Patent GB-971170-A (GB)
Title: Process for producing dimers and polymers of acetylenic compounds
IPC: C08F10/00
Filed: 1961-03-30
Abstract: Carbon is obtained by igniting a film of a polymeric, polyacetylenic compound obtained by oxidizing a compound containing at least two terminal acetylenic groups (-CC­H) (see Division C3).  In a preferred embodiment the polymer is derived from meta-diethynyl benzene; the polymer is dissolved in chlorobenzene, nitrobenzene or tetrachlorethane and cast on a glass plate and the solvent evaporated.  The film decomposes above 180 DEG  C. to leave a coherent carbon film.ALSO:Compounds containing two conjugated acetylenic linkages are obtained by reacting a compound containing a terminal acetylenic group (-C­CH) with oxygen in the presence of a solution of a cuprous salt-tertiary amine complex, said cuprous salt being one for which a corresponding cupric salt exists.  The acetylenic group may be attached to an aliphatic or aromatic radical which may contain as substituents, halogen, -OH, -OR, -OCOR, -COOR, -COR, -CONH2, -CONHR, -CONR2, -CH, -SH, -SR, -SSH, -SSR, -SOR, -NO2, -SO2R, -NH2, -NHR or -NR2 e.g. 5-fluoro-1-pentyne, 3-chloro-3-phenylpropyne, 3-bromopropyne, 3-chloro-1-butyne, ethynylpyridines, 3-butyne-1-ol, 2-propyne-1-ol, N-propynyl-aniline, propiolic acetate, propiolic amide, propiolophenone, 2-propynylamine, N,N-dimethylpropynylamine 2-propynyl sulphide, methyl-3-butynoate, 3-butyne-2-ol, 3-butyne-2-one, parabromophenylacetylene, nitrophenyl-acetylene and 1-ethynyl-cyclohexanol.  The cuprous salt is preferably the chloride but others are specified and many tertiary amines are specified including heterocyclic amines and di-tertiary amines; preferably N-aryl amines are not used.  Excess amine may be used to dissolve the complex and other solvents may be present, e.g. alcohols, ketones, hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether esters or sulphoxides.  Oxygen is bubbled into the mixture as such or diluted with nitrogen, helium or argon or as air. The reaction mixture is cooled if necessary to prevent the temperature rising above 100 DEG C. and the reaction is terminated by addition of an acid by pouring into a non-solvent for the product or by adding a copper chelating agent.ALSO:Polymeric polyacetylenic compounds are obtained by reacting acetylene or a compound containing two or more terminal acetylenic groups (-C==CH) with oxygen in the presence of a cuprous salt-tertiary amine complex, the cuprous salt being one for which a corresponding cupric salt exists. The products are linear polymers formed for example according to the equation: [-C==C-R-C==C-]n <FORM:0971170/C3/1> where n is usually at least 10 and probably at least 50. Compounds containing two terminal acetylenic groups are preferred, compounds with one such group being added as a chain stopper if required; compounds with three or more acetylenic groups yield three-dimensional, cross-linked, insoluble, infusible polymers. The radical to which the acetylenic groups are attached may be aliphatic or aromatic, hydrocarbon or substituted hydrocarbon, e.g. 1,4-pentadiyne, 1,5-hexadiyne, 1,6-heptadiyne, 1,7-octadiyne, 1,8-nonadiyne 1,11-dodecadiyne, o-, m-, or p-diethynyl benzene, or diethynyl naphthalenes, anthracenes, pyridines or pyrimidines. The polymers and copolymers obtained from m-diethynyl benzene are soluble in chlorobenzene, nitrobenzene, or tetrachloroethane above 100 DEG C. and can be cast, e.g. on glass, to produce tough transparent films stable up to 180 DEG C. The cuprous salt is preferably the chloride but others are specified and many tertiary amines are specified including heterocyclic amines and di-tertiary amines; preferably N-aryl amines are not used. Excess amine may be used to dissolve the complex and other solvents may be present, e.g. alcohols, ketones, hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether esters or sulphoxides. Oxygen is bubbled through the mixture as such or diluted with nitrogen, helium or argon or as air. The reaction mixture is cooled to prevent the temperature rising above 100 DEG C. and the reaction is terminated by adding an acid, by pouring into a non-solvent for the product or by adding a copper chelating agent.ALSO:Compounds containing two conjugated acetylenic linkages are obtained by reacting a compound containing a terminal acetylenic group (-C ­ CH) with oxygen in the presence of a solution of a cuprous salt-tertiary amine complex, said cuprous salt being one for which a corresponding cupric salt exists. The acetylenic group may be attached to an aliphatic or aromatic radical e.g. acetylene, propyne, 1-butyne, 3-methyl-1-butyne, 3-phenylpropyne, 1 - pentyne, 3 - ethyl - 3 - methyl - 1 - pentyne, 1 - dodecyne, 1 - octadecyne, phenylacetylene, ethynylnaphthalenes, ethynylanthracenes.  The cuprous salt is preferably the chloride but others are specified and many tertiary amines are specified including heterocyclic amines and di-tertiary amines; preferably N-aryl amines are not used.  Excess amine may be used to dissolve the complex and other solvents may be present, e.g. alcohols, ketones, hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether esters or sulphoxides. Oxygen is bubbled into the mixture as such or diluted with nitrogen, helium or argon or as air. The reaction mixture is cooled if necessary to prevent the temperature rising above 100 DEG C. and the reaction is terminated by addition of an acid by pouring into a non-solvent for the product or by adding a copper chelating agent.ALSO:Clear, tough coatings on glass are obtained by casting a solution of a polyacetylenic compound containing meta-diethynyl benzene groups with or without para-diethynyl benzene or diethynyl alkane groups, i.e. containing the recurring structure [-C­C-R-C­C-]n, and evaporating the solvent.  On heating above 180 DEG C. the film is converted to a coherent coating of carbon.