Polyamides via Chapman rearrangement
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 6, June, 2008
1251
N,NꢀDiphenylbenzamide (9) was synthesized by the rearrangeꢀ
ment of benzanyl imino ester under argon, the reaction time 13 h,
m.p. 179.5—179.8 °C (cf. data in Ref. 8: m.p. 179.6 °C).
the rate of the flow 0.3 mL min–1; the Maxima system was used
for the data processing, polystyrene standards were used for the calꢀ
ibration.
Starting PPID 4 and 5 were obtained in a threeꢀneck flask
50 mL) equipped with a stirrer, inlet and outlet for argon. Bispheꢀ
Film materials were obtained by the pouring of 18—20% soluꢀ
tions of a polymer in DMF on the glass support.
(
nol 1 (0.01 mol) and Nꢀmethylꢀ2ꢀpyrrolidone (20 mL) were placed
into it sequentially in the flow of argon, and the mixture was
homogenized. Then, triethylamine (0.02 mol) and imidoyl chloride
References
2
or 3 (0.01 mol) (see Ref. 1) were added with vigorous stirring.
1
2
3
. D. B. Sanzhizhapov, Yu. V. Tonevitskii, D. M. Mognonov, Yu.
E. Doroshenko, Zh. Prikl. Khim., 2003, 76, 642 [J. Appl. Chem.,
Int. Ed., 2003, 76, 642].
. L. V. Sokolov, V. D. Gerasimov, V. M. Savinov, V. K. Belyakov,
Termostoikie aromaticheskie poliamidy [Thermostable Aromatic
Polyamides], Khimiya, Moscow, 1975, 237 pp. (in Russian).
. V. F. Burdukovskii, D. M. Mognonov, S. R. Allayarov, S. O.
Botoeva, Zh. P. Mazurevskaya, Izv. Akad. Nauk, Ser. Khim.,
The homogenized reaction mixture was placed into the heating bath
and the temperature was raised to 170—180 °C. After 17—18 h,
the mixture was poured into 2% aqueous ammonia, a precipitate was
filtered off, gradually washed with 1% aq. sodium bisulfite and
water, and dried in a vacuum oven at 60—70 °C until the weight
is constant.
Polymers PAPA 6 and PBA 7 were synthesized by the rearꢀ
rangement of the corresponding PPID under argon at the temperaꢀ
tures and reaction times given in Table 1.
Polymers 6 and 7 were obtained also under argon by the
rearrangement of 10—15% solutions of the corresponding PPID
in DPE. The temperatures and reaction times are given in Table 1.
IR spectra were recorded on a Specord IRꢀ75 and Specord
URꢀ20 spectrophotometers in the range of wave numbers
2
004, 1703 [Russ. Chem. Bull., Int. Ed., 2004, 53, 1703].
4
5
. A. W. Chapman, J. Chem. Soc., 1927, 1743.
. B. Ya. Teitel´baum, Termomekhanicheskii analiz polimerov [Therꢀ
momechanical Analysis of Polymers], Nauka, Moscow, 1979,
2
36 pp. (in Russian).
6
. M. Hirooka, T. Kato, J. Polym. Sci. B, 1974, 12, 31.
000—400 cm–1. The samples were prepared in KBr pellets.
C NMR spectra were recorded on a Varian VXRꢀ500S specꢀ
7. F. G. Fabulyak, Moleculyarnaya podvizhnost´ polimerov v povꢀ
erkhnostnykh sloyakh [Molecular Lability of Polymers in
the Surface Layers], Naukova Dumka, Kiev, 1983, 144 pp.
4
1
3
trometer (400 MHz) in DMSOꢀd6 with the concentrations of
(in Russian).
1
0—15 wt %, Me Si was used as the internal standard.
4
8
. Svoistva organicheskikh soedinenii [Properties of Organic Comꢀ
pounds]. Handbook, Ed. A. A. Potekhin, Khimiya, Leningrad,
1984, 512 pp. (in Russian).
Dynamic thermogravimetric analysis was carried out on a МOМ
Qꢀ1000 derivatograph (Hungary) in air at the rate of heating
5
–1
deg min , Al O was used as the comparison substance. Thermoꢀ
2 3
mechanical analysis was performed on a Tsetlin apparatus at the
–1
constant load of 0.08 MPa and the rate of heating 100 deg h . Gel
permeation chromatography of polymers was carried out on a Waters
chromatograph with UꢀStyragel Linear as the column packing,
refractometer detector, THF was used as the solvent, Т = 20 °C,
Received September 14, 2007;
in revised form January 17, 2008