ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Derivatives of phosphonated polypropylene

Z. Maňásek, D. Belluš, and B. Böhmer

Slovak Academy of Sciences, Bratislava

Abstract: Atactic polypropylene (I) was chlorophosphonated with PCl₃ and O (Schroeder and Sopchak, CA 55, 12913h) to form a polymer (II) (0.17 mole P introduced per 100 g.), and the reactive POCl₂ groups were esterified to the extent of 70-85% by reaction with Na alcoholates. The Me and allyl esters that were prepd. have the same appearance as hydrolyzed II. The dodecyl esters possess good plasticity, and the di- and polyhydroxy compds. yield branched products of II with good thermomech. properties. By treating II with alcs., in the presence of tertiary amines for trapping the liberated HCl, products of a lower degree of esterification are obtained. Amidation of II to the extent of 90% yielded brittle derivs., insol. in org. solvents. By treating cellulose, previously wet with pyridine, with a 2% soln. of II in xylene for 48 hrs. at 30°, a stiff and impermeable deriv. was obtained after extn. of the excess II with Et₂O. Hydroxyethyl cellulose reacted in a similar way. It is presumed that a thin superficial layer of branched polymer is formed through the formation of phosphonate groups. Isotactic I (threads or film) was chlorophosphonated to form a polymer (III) by repeated immersions into PCl₃ followed by exposure to O, or alternatively by previously ozonizing I (0.22 mole O3/l. O at 21° for 4 hrs.), immersing it in PCl₃, and then exposing it at 60° in N. More intensive phosphonation resulted in the destruction of I (min. mech. stability preserved with 0.63% P). Hydrolyzed III has a greater capacity to adsorb moisture and dyes. Stabilizers, such as 2,2'-dihydroxy-4-methoxybenzophenone or 2,2'-methylenebis(4-methyl-6-tert-butyl)phenol, or their mixts., were fixed on I to form a polymer (IV) by treating III with a soln. of stabilizer and PhNEt₂ in xylene and then exposing for 1 hr. in N at 115°. Hydrolyzed III, and esp. IV, show, as compared to I, excellent stability towards O at 150°, as well as towards ultraviolet radiation, in regard to their mech. properties. Only extn. of IV for 10 hrs. with Me₂CO decreased its stability to any considerable extent.

Full paper in Portable Document Format: 175a318.pdf (in Slovak)

Chemical Papers 17 (5) 318–329 (1963)