| 摘要 |
Polycarbodiimides are prepared by heating to at least 120 DEG C. in the presence of a catalyst at least one aliphatic or cycloaliphatic di- or poly-isocyanate having all its isocyanate groups directly attached to secondary or tertiary carbon atoms and/or at least one aromatic di- or polyisocyanate having all its isocyanate groups directly attached to a carbon atom of a benzene ring which has at least one organic radical containing 2-18 carbon atoms in the orthoposition thereto, the catalyst being one which is known to promote the trimerization to isocyanuric acid rings of organic unhindered isocyanates. Suitable catalysts include tertiary amines, tertiary amino ethers, unsubstituted or substituted pyridines, alkali metal hydroxides and salts, salts of carboxylic acids, and organo-metallic compounds, many catalysts being specified. The polyisocyanates may be unsubstituted or substituted and may also be previously reacted with mono- or polyhydric alcohols, phenols, amines, hydroxy-polyethers, polyamides, mercapto-polythioethers, hydroxypolyesters, or polyacetals, to give polymers containing free isocyanate groups. p Numerous starting materials are specified. In examples, (2) and (13) 1,3,5-triisopropylbenzene-2,4-diisocyanate, (7) 1,3,5-triisopropylbenzene-2,4,6-triisocyanate, (8) 1-methyl-3,5-diethylbenzene-2,6-diisocyanate, and (10) 1,3,5-triethylbenzene-2,4-diisocyanate, are converted to polycarbodiimides. Example 11 describes the reaction of 1,3,5-triisopropylbenzene-2,4-diisocyanate with octadec-9-ene-1,12-diol to give a polyurethane containing free isocyanate groups which is then converted to a polyurethane polycarbodiimide. Example 12 describes the reaction of 1,3,5-triisopropylbenzene-2,4-diisocyanate with a linear hydroxy-polyester containing adipic acid and diethylene glycol units to give a polyester polyurethane containing free isocyanate groups which is then converted to a polyester polyurethane polycarbodiimide. Specification 851,936 is referred to.ALSO:Carbodiimides are prepared by heating to at least 120 DEG C. in the presence of a catalyst at least one aliphatic or cycloaliphatic isocyanate having all its isocyanate groups directly attached to secondary or tertiary carbon atoms, and/or at least one aromatic isocyanate having all its isocyanate groups directly attached to a carbon atom of a benzene ring which has at least one organic radical containing 2-18 carbon atoms in the ortho-position thereto, the catalyst being one which is known to promote the trimerisation to isocyanuric acid rings of an unhindered organic isocyanate. Suitable catalysts include tertiary amines, tertiary amino ethers, unsubstituted or substituted pyridines, alkali metal hydroxides and salts, salts of carboxylic acids, and organo-metallic compounds. Many catalysts are specified. The isocyanates may be unsubstituted or substituted by, for example, alkoxy, nitro, halogen, carboethoxy, thioether, disulphide, sulphone and sulphonamido groups. The isocyanates may be polyisocyanates reacted previously with mono- or polyhydric alcohols, phenols, amines, hydroxy-polyethers, polyamides, mercapto-polythioethers, polyesters containing free hydroxyl groups, or polyacetals to give polymers containing free isocyanate groups (see Group IV(a)). Numerous substituted and unsubstituted mono- and polyisocyanates are mentioned. The amount of catalyst is preferably 0.01 to 10% by weight of the isocyanate and the reaction temperature is preferably 120-300 DEG C. The reaction may be carried out in inert gases or solvents. When polyisocyanates are used initially high molecular weight polycarbodiimides are obtained which may be employed in combination with compounds containing reactive hydrogen atoms (see Group IV(a)). The isocyanates may be prepared by phosgenation of the corresponding amines. In examples, on heating with sodium phenate, (1) 1-isocyanato-2,6-diisopropylbenzene gives, after purification, di-(2,6-diisopropylphenyl) carbodiimide; similarly (4) 2,6-diethylphenyl isocyanate, (5) 2,4-diisopropylphenyl isocyanate, (6) 2,6-diethoxyphenyl isocyanate, and (9) 1-methyl-1-cyclohexyl isocyanate give the corresponding carbodiimides. In further examples, using potassium hydroxide, (3) 2,6-di-sec-butyl-phenyl isocyanate gives di-(2,6-di-sec-butyl-phenyl) carbodiimide; (14) 1,2,2-trimethyl propyl isocyanate gives N,N1-bis-3-(2,2-dimethylbutyl)-carbodiimide; (15) diethylmethyl isocyanate gives N,N1-bis-(3-amyl)-carbodiimide. Specification 851,936 is referred to.
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