SynopsisSoluble chloromethylated polystyrene and its copolymers with vinylidene chloride as well as poly(pheny1 oxides) brominated in the side chains and in the ring were synthesized and characterized in detail by NMR. The halogenated polymers were phosphonylated with alkyl phosphites. Uncrosslinked polymers with pendent phosphonate groups were prepared in the presence of etheral solvents, which solvate the ionic intermediates of the Arbuzov reaction. These polyphosphonates are highly hygroscopic and are soluble in a variety of solvents. Their 2';s are in the range of 50-175OC. Their thermal behavior was analyzed on the basis of thermogravimetric measurements combined with mass-spectrometric analysis. Poly(styrene phosphonate) seems to be the most stable, and its thermal decomposition starts at -330°C. The polymeric phosphonates are compatible with an unusually large number of polymeric systems and seem to form "true" polymeric alloys with acetylcellulose.

Molar ratio olefin : sulphonyl chloride. Notes: (1) Reaction under reflux. (2) Catalyst dissolved in acrylonitrile. (3) See Experimental Calculated on sulphonyl chloride charged. section. (4) Yield calculated on converted sulphonyl chloride : 05 yo.

SynopsisThe anionic polymerization of 1.3-cyclohexadiene (1.3-CHD) was investigated in temperatures that ranged from 25 to -77OC. Initiation by lithium naphthalene (N;,Li+) in tetrahydrofuran at -2OOC yields polymers with fairly narrow molecular weight distribution. The of t.hese polymers so prepared is ca. 20,000. Polymerization of 1.3-CHD conducted a t room temperature is accompanied by the dehydrogenation and disproportionation of the monomer, especially when NT,K+ acts as initiator.The mechanism of the initiation of the polymerization of 1.3-CHD by N:,Li+ was elucidated and the rate constants at -2OOC in tetrahydrofuran of the elementary reactions were determined. It was established that the dianions formed by disproportionation of N;,Li+ act as effective initiators for 1.3-CHD. The adducts formed constitute the cyclohexanyl and naphthyl carbanionic groups. The former carbanions ( A , , ,-275 nm) propagate the polymerization. The initially formed dimeric adducts are stabilized by the separation of the carbanionic end groups by the additional monomer units. Chain transfer to the monomer limits the growth of the polymers. The isomerization of the cyclohexadienyl anions, formed as result of chain transfer, may be followed by the elimination of lithium hydride. The latter reaction represents a termination step. Addition of 1.4-CHD to the reaction mixture enhances the chain transfer and the termination.Oligomers are formed when hexamethylphosphoramide is used as a solvent.

Carbon tetrachloride is added to olefins and vinylic monomers under the catalytic influence of iron (11, 111) or copper (1, 11) chloride, in a variety of solvents at 70-145'.Copper chloride completely suppresses telomerization. A free-radical chain mechanism is proposed for the addition] in which metal chloride participates in the propagation as a chlorine-atom transfer agent, thereby much enhancing the apparent reactivity of carbon tetrachloride (" redox-transfer 'I). Experimental support for this mechanism is presented. The reaction with but-2-ene gives a mixture of diastereoisomeric adducts, the composition of which changes with catalyst] and, for copper-catalysis, also with the solvent and with the excess of chloride ion. cis-and trans-But-2-ene give the same ratio of diastereoisomers.The initiation mechanism is discussed. At 82", ferric chloride induces addition of carbon tetrachloride to but-2-ene only in the presence of a reducing agent. This enables one to estimate the kinetic chain-length, which has a much larger value than for a peroxide-induced reaction.

SynopsisThe solubility of benzene in the polymeric alloys (P/A) consisting of polyphosphonates (PPN) and acetyl cellulose (AC) is nearly two orders of magnitude larger than that of cyclohexane. The preferential absorption of benzene by P/A membranes is also maintained upon its dilution with cyclohexane, though the solubility of the latter in the P/A membranes is affected by their swelling with benzene. Absolute values of solubilities increase exponentially with increase in the weight fraction of PPN in P/A membranes. They are also affected by the thermal and solvent "history" of a membrane. For the sorption of benzene by a P/A-50 membraneThe diffusion coefficients of benzene in the solvent-swollen membranes are strongly concentration dependent and increase exponentially up to -10-cm2/sec with the increase in the volume fraction of benzene. Values of Do are of the order of 10-1' to 10-10 cm2/ sec. Sorption experiments indicate a pronounced time dependence of the diffusion coefficients. Self-diffusion experiments conducted with 14Glabeled benzene revealed that values of D* derived from the steady-state permeation measurements are in certain membranes much larger than those derived from the "time-lag." It was observed that the discrepancies between the two sets of values depend strongly upon the thermal "history" of the membranes and vanish when the membranes are swollen to a high degree a t elevated temperatures. The above phenomenon is discussed in terms of differences in the membrane structure; a model is propded. The apparent energy of activation of diffusion of benzene at 10-40"C in the swollen P/A-50 membrane E B~ = 14.4 kcal/mole was derived from the temperature dependence of the self-diffusion coefficients. For the same temperature range a t C(B) 4 0, EeDO = 8.3 kcal/mole was derived from the final slopes of the desorption curves. The small difference between the energies of activation in a swollen and in an unswollen system is due to the fact that a t room temperature it remains below T, even upon extensive swelling with benzene.