Patent GB-758728-A (GB)
Title: A process for manufacturing synthetic resins from epoxide compounds
IPC: C08G59/42
Filed: 1953-11-02
Abstract: Epoxy compounds containing the grouping <FORM:0758728/IV(a)/1> and also containing at least two epoxy groups each of which is linked to adjacent carbon atoms of a cyclohexyl ring are heated with a polycarboxylic acid or anhydride or chloride thereof, preferably with the addition of an aliphatic epoxide compound. The epoxycyclohexane compounds are made by hydrogenating, dehydrating and epoxidizing the corresponding aromatic hydroxy compounds, e.g. dihydroxydiphenyl, diphenylolpropane or phenol-aldehyde condensates, e.g. novolacs. Hydrogenation and dehydration may be effected as described in German Specification 864,300.  Preferred epoxycyclohexane compounds are: I <FORM:0758728/IV(a)/2> obtained from diphenylol propane; II <FORM:0758728/IV(a)/3> (where n = 0-8) obtained from a phenolformaldehyde condensate. A compound III <FORM:0758728/IV(a)/4> (where m = 0-3) is obtained as a by-product in the splitting-off of water from the perhydrodiphenylolpropane intermediate obtained in producing compound I above, and the cyclohexene rings in this compound may be epoxidized to yield other suitable compounds for the invention.  Preferred aliphatic epoxide compounds for use in admixture with the cyclohexane compounds are epoxidized linseed oil, sperm oil, unsaturated fatty acids or alcohols, unstaturated esters. Suitable polycarboxylic acids for use in the invention are maleic, succinic, adipic, sebacic, phthalic, isoor tere-phthalic, or their hydrogenation products.  They may be used as anhydrides or chlorides. The products are particularly suitable as casting resins, adhesives or in solution as lacquers. Fillers may be incorporated, e.g. glass fibres, glass powder, metal powder, colouring materials, ceramic materials or inorganic oxides.  In Example (1) perhydrodiphenylolpropane is dehydrated, producing a soft resinous residue and a distillate which is a mixture of isomeric dicyclohexenylpropane which is then epoxidized.  The product includes a main fraction with 11 per cent epoxide oxygen, a final fraction with 10 per cent, and a residue with 4 per cent which is a brittle yellowish resin.  The main fraction is employed in examples: (3) with epoxidized linseed oil and phthalic acid; (4) with epoxidized linseed oil and adipic acid; (5) with an epoxide obtained from glycerine, epichlorhydrin and stannic chloride, together with phthalic or adipic anhydride; (6) with the diepoxide of dioleylphthalate and phthalic or adipic anhydride; (9) with diepoxidized dioleylphthalate, phthalic anhydride and crushed glass wool; (11) with linseed oil epoxide, phthalic and adipic acid anhydrides in acetone solution.  In several of the examples the resins are used for gluing metals, e.g. aluminium or duralumin together.  Example (8) uses the final fraction of Example (1) together with epoxidized oleyl alcohol and phthalic or maleic acid anhydride.  In Example (2) a phenol formaldehyde novolac is hydrogenated, dehydrated and epoxidized. The product is hardened in Example (7) with linseed oil epoxide and phthalic or adipic acid anhydride.ALSO:Compounds containing the grouping <FORM:0758728/IV(a)/1> and also at least two epoxide oxygen atoms each linked to two adjacent carbon atoms of a different cyclohexane ring are produced from the corresponding aromatic hydroxy compounds by hydrogenation, dehydration and epoxidation.  Suitable aromatic hydroxy starting materials are dihydroxydiphenyl, diphenylolpropane or phenolformaldehyde condensates.  These may be hydrogenated and dehydrated by the method of German Specification 864,300. Peroxidation is preferably effected with a paraboxylic acid or, if desired, by addition of hypochlorous acid followed by elimination of HCl.  In Example (1), diphenylolpropane is perhydrogenated to a crystalline product (M.P. 181-182 DEG  C.) which is heated while stirring with b -naphthalene sulphonic acid and a dehydration mixture made by mixing potassium bisulphate and dry sand.  The residue is saturated with ether, washed, dried and distilled in vacuo.  The main fraction (mixed isomeric dicyclohexenyl propanes) boils at 98-111 DEG C. at 1.8 mms. Hg.  A soft stringy resinous residue remains.  The main fraction is oxidized with 61 per cent peracetic acid (in acetic acid) in ethereal solution.  The raw epoxide, distilled in vacuo, yields a fraction boiling at 120-135 DEG  C. at 2.3-2.5 mms. Hg and having 2.7 per cent epoxide oxygen, a fraction boiling at 140-160 DEG C. at 0.8-1.2 mms. Hg with 11 per cent epoxide oxygen, and a fraction boiling at 160-165 DEG  C. at 1 mm. Hg with 10 per cent epoxide oxygen.  A yellowish resinous residue with 4 per cent epoxide oxygen remains.  In Example (2) a hydrogenated novolac is dehydrated with phosphorus pentoxide as described in German Specification 864,300, dissolved in ether and oxidized with peracetic acid.  The physical properties of the product are mentioned.  The products are used (see Group IV (a)) together with mono- or polyepoxy compounds obtained by peroxidation of unsaturated compounds, e.g. linseed oil, sperm oil, esters of unsaturated alcohols with polybasic carboxylic acids such as esters of allyl or oleyl alcohol with phthalic, pyromillitic, succinic, adipic or sebacic acid.  Such compounds may also be prepared by reacting epichlorhydrin with the salts of such acids.