450 IONIC CHAIN POLYMERIZATION

double bond, carbonyl double bond, and the two double bonds in an alternating manner,
respectively [Pregaglia et al., 1963; Yamashita and Nunamoto, 1962]. Polymerization

CH3 C(CH3)2 CH3 C(CH3)2

C CO C O C CO O C
CH3 CH3
XLVII XLVIII XLIX

through the more polar carbonyl group to form the polyacetal is favored by solvents of
high polarity. Polymerization of the less polar alkene group, either completely to form the
polyketone or partially to form the polyester, is favored by nonpolar solvents. Polyketone
formation is favored by Li, Mg, and Al counterions, and polyester by Na and K.

5-7b Hydrogen-Transfer Polymerization of Acrylamide

The polymerization of acrylamide (or methacrylamide) by strong bases such as sodium, orga-
nolithium compounds, and alkoxides yields a polymer structure

nCH2 CH CO NH2 CH2 CH2 CO NH n ð5-135Þ

which is quite unexpected [Bush and Breslow, 1968; Camino et al., 1970, 1977; Otsu et al.,
1976]. The polyamide structure of the polymer has been confirmed by the hydrolysis of the
polymer to 3-aminopropanoic acid.
The polymerization mechanism involves addition of the anionic initiator to the carbon–
carbon double bond of the monomer

B– + CH2 CHCONH2 BCH2 CHCONH2 ð5-136Þ

followed by proton abstraction from another monomer molecule to form the amide anion (L)

BCH2 CHCONH2 + CH2 CHCONH2

BCH2CH2CONH2 + CH2 CHCONH ð5-137Þ

L

The amide anion initiates polymerization via a similar reaction sequence by addition of L to
monomer. Propagation follows in a like manner:

CH2 CHCONH CH2CH2CONH n

H + CH2 CHCONH
LI
monomer
CH2 CHCONH CH2 CHCONH CH2CH2CONH n
H

CH2 CHCONH CH2CH2CONH H + CH2 CHCONH ð5-138Þ

(n + 1)

This polymerization follows a path that is quite different than any of the previously discussed
polymerizations. The propagating center is not an ion or a radical but is the carbon–carbon
double bond at one end of the propagating species LI. In addition, it is not the monomer but
 MISCELLANEOUS POLYMERIZATIONS 451

the monomer anion L that adds to the propagating center. The evidence for this polymeriza-
tion mechanism comes from analysis for the alkene end group. This mechanism is very simi-
lar to that for the anionic ring-opening polymerization of cyclic amides (Sec. 7-3c). By
analogy to the latter, the monomer anion can be referred to as activated monomer. The over-
all polymerization reaction is often referred to as a hydrogen-transfer polymerization.
Polymerization of acrylamide does not proceed entirely through the hydrogen-transfer
route under all reaction conditions. Polymers with mixed structures, resulting from concur-
rent hydrogen-transfer polymerization and normal polymerization through the carbon–
carbon double bond, occur in some cases. The relative extents of the two modes of propaga-
tion are affected by the initiator, solvent, monomer concentration, and temperature [Imanishi,
1989]. The polymerization of N,N-dimethylacrylamide proceeds exclusively through the
carbon–carbon double bond because there are no amide hydrogens for transfer [Kobayashi
et al., 2000; Nakhmanovich et al., 2001].

5-7c Polymerization and Cyclotrimerization of Isocryanates

Isocyanates are polymerized through the carbon–nitrogen double bond to 1-nylons by anionic
initiators such as metal alkyls, sodium naphthalene, and sodium cyanide [Bur and Fetters,

R
nR N C O N CO ð5-139Þ
n

1976; Dabi and Zilka, 1980; Eromosele and Pepper, 1987; Kresta et al., 1979]. The polymer-
ization has a low ceiling temperature and cyclotrimerization to the isocyanurate is the major
reaction at ambient temperatures and above.

5-7d Monomers with Triple Bonds

Alkynes have been polymerized using ionic and radical initiators, but the polymer molecular
weights are low. High molecular weights are obtained by using Ziegler–Natta coordination
catalysts (Sec. 8-4d-2) [Chien et al., 1980]. The polymers are of considerable interest in
terms of their potential as (semi)conducting materials.

R
nRC CH C CH ð5-140Þ
n

Nitriles have been polymerized by radical and ionic initiators. The polymer structures are
often quite complex, although anionic polymerization yields the cleanest reaction [Wohrle,
1972, 1983; Wohrle and Knothe, 1988].

R
nRC N C N ð5-141Þ
n

Polymerization of isocyanides to polyiminomethylenes is best achieved with cationic

initiators, although anionic and radical polymerizations also occur [Millich, 1988].

NR
R NC C ð5-142Þ
n