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Several considerations are common to all processes for step polymerizations in order to achieve high molecular weights. One needs to employ a reaction with an absence or at least a minimum of side reactions, which would limit high conversions. Polymerizations are carried out at high concentrations to minimize cyclization and maximize the reaction rate. Highpurity reactants in stoichiometric or near-stoichiometric amounts are required. The molecular weight is controlled by the presence of controlled amounts of monofunctional reagents or an excess of one of the bifunctional reagents. Equilibrium considerations are also of prime importance. Since many step polymerizations are equilibrium reactions, appropriate means must be employed to displace the equilibrium in the direction of the polymer product. Distillation of water or other small molecule products from the reaction mixture by suitable reaction temperatures and reduced pressures are often employed for this purpose. Table 2-8 shows values of some kinetic and thermodynamic characteristics of typical step polymerizatiosn [Bekhli et al., 1967; Chelnokova et al., 1949; Fukumoto, 1956; Hamann et al., 1968; Malhotra and Avinash, 1975, 1976; Ravens and Ward, 1961; Saunders and Dobinson, 1976; Stevenson, 1969; Ueberreiter and Engel, 1977]. These data have implications on the temperature at which polymerization is carried out. Most step polymerizations vb.net merge pdf files Merge PDF files from C# / VB.NET applications - GemBox
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Jan 22, 2019 · Merge Multiple PDF Files Into Single PDF Using Itextsharp in C# .... for final year students in Asp.Net, MVC, C#, Vb.Net, SQL Server, Angular Js, ... Uncatalyzed unless otherwise noted. 1 cal 4.184 J. Acid-catalyzed. d Catalyzed by Sb2O3. e k1 value. f k2 value. g Average k for all functional groups. h Base-catalyzed. proceed at relatively slow rates at ordinary temperatures High temperatures in the range of 150 200 C and higher are frequently used to obtain reasonable polymerization rates Table 2-8 shows that the rate constants are not large even at these temperatures Typical rate constants are of the order of 10 3 L mol 1 s 1 There are a few exceptions of step polymerizations with signi cantly larger k values, for example, the polymerization reaction between acid halides and alcohols The need to use higher temperatures can present several problems, including loss of one or the other reactant by degradation or volatilization Oxidative degradation of polymer is also a potential problem in some cases The use of an inert atmosphere (N2, CO2) can minimize oxidative degradation. THE UNITED STATES IN THE TWENTIETH CENTURY: 1946 1990 Bulk or mass polymerizations is the simplest process for step polymerizations, since it involves only the reactants and whatever catalyst, if any, which is required [Menikheim, 1988] There is a minimum of potentialities for contamination, and product separation is simple Bulk polymerization is particularly well suited for step polymerization because high-molecular-weight polymer is not produced until the very last stages of reaction This means that the viscosity is relatively low throughout most of the course of the polymerization and mixing of the reaction mixture is not overly dif cult Thermal control is also relatively easy, since the typicaly reaction has both a modest activation energy Ea and enthalpy of polymerization H Although some step polymerizations have moderately high activation energies, for example, 1004 kJ mol 1 for the polymerization of sebacic acid and hexamethylene diamine (Table 2-8), the H is still only modestly exothermic. The exact opposite is the case for chain polymerizations, which are generally highly exothermic with high activation energies and where the viscosity increases much more rapidly Thermal control and mixing present much greater problems in chain polymerizations Bulk polymerization is widely used for step polymerizations Many polymerizations, however, are carried out in solution with a solvent present to solubilize the reactants, or to allow higher reaction temperatures to be employed, or as a convenience in moderating the reaction and acting as a carrier 2-8b Different Reactant Systems. vb.net itextsharp merge pdf files Auto merge 2 PDF file to 1 PDF | The ASP.NET Forums
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