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protonates lactam and propagation continues. The sequence is the same as in Eqs. 7-52 and 7-53 except for the propagating chain possessing a carboxyl end group instead of lactam end group. Hydrolytic polymerization is simply a special case of cationic polymerization. [The commercial processes often add E-aminocaproic acid or the 1 : 1 ammonium carboxylate salt from a diamine and diacid (Eq. 2-128) along with water. This is a faster route to initiation as it supplies amine and carboxyl groups at the very beginning instead of waiting for hydrolysis of the lactam to supply those groups.] The overall rate of conversion of E-caprolactam to polymer is higher than the polymerization rate of E-aminocaproic acid by more than an order of magnitude [Hermans et al., 1958, 1960]. Step polymerization of E-aminocaproic acid with itself (Eq. 7-57) accounts for only a few percent of the total polymerization of E-caprolactam. Ring-opening polymerization (Eq. 7-58) is the overwhelming route for polymer formation. Polymerization is acidcatalyzed as indicated by the observations that amines and sodium E-aminocaproate are poor initiators in the absence of water and the polymerization rate in the presence of water is rst-order in lactam and second-order in COOH end groups [Majury, 1958]. Although step polymerization of E-aminocaproic acid with itself is only a minor contribution to the overall conversion of lactam to polymer, it does determine the nal degree of polymerization at equilibrium since the polymer undergoes self-condensation. The nal



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Nov 8, 2012 · PDF Focus.Net - How to convert PDF to Word using C#. SautinSoft.Duration: 4:17 Posted: Nov 8, 2012

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13 Jul 2015 ... Convert PDF to Word Using C# The first step will be to get the PdfBox package using the Nuget Package Manager. Now, import the following DLLs into your .cs file: The third step will be to install the DocX NuGet Package from the NuGet Package Manager: Let's read a PDF file and try to get the text from it.

degree of polymerization is dependent in large part on the equilibrium water concentration (Sec. 2-4). Most of the water used to initiate polymerization is removed after about 80 90% conversion in order to drive the system to high molecular weight. Molecular weight control at a desired level also requires control of the initial water and monomer concentrations (7-2b-5-c) and the addition of small but speci c amounts of a monofunctional acid (Sec. 2-6). The MWD is essentially the Flory most probable distribution except for the presence of monomer and cyclic oligomers. The nal product in the industrial polymerization of E-caprolactam contains about 8% monomer and 2% cyclic oligomer [DiSilvestro et al., 1987; Reimschuessel, 1977; Zimmerman, 1988]. About one-half of the cyclic fraction is the cyclic dimer with the remaining onehalf consisting mostly of the trimer and tetramer, although small amounts of cyclics up to the nonamer have been identi ed [Rothe, 1958; Zahn, 1957]. Cyclic oligomers are formed when any of the propagations discussed above occur intramolecularly (both for cationic and hydrolytic polymerizations). The monomer and cyclic oligomer are removed in the industrial production of poly(E-caprolactam) by extraction with hot water (or vacuum). The water content of the nal product is lowered to less than about 0.1% by vacuum drying at 100 200 C and about 1 torr pressure. Amidines are formed in hydrolytic polymerizations of lactams but do not limit the polymer molecular weight. Molecular weight buildup is not impeded since the carboxyl end groups of growing polymer are quite reactive toward amidine groups [Bertalan et al., 1984].

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e(t'-t)a e i(t'-t) w of3(t').

7-3c 7-3c-1

Now use that ~ : I<: to do the integral on the right-hand side above by the method of steepest descent and derive (7.105).

Strong bases such as alkali metals, metal hydrides, metal amides, metal alkoxides, and organometallic compounds initiate the polymerization of a lactam by forming the lactam anion XXXIV [Hashimoto, 2000; Sebenda, 1989; Sekiguchi, 1984], for example, for Ecaprolactam with a metal

7.2 Use the method of Heaviside's operational calculus described in 2 to show that with 1) given by (7.118), the particular solution of (7.116) is given by (7.119). 7.3 Do the integral in (7.77) explicitly by contour integration using the dielectric permittivity (7.122). 7.4 Using (7.98) and (7.124), calculate the commutator of E{v) with H mat Substitute the result in the left-hand side of (7.125). Substitute E{v) in the right-hand side of (7.125) by its expression in (7.124). You have now an equation of the form oo C1{v)E + Jo d11 C2 {v, 11)"Y{11) = O. Notice that if you take the commutator of both sides of this equation with Et, only the term proportional to E survives. Analogously, if y, u take the commutator of this equation with yt (11), only the term propo~ional to Y (11) survives. We can make an analogy between the set of operators {B, Y (11)} and a set of orthogonal vectors and between the commutator and the inner product oo of these vectors. In other words, C 1 (v)E + Jo d11 C2 {v,11)y{11) = 0 implies the equations C 1 {v) = 0 and C2 {v, 11) = O. Show that the latter equations are given by (7.128) and (7.129). 7.5 Assume that E can be expressed as a linear combination of the

1 H2 2

E(v),

There are advantages and disadvantages with almost any choice of base. The use of weaker bases produces a lower concentration of lactam anion unless the equilibrium is pushed to the right. The use of an alkali metal or metal hydride gives a high concentration of lactam anion, but side reactions contaminate the product with amines and water that destroy reactive initiating and propagating species. The use of most bases contaminates the system with the conjugate acid (BH) of the base, and this also destroys reactive species. The preferred method of initiation consists of preforming and purifying the lactam anion followed by addition to the reaction system.

dv C{v)B{v).

The lactam anion reacts with monomer in the second step of the initiation process by a ring-opening transamidation to form the primary amine anion XXXV. Species XXXV, unlike

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