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where R is the first layer of adjustable parameters or weights in the MLP model. Then the function (termed the activation function of the network) is applied to each element of y. In the diagrammatic representation of the MLP (Figure 2.1), this is applied separately a t each unit in the hidden and output layers (the circles represent the computational units where this is done). However, in the algebraic representation, we consider f~ a mapping from to each of its coordinates. to ( 0 , l ) that applies the same one-variable function, The resulting vector f ~ ( y is then augmented by the addition of a 1 so that )

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7-88

Goethals, 1989a,b; Kobayashi and Saegusa, 1984, 1986; Kobayashi and Uyama, 2002; Kobayashi et al., 1990a,b; Kubisa, 1996; Tomalia and Killat, 1985]. Propagation proceeds via nucleophilic attack of monomer on the C bond of an oxazolinium ion: O

7-89

(just as the original data vector was augmented). This now forms the data input to the next and, in this case final, layer of the network. So we have

LI can be hydrolyzed to the corresponding polyamine LII. This is the only route to linear polyethyleneimine (m 2) [Tanaka et al., 1983]. The polymerization of ethyleneimine yields a highly branched and cyclized product. exo-Imino cyclic compounds (LIII) such as iminocarbonates (Y O), 2-imino-1,3-oxzolidines (Y NR), and 2-iminotetrahydrofurans (Y CH2 ) have also been polymerized:

7-90

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An alternate approach to forming polymers by ring opening of 2-oxazolines involves the 2-mercaptoalkyl-2-oxazoline LIV, which polymerizes to LVII on heating [Gunatillake

and mlp(l) = Z = fQ(z) = f Q ( T [ l ,

et al., 1987] (Eq. 7-91). The reaction occurs through the zwitterion intermediate LV formed by proton transfer from sulfur to nitrogen. This reaction is a step polymerization of the zwitterion (an AB reactant). The zwitterion reacts with itself through nucleophilic attack of S on

7-91

the oxazolinium ring to break the C bond and form a propagating zwitterion (LVI). Pro O pagation continues in the same way to form the polymer LVII. 2-Carboxyalkyl-2-oxazolines polymerize in a similar manner with nucleophilic attack of carboxylate anion on the oxazolinium ring [Gunatillake et al., 1988].

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(2.1)

7-7 SULFUR HETEROCYCLICS The 3- and 4-membered cyclic sul des, referred to as thiiranes (also episul des) and thietanes, respectively, are easily polymerized by both cationic and anionic initiators, such as

7-92

the polymerization of ethylene sul de to poly(ethylene sul de) [IUPAC: poly(sulfanediylethylene)] [Aida et al., 1990; Boileau, 1989; Boucard et al., 2001; Goethals, 1989a,b; Kubisa, 1996; Sigwalt and Spassky, 1984]. Polymerization is more facile than with the corresponding cyclic ethers because of the more polarizable carbon sulfur bond. This also explains the polymerization of the thietanes by anionic initiators. However, cyclic sul des are less strained than their oxygen analogs because of the larger size of the sulfur atom, and the 5-membered ring tholane (tetrahydrothiophene), unlike tetrahydrofuran, does not undergo polymerization. There are no reported polymerizations of larger-sized cyclic sul des. By analogy to the cyclic ethers, the propagating species in cyclic sul de polymerization are considered to be the cyclic sulfonium (LVIII) and sul de anion (LIX) for cationic and anionic polymerization, respectively.

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