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

摘要

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.