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The most simple and commonly used nomenclature system is probably that based on the source of the polymer. This system is applicable primarily to polymers synthesized from a single monomer as in addition and ring-opening polymerizations. Such polymers are named by adding the name of the monomer onto the pre x poly without a space or hyphen. Thus the polymers from ethylene and acetaldehyde are named polyethylene and polyacetaldehyde, respectively. When the monomer has a substituted parent name or a multiworded name or an abnormally long name, parentheses are placed around its name following the pre x poly. The polymers from 3-methyl-1-pentene, vinyl chloride, propylene oxide, chlorotri uoroethylene, and E-caprolactam are named poly(3-methyl-1-pentene), poly(vinyl chloride), poly(propylene oxide), poly(chlorotri uoroethylene), and poly(E-caprolactam), respectively. Other examples are listed in Table 1-2. The parentheses are frequently omitted in common usage when naming polymers. Although this will often not present a problem, it is incorrect and in some cases the omission can lead to uncertainty as to the structure of the polymer named. Thus the use of polyethylene oxide instead of poly(ethylene oxide) can be ambiguous in denoting one of the following possible structures:



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where the contours C and o are shown in the Figure F.2. The two integrals in the middle line of (F.II) yield the principal part. The integral in last line yields lim





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Converting Image Files to PDF - CodeProject
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lost reactant. The amount of added reactant must be precisely calculated based on a chemical analysis of the r value for the reaction system as a function of conversion. Also the additional amount of the lost reactant must be added at the appropriate time. Premature addition or the addition of an incorrect amount results in performing the polymerization at other than the required stoichiometric ratio. There is a reaction condition in which high polymer molecular weights have been obtained independent of the stoichiometric ratio when one of the two monomers is only slightly soluble in the reaction mixture and is present in excess. An example is the reaction of bis(o-aminophenol) with terephthalic acid in polyphosphoric acid (Sec. 2-14h) [So, 2001]. Bis(o-aminophenol) is soluble but terephthalic acid is only slightly soluble in the reaction mixture. At any instant the polymer chain ends are those from the soluble monomer bis(oaminophenol), but these chain ends react quickly with the small amount of dissolved terephthalic acid, and then there is reaction again with bis(o-aminophenol). Polymerization proceeds to high molecular weight because there is a continuous dissolution of terephthalic acid to maintain its saturation concentration. On the other hand, high molecular weights are not achieved when the soluble monomer is present in excess. Similar results have been reported for the polymerization of terephthalic acid with ethylene glycol, p-dichlorobenzene with sodium sul de, and some aromatic diacid chlorides with aromatic diamines [Goodman, 1988; Liou and Hsiao, 2001a]. 2-6c Kinetics of Nonstoichiometric Polymerization

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0 lim i dO -+0+ 11" -i7rJ(O).

The kinetics of polymerizations involving nonstoichiometric amounts of A and B functional groups can be handled in a straightforward manner. Consider the external acid-catalyzed A plus B polymerization with r < 1. The polymerization rate, de ned as the rate of A B disappearance of the functional groups present in de cient amount, is given by

d A k A B dt 2-82

d (ee'8)

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The following stoichiometry holds:

. ee,8

A 0 A B 0 B 2-83

J (eei8 )

where A 0 and B 0 are the initial concentrations of A and B groups. Combination of Eqs. 2-82 and 2-83 followed by integration [Moore and Pearson, 1981] yields

(F.12)

! 1 A 0 B kt ln B 0 A 0 B 0 A 2-84

1 dx P- f(x) =

ln B ln r B 0 1 r kt A 2-85

1 f(x)

A plot of ln B = A versus t is linear with a positive slope of B 0 1 r k and an intercept of ln r. When r is close to unity the polymerization rate is adequately described by the expressions in Secs. 2-2a and 2-2b for the case of r 1. Only when r is considerably different from unity does it become necessary to use Eq. 2-85 or its equivalent. Most step polymerizations

are carried out with close to stoichiometric amounts of the two reacting functional groups. The main exceptions to this generalization are some of the reaction systems containing polyfunctional reactants (Secs. 2-10 and 2-12).

1 dx - f(x) }

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2-7 MOLECULAR WEIGHT DISTRIBUTION IN LINEAR POLYMERIZATION The product of a polymerization is a mixture of polymer molecules of different molecular weights. For theoretical and practical reasons it is of interest to discuss the distribution of molecular weights in a polymerization. The molecular weight distribution (MWD) has been derived by Flory by a statistical approach based on the concept of equal reactivity of functional groups [Flory, 1953; Howard, 1961; Peebles, 1971]. The derivation that follows is essentially that of Flory and applies equally to A and stoichiometric A plus B types B A B of step polymerizations. 2-7a Derivation of Size Distributions

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