Cryoscopic molecular weight determinations of the polymers was made by using a Beckmann thermometer and a Hershberg melting point apparatus. p-Xitrotoluene, ri1.p. 51.7", Kt 0.78, mas used as solvent. Catalytic hydrogenation of N,N-divinylaniline was performed in a volumetric microhydrogenation apparatus. Raney nickel, 10yo palladium-on-charcoal and platinum dioxide were all successfully used as catalyst. Either absolute ethanol or diglyme were used as solvent. The product isolated from catalytic hydrogenation of N,Ndivinylaniline formed a picrate salt as yellow needles, m.p. 140'. T h e melting point was identical to t h a t of diethylaniline picrate prepared in the same way (lit.13 142'). Mising the two picrates did not cause a lowering of the melting point. Attempted preparation of the picrate of S,S-diviiiylaniline by the same method gave only a brown resinous material melting over a range of 114' to 125'. Determination of residual double bonds in polymers and copolymers by catalytic hydrogenation was made according to the same general procedures as in the hydrogenation of the monomer. Diglyme was used as solvent in most cases on account of the solubility of the polymers. T h e polymers were introduced t o the solvent-catalyst mixture after the system had been allowed t o come to equilibrium either by dropping the preweighed sample from the sample container inside t h e vessel or by injecting into the system a measured quantity of the diglyme solution of the polymer. T h e latter method was necessary for many fluffy or powdery samples which could not be weighed properly in the sample
container. Uiglyrue was prepurified t o ireiiiovc peroxide and kept under a nitrogen atmosphere. In e:ich case the reaction was nlloived to run at least 18 lioui-u t o cusure completion of the reactioii. The infrared spectrum of S,S-divinyIaniline shu\wd t h e pertinent peak5 as s!iown in Table ST'II.
TABLE XVII INFRARED ABSORPTIOS BASDS Wave length, p
Intensiiy
3,30 6 . 03sh 6 . 10sh 6.20sh 6.28 6.69 7.08 7.30 7.42 7.62
n'eak Medium Strong 1'. strong Y.strong Strong Medium Medium Strong Strong Strong I-. strong
i.80
S . iKi
FOR
X,S-DIVISYLASII,ISE
XVnve length,
8.32 S.96 9.35 9.45 9.S0 10.22sh 10.37 10.62 12.30 13.10 14.35 14. si)
p
Intensity
1- 5t1ong n'eak Weak IVeak Wedk Mediuiii V.strong IX'eak V. strong Strong V strong Mediuni
T h e disappearance or diminishing of the strong shoulders in the 6.0 to 6.2 p region of the spectra clf polymers and copolymers leaving only n sharp band a t 6.25 p similar t o t h a t of diethylaniline K:LS used as a critcrioti lor the re(13) R. I . Shriner and I
