| 摘要 |
<p>Polyether compounds are made by condensing an unsaturated polyhydroxy compound or its ether of the general formula: <FORM:0877913/IV (a)/1> where R1 is a hydrogen atom or an alkyl or aromatic radical, R2 is an aliphatic, cycloaliphatic or aromatic radical, R3 is an aromatic radical or an a , b -unsaturated aliphatic residue and X is an integer of from 2-6 with a different dihydric or polyhydric aliphatic, cycloaliphatic or aromatic alcohol in the presence of an acid catalyst. Specified catalysts are p-toluene sulphonic acid, p-toluene sulphonic acid esters, benzene sulphonic acid, benzene sulphonic acid esters, phosphoric acids and esters thereof and acidic montmorillonites. Reaction solvents, e.g. methyl naphthylene, decalin or diphenyl ether may be used in the condensation. Specified unsaturated polyhydroxy compounds are the degradation products of condensation products of formaldehyde with aromatic hydrocarbons, p-xylene glycol, o-xylylene glycol, 1, 3, 4-trimethylol benzene, 1, 3-dimethyl-4, 6-xylylene glycol, 1, 5-bis-hydroxy methyl naphthalene, 4, 41-bis-hydroxy methyl diphenyl ether, 1, 4-bis-hydroxy methyl thiophene and heptadiene (2, 5)-di-1, 7-ol and the methyl, ethyl, propyl or allyl ethers thereof. Specified dihydric and polyhydric aliphatic, cycloaliphatic or aromatic alcohols are diethylene glycol, triethylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, pentachlorophenyl glycerine ether, trimethylol propane, glycerine, pentaerythritol, the di-b -hydroxyethyl ethers of 4, 41-dihydroxydiphenyl dimethyl methane, of 1,5-dihydroxy naphthalene and of hydroquinone, tripropane monoallyl or diallyl ether, polypropylene oxide, polytetrahydrofuran, partially saponified polyvinyl acetate and hydroxy ethylated phenol-formaldehyde resins. In the examples, polyethers are made by reacting: (1) and (2) the degradation product of a xylene-formaldehyde condensate and trimethylol propane; (3) a degradation product of a xylene-formaldehyde condensate, trimethylol propane and butane dihydroxyethyl glycol; (4) a degradation product of a xylene-formaldehyde condensate, trimethylol propane and hexanediol-1, 6; (5) a degradation product of a xylene-formaldehyde condensate, trimethylol propane and 1, 4-butylene glycol; (6) 1, 3-dimethyl-4, 6-xylylene glycol dimethyl ether, triethylene glycol and trimethylol propane; (7) 1, 3-dimethyl-4, 6-xylene glycol dimethyl ether, triethylene glycol and trimethylol propane; (8) 1, 3-dimethyl-4, 6-xylylene glycol dimethyl ether and trimethylol propane; (9) 4, 41-dimethoxymethyl-diphenyl oxide and 4, 41-butane dihydroxy ethyl ether; (10) hexanediol-1, 6 and 4, 41-dimethoxymethyl-diphenyl oxide; (11) p-xylylene glycol, triethylene glycol and trimethylol propane; (12) 1, 3-dimethyl-4, 6-xylylene glycol, butane dihydroxy ethyl ether and trimethylol propane and (13) 1, 4-diallyl hydroxy-butene-2 and butane dihydroxy ethyl glycol ether.ALSO:Polyether compounds are made by condensing an unsaturated polyhydroxy compound of the general formula <FORM:0877913/IV (b)/1> or <FORM:0877913/IV (b)/2> where R1 is a hydrogen atom or an alkyl or aromatic radical, R2 is an aliphatic, cycloaliphatic or aromatic radical, R3 is an aromatic radical or an a ,b -unsaturated aliphatic residue and X is an integer from 2 to 6 with a different dihydric or polyhydric aliphatic, cycloaliphatic or aromatic alcohol in the presence of an acid catalyst. Specified catalysts are p-toluene sulphonic acid and esters thereof, benzene sulphonic acid and esters thereof, phosphoric acids and esters thereof and acidic montmorillonites. Reaction solvents e.g. methyl naphthylene, decalin or diphenyl ether may be used in the condensation. Specified unsaturated polyhydroxy compounds are the products formed by the degradation in the presence of acidic catalysts e.g. p hydrochloric, sulphuric, phosphoric or sulphonic acids, boron fluoride or sulphur dioxide of condensation products of formaldehyde with aromatic hydrocarbons, p-xylene glycol, o-xylylene glycol, 1,3,4-trimethylol benzene, 1,3-dimethyl-4,6-xylylene glycol, 1,5-bis-hydroxy methyl naphthalene, 4,41-bis-hydroxy methyl diphenyl ether, 1,4-bis-hydroxy methyl thiophene and heptadiene (2,5)-di-(1,7)-ol and the methyl, ethyl, propyl or allyl ethers thereof. Specified dihydric and polyhydric aliphatic, cycloaliphatic or aromatic alcohols are diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, pentachlorophenyl glycerine ether, trimethylol propane, glycerine, pentaerythritol, the di-b -hydroxy ethyl ethers of 4,41-dihydroxy diphenyl dimethyl methane, of 1,5-dihydroxy naphthalene and of hydroquinone and tripropane monoallyl or diallyl ether. In the examples polyethers are made by reacting (1) and (2) trimethylol propane and a degradation product made by reacting a xylene-formaldehyde condensate in the presence of p-toluene sulphonic acid; (3) a degradation product as in Example (1), trimethylol propane and butane dihydroxy ethyl glycol; (4) a degradation product as in Example (1), trimethylol propane and hexanediol-1,6; (5) a degradation product made by heating methanol with a xylene-formaldehyde condensate, trimethylol propane and 1,4-butylene glycol; (6) 1,3-dimethyl-4,6-xylylene glycol dimethyl ether made by reacting 1,3-dimethyl-4,6-dichloromethyl benzene with methanol in the presence of caustic soda, triethylene glycol and trimethylol propane; (7) 1,3-dimethyl-4,6-xylene glycol dimethyl ether, triethylene glycol and trimethylol propane; (8) 1,3-dimethyl-4,6-xylylene glycol dimethyl ether and trimethylol propane; (9) 4,41-dimethoxy methyl diphenyl oxide and 4,41-butane dihydroxyethyl ether, (10) 4,41-dimethoxymethyl-diphenyl oxide and hexanediol-1,6; (11) p-xylylene glycol, triethylene glycol and trimethylol propane; (12) 1,3-dimethyl-4,6-xylylene glycol, butane dihydroxy ethyl ether and trimethylol propane and (13) 1,4-diallyl hydroxy-butene-2 and butane dihydroxy ethyl glycol ether.</p> |
