| 摘要 |
1,156,222. Polycarbonates. UNION CARBIDE CORP. 6 June, 1966 [7 June, 1965], No. 25047/66. Heading C3R. Polycarbonates are made by reacting phosgene with a cyclobutanediol or an alkyl substituted cyclobutanediol at 10‹ to 150‹ C. in the presence of 2 to 20 parts per part of diol of a liquid organic compound containing a sterically unhindered heterocyclic, tertiary nitrogen atom, at least the ultimate 1% of the stoichiometric amount of phosgene being added at a rate not to exceed 1% of the stoichiometric quantity per 4 minutes. Up to 50 mol. per cent of the cyclobutanediol may be replaced by other diols, e.g. C 3-10 alkylene glycols, di- or tri-ethylene glycol, cyclopentanediols, cyclohexanediols, furanediols, cyclohexanedimethanols, cyclohexane - diethanols, bis - (hydroxyethoxy) cyclohexanes and dipropylcyclohexane - diols. The heterocyclic organic compound may be a substituted or unsubstituted pyrimidine, pyridine, N-alkyimidazole or quinoline. The reaction medium may also include an inert solvent or diluent, e.g. a hydrocarbon or chlorinated hydrocarbon. The phosgenation may be effected (i) by a continuously slow rate of addition of phosgene at 50‹ to 130‹ C., the polycarbonate being heated at 80‹ to 130‹ C. when reaction is effected below 60‹ C.; (ii) first at a rapid rate at 10‹ to 60‹ C. and then at a slow rate at 100‹ to 110‹ C., the latter preferably being during the addition of the last 1 to 10% of the stoichiometric amount of phosgene; or (iii) first at a fast rate at 10‹ to 40‹ C. during which 30 to 49% of the stoichiometric amount of phosgene is added, secondly at a further fast rate at 60‹ to 75‹ C. during which 50 to 69% of the stoichiometric amount of phosgene is added, and thirdly at a slow rate at 100‹ to 130‹ C. during which 1 to 10% of the stoichiometric amount of phosgene is added. Examples describe the preparation of a polycarbonate of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol or a mixture thereof with 1,4-cyclohexanedimethanol. Reference has been directed by the Comptroller to Specifications 925,139, 962,913, 1,011,283. |
