GB1178308A - Improvements in or relating to Method of Modifying Unsaturated Polymers with Carbon Monoxide and Products thus Obtained. - Google Patents

Abstract

1,178,308. Treating unsaturated polymers with carbon monoxide. SOC. AUXILIAIRE DE L'INSTITUT FRANCAIS DU CAOUTCHOUC. 16 May, 1967 [17 May, 1966], No. 22655/67. Headings C3E and C3P. An unsaturated polymer is modified by reacting a mixture of the polymer and a solvent for CO with CO, if desired associated with another reagent, in the absence of oxygen and, if desired, in the presence of a catalyst, the CO being introduced into the said mixture kept at a temperature of from- 80‹ C. to 10‹ C. to promote its dissolution and the reaction mixture thus obtained being subsequently heated to a temperature of from 0‹ to 240‹ C. under a pressure of 1 to 100 atmospheres to produce the desired reaction. The polymer may be a natural or synthetic rubber. In one embodiment A, an ethylenically unsaturated polymer is reacted with CO under pressure in the presence of water, a monocarboxylic acid, an alkanol or phenol, ammonia, an alkyl or aryl amine or a thiol, and an organometallic catalyst. An unsaturated polymer containing aromatic nuclei is reacted in embodiment B with a mixture of CO and HCI, or a compound yielding such a mixture. In embodiments C and D an ethylenically unsaturated polymer is reacted with CO, without any co-reagent, in the presence of a free radical catalyst, an ionic catalyst, an acid or a mineral salt. In examples, the following reaction mixtures are treated with CO: natural rubber, CHCl 3 , AlCl 3 -CH 3 NO 2 , the resulting polymer being heated in xylene in the presence of benzidine; polyisoprene, toluene and PdCI 2 ; rubber, toluene, water and a NaCl-AlCl 3 eutectic mixture, the modified rubber being heated in the presence of ethylene glycol and H 2 S0 4 ; polyisoprene, toluene and BF 3 -acetic anhydride complex; 1,4-cis-polybutadiene, 1,4- trans - polychloroprene or an isobutylene - isoprene rubber, chlorobenzene, water and AlCl 3 - CH 3 NO 2 complex; natural rubber, chlorobenzene and paramenthane hydroperoxide, ditertiary butyl peroxide, chlorobromodimethylhydantoin or benzoyl peroxide; natural rubber, toluene, acetic anhydride and cobalt naphthenate; rubber, chlorobenzene and cobalt naphthenate, the reaction mixture being saturated with H 2 5 prior to the reaction with CO; rubber, chlorobenzene, cobalt naphthenate and water; rubber, CCl 4 and AgNO 3 ; natural rubber latex or polybutadiene latex, the CO being generated in situ by reaction of sodium formate and H 2 50 4 and the modified polybutadiene being treated with HC1; butadiene-styrene rubber, cyclohexane, AlC1 3 and OuCi 2 , the mixture being treated with a CO + HCl mixture and the modified copolymer being treated with potash or oxidized.