Patent GB-855199-A (GB)
Title: Monoepoxide of cyclopentadienes, their derivatives and processes for the preparation
IPC: C07D303/04
Filed: 1957-06-17
Abstract: The invention comprises (i) polyether homopolymers of cyclopentadiene monoepoxide or alkyl derivatives thereof containing 1-4 carbon atoms in the alkyl group; (ii) copolymers of the cyclopentadiene monoepoxides with another epoxide; (iii) resinous polyesters of the cyclopentadiene monoepoxides or the 3, 4- or 3, 5-cyclopentene diols obtained therefrom by hydrolysis, with a dibasic acid or anhydride, with or without another glycol, and their preparation by reaction of the components; (iv) polymers of the polyesters in (iii) above, and their preparation by reacting the polyester with an organic peroxide in the presence of an ethylenically unsaturated compound; (v) a method of preparing a polymer by reacting a polyester as in (iii) above with sulphur or sulphur chloride; (vi) a resinous condensation product of a di- or poly-isocyanate with a polyester as in (iii) above, and its preparation by reaction of the components; and (vii) a mixed resinous polyester of a dicarboxylic acid, a saturated dihydric alcohol, and the aforesaid 3, 4- or 3, 5-cyclopentene diols. Specified epoxides for preparing copolymers as in (ii) above are ethylene, 1, 2-propylene, butylene and styrene oxides, butadiene monoxide, allyl 2, 3-epoxybutyrate and glycidol and its methyl and allyl ethers; specified dibasic acids and anhydrides for preparing polyesters as in (iii) above are phthalic, adipic, succinic, azelaic, malonic, tartaric, itaconic, maleic and fumaric acids, and phthalic and maleic anhydrides; specified ethylenically unsaturated compounds for use in (iv) above are styrene, vinyl acetate, methyl methacrylate, methyl acrylate, and diallyl phthalate and maleate and ethylene glycol bis(diallyl carbonate) and the corresponding methallyl esters; specified isocyanates for (vi) above are 4, 41-diphenyl di-isocyanate, toluene diisocyanate, 1, 5-naphthalene di-isocyanate and toluidene di-isocyanate; specified dihydric alcohols for (vii) above are alkylene glycols and polyglycols, styrene glycol, and phthalyl alcohol.  In other reactions mentioned, ether-alcohols are prepared by reacting cyclopentadiene monoepoxide with polyhydric alcohols such as polyvinyl alcohol, "Cellophane" (Registered Trade Mark), starch, alkylene glycols, glycerine, ethyl tartrate, and solid high molecular weight polyethylene oxides (M.W. > 1000). The products may be used as plasticizers or modifying agents in the production of resins and synthetic rubbers.  Specifications 735,974, 754,359 and 756,857 are referred to.ALSO:The invention comprises the monoepoxides of cyclopentadiene and alkyl substituted derivatives thereof containing 1-4 carbon atoms in the alkyl group, and their preparation by reacting the corresponding cyclopentadienes in a liquid medium with a peracid of a weak carboxylic acid of pK at least 0,5 while maintaining the reaction mixture substantially free from water in the liquid state and also essentially free from carboxylic acids by means of a sufficient amount of an alkali which does not produce hydroxyl ions (such as an alkaline-reacting salt) or of magnesium hydroxide or oxide, which consume the carboxylic acid as rapidly as it is formed.  The peracid may be formed in situ, and may be used as the aliphatic aldehyde peracylate, the aldehydic portion containing up to 6 carbon atoms.  The epoxides of the invention react with water to produce cyclopentene -3, 4- or -3, 5-diols; with alcohols and phenols to produce hydroxycyclopentenyl ethers and (in the case of polyhydric alcohols) polyethers; with acid chlorides, phosgene or chloroformates to produce the chlorocyclopentenyl derivatives; and with amines and amides to produce the N- hydroxycyclopentenyl compounds; examples of these classes of reactants include saturated and unsaturated aliphatic monohydric alcohols, phenols and substituted phenols; alkylene glycols and polyglycols, styrene glycol, erythrol, phthalyl alcohol, sugar, and polyhydric phenols; acyl chlorides, including phthalyl and oxalyl chlorides; ammonia, alkylamines, arylamines, alkylene and arylene diamines, melamine, ammeline, ammelide and cyanamide (mono, di and tri-cyclopentenolamines may be prepared); alkyl chloroformates, allyl, phenyl cinnamyl, resorcinol, 2-nitroethyl, cholesteryl chloroformates, and ethylene glycol and diethylene glycol bis-chloroformates.  The epoxides of the invention may be polymerized (see Group IV(a)).  Specifications 735,974, 754,359 and 756,857 are referred to.