nevertheless, direct polymer/additive mixture analysis has been reported [22,23], which is greatly aided by tandem MS. Coupling of mass spectrometry and a flowing liquid stream involves vaporisation and solvent stripping before introduction of the solute into an ion source for gas-phase ionisation (Section 1.33.2). Widespread LC-MS interfaces are thermospray (TSP), continuous-flow fast atom bombardment (CF-FAB), electrospray (ESP), etc. Also, supercritical fluids have been linked to mass spectrometry (SFE-MS, SFC-MS). A mass spectrometer may have more than one inlet (total inlet systems). 

The book is divided into three sections. The first section provides a general overview of the fundamentals of supramolecular polymers. In Chapter 1, Thibault and Rotello provide a brief introduction to these systems and in Chapter 2, Azagarsamy, Krishnamoorthy, and Tha5mmanavan describe the rapidly emerging area of amphiphilicity in polymer and dendrimers self-assembly. Interactions at interfaces are sometimes similar but often quite different than those in solution, a topic covered by Loveless, Kersey, and Craig in Chapter 3. 

Barnes, H. A., Hutton, J. F., and Walters, K., An Introduction to Rheology, Elsevier, Amsterdam, Netherlands, 1989. (Undergraduate and graduate levels. A practical introduction to the rheology of suspensions and polymer solutions. Chapter 2 presents introductory concepts and measurement techniques at the undergraduate level. Effects of colloidal interactions are not described.)... 

To a solution of 40 g (1.0 moles) of sodium hydroxide in 500 ml of methanol was added 242 g (l.Omoles) of 2.6-dichloro-4-bromophenol. The pH was adjusted between 9.0 and 10.0 (preferably 9.5) by means of one or another of the reactants. The pH was determined by diluting a 2.5 g aliquot with 100 ml of 50% aqueous methanol. The alcohol and water were removed by distillation, fn a one liter round bottom flask there was introduced 100 g of the sodium salt of 2.6-dichloro-4-bromophenol, 350 ml of chlorobenzene and 40 ml of N,N-dimethylformamide. The mixture was agitated until the salt was in solution then immediately there was added 26 ml of dimethylsulfoxide. A suspension forms. The air was removed by alternate evacuation and introduction of nitrogen then there was added 1.0 g of benzoyl peroxide dissolved in 10 ml of toluene. The mixture was stirred for 80 min at 29—33° C then for 5 hours at 54—59° C. The formation of polymer was indicated by the disappearance of the particles of the suspension and an increase in the viscosity of the solution. The polymer was isolated by precipitation into acetone. After filtration the polymer was washed thoroughly with water, then with acetone and then dried at 100° C. There was obtained 60 g (theoretical) of poly-(2.6-dichloro-1.4-phenylene ether). 

Since this chapter is concerned with block copolymers in dilute solution, it is useful to include a definition of the dilute regime for polymer solutions in the Introduction. This regime extends up to a volume fraction above which swollen coils overlap (de Gennes 1979) ... 

T want to finish this introduction by a short sketch of the history of the subject. The physics of dilute polymer solutions by now has been ail active field for about TO years. Much of the early work is connected to the name of Flory and summarized in his classic books [Flo53, Fit>69], Up to about. 1970 much theoretical or experimental work concentrated on the behavior in the dilute limit, where via virial expansions the problem can be reduced to considering only a few interacting chains. The development led to the so-called two parameter theories , which essentially expand quantities like Rg or A2 in powers of z, In 1971 these developments were most carefully reviewed in a book by Yamakawa [Yam.71]. 

One of the major innovations in combinatorial and medicinal chemistry in recent years aiming at efficient diversity-oriented synthesis has been the implementation of polymer reagents in polymer-assisted solution phase (PASP) synthesis. This contribution will present—following an introduction to the field—a concept of advanced polymer reagents based on reactive intermediates and active reactants that should extend the scope PASP synthesis significantly. Experimental procedures describing preparation and use of the novel polymer reagents are included. 

Teraoka, I. Polymer Solutions. An Introduction to Physical Properties. Wiley Sons, Inc. New York, 2002. 

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