| 摘要 |
The invention comprises substantially linear polyesters of phosphorous acid said polyesters having an OH number of from 30 to 800 and comprising at least two free hydroxyl groups and at least two phosphorous acid ester residues in the molecule, each of which residues contains an unsubstituted or halogen-substituted alkoxy or cycloalkoxy radical with 1 to 6 carbon atoms bonded to the phosphorus atom. They may be obtained by reacting at elevated temperature a trialkyl or tricycloalkyl phosphite said alkyl or cycloalkyl radicals each containing up to 6 carbon atoms and each of which groups may be substituted by a halogen atom with an organic dihydroxy compound containing at least four atoms between the OH groups at least 2.2 but less than 6 OH groups of the dihydroxy compound being present for each mol of the phosphite. The phosphorous acid ester is preferably a tri(b -chloroalkyl)-phosphite and the dihydroxy compound is preferably a polyalkylene glycol but other dihydroxy compounds are also suitable including 1,4-butane diols, hexane-1, 6-diol, butene 1,4-diol, butinel, 4-diol, hydroxyalkylated phenols, amino alcohols, e.g. N-methyl diethanolamine, hydroxyalkyl-esters of polycarboxylic acids, 2,21-dihydroxydialkyl sulphides and disulphides and linear and branched polyesters and polyethers containing terminal hydroxy groups and having a molecular weight not exceeding 5,000. The dihydroxy compound can be used in admixture with a higher organic polyhydroxy compound or with an organic dihydroxy compound containing two or three atoms between the OH groups, e.g. ethylene- or tri-methylene glycol, trimethylol propane, pentaerythritol, glycerine -1- pentachlorophenyl ether or triethanolamine. The dihydroxy compounds containing at least 8 atoms between the OH groups may be substituted e.g. by nitro, alkoxy or carboxylic acid ester groups and particularly by halogen atoms. The transesterification is preferably effected at from 60 DEG to 180 DEG C. if desired under reduced pressure so that the monohydric alcohol which is liberated from the phosphite is continuously distilled off. The reaction should be carried out in the substantial absence of water. A catalyst is not necessary although an alkaline or acidic catalyst may be used if desired. The products are useful for the production of epoxide resins, as lubricants, and as plasticizers or stabilizers for halogen-containing polymers. Examples are given for the production of linear polyesters from (1) trichloroethyl phosphite and triethylene glycol, (2) trichlorethyl phosphite and a mixture of triethylene glycol and glycerine -1- pentachlorophenyl ether, (3) trichloroethyl phosphite and 1, 6-hexane diol, (4) triethyl phosphite and triethylene glycol, (5) triethyl phosphite and a mixture of triethylene glycol and glycerin -a - chlorohydrin, and (6) triethylene glycol and a mixture of triethyl phosphite and trichloroethyl phosphite.ALSO:The invention comprises substantially linear polyesters of phosphorous acid said polyesters having an OH number of from 30 to 800 and comprising at least two free OH groups and at least two phosphorous acid ester residues in the molecule, each of which residues contains an unsubstituted or halogen-substituted alkoxy or cycloalkoxy radical with 1 to 6 carbon atoms bonded to the phosphorus atom. They may be obtained by reacting at elevated temperature an appropriate trialkyl or tricycloalkyl phosphite which may be substituted by a halogen atom with an organic dihydroxy compound containing at least four atoms between the OH groups, at least 2.2 but less than 6 OH groups of the dihydroxy compound being present for each mol of the phosphite. The phosphite is preferably a tri(b -chloroalkyl)-phosphite and the dihydroxy compound is preferably a polyalkylene glycol but other dihydroxy compounds are specified e.g. 1, 4-butane diols, hexane 1, 6-diol butene 1, 4-diol, butine-1, 4-diol, hydroxy alklyated phenols, appropriate amino alcohols, e.g. N-methyl diethanolamine, hydroxyalkyl esters of polycarboxylic acids, 2, 21-dihydroxydialkyl sulphides and disulphides and linear and branched polyesters and polyethers containing terminal OH groups and having a molecular weight not exceeding 5,000. The dihydroxy compound can be used in admixture with a higher organic polyhydroxy compound or with an organic dihydroxy compound containing 2 or 3 atoms between the OH groups, e.g. ethylene- or tri-methylene glycol, trimethylol propane, pentaerythritol, glycerine-1-pentachlorophenyl ether or triethanolamine. The dihydroxy compounds containing at least 4 atoms between the OH groups may be substituted, e.g. by nitro, alkoxy or carboxylic ester groups and particularly by halogen atoms. The transesterification is preferably effected at 60 to 180 DEG C. if desired under reduced pressure and should be carried out in the absence of water. A catalyst is not necessary but an alkaline or acidic catalyst may be used if desired. The products are useful for the production of epoxide resins, as lubricants, and as plasticisers or stabilisers for halogen-containing polymers. Examples are given for the production of linear polyesters from (1) trichloroethyl phosphite and triethylene glycol, (2) trichloroethyl phosphite and a mixture of triethylene glycol and glycerine -1- pentachlorophenyl ether, (3) trichloroethyl phosphite and 1, 6-hexane diol, (4) triethyl phosphite and triethylene glycol, (5) triethyl phosphite and a mixture of triethylene glycol and glycerin -a - chlorohydrin, and (6) triethylene glycol and a mixture of triethyl and trichloroethyl phosphites. |
