| 摘要 |
<p>1390672 Phosphorus-containing perfluoroalkyl derivatives CIBA-GEIGY AG 24 Feb 1972 [25 Feb 1971 29 Dec 1971] 8653/72 Headings C2P and C2C [Also in Division D1] Perfluoralkyl compounds containing phosphorus are obtained by reacting a perfluoroalkylalkene with a phosphorus trihalide with exclusion of moisture and in the presence of oxygen or an oxygen-containing gas. Specified phosphorus trihalides are PC1 3 , PBr 3 and PI 3 and when the former is used for reaction with a perfluoroalkene of the formula where R 2 and R 3 each denote H or an unbranched or branched hydrocarbon radical and R is a C 1 -C 22 perfluoroalkyl radical (which is defined as an alkyl radical in which all the H atoms are replaced by F or all except a terminal (#) hydrogen atom are replaced by F) the products have the general formula wherein R denotes a perfluoroalkyl radical with 1 to 22 carbon atoms, A denotes a radical of the formula wherein R is bonded to the carbon atom (1) or (2), for each -(O) n-1 POCl 2 radical n is 1 or 2 with the proviso that in the case of formula (3) for n = 1a-(O) n-1 POOl 2 radical is bonded to at least one of R 2 and R 3 and for n = 2 to carbon atom (1) and, optionally, to at least one of R 2 and R 3 , and in the case of formula (4) for n = 1 or 2 a -(O) n-1 POCl 2 radical is bonded to at least one of R 2 <SP>11</SP> and R 3 <SP>11</SP> ; R 2 and R 3 each denote a hydrogen atom or an unbranched or branched hydrocarbon radical or a radical derived from an unbranched or branched hydrocarbon radical obtained by splitting off hydrogen atoms, to provide for R 2 and R 3 together up to 7 sites for the phosphorus-containing radicals, R<SP>11</SP> 2 is as defined under R 2 , and R 2 , R 3 and R 2 <SP>11</SP> are not hydrogen when a phosphoruscontaining radical is bonded thereto, R<SP>11</SP> 3 denotes a radical derived from an unbranched or branched hydrocarbon radical by splitting off hydrogen atoms to provide for R<SP>11</SP> 2 and R<SP>11</SP>3 together 1 to 8 sites for the phosphorus-containing radicals. The invention also includes as novel products those compounds having the above formula wherein R is a perfluoroalkyl radical (as defined above) containing 4 to 14 carbon atoms, R 2 R<SP>11</SP> 2 and R 3 are as defined above but when they are hydrocarbon radicals contain 1 to 18 carbon atoms, and R<SP>11</SP>3 is as defined above but is derived from an alkyl radical having 1 to 18 carbon atoms and r is 1 to 8. The molar ratio of the phosphorus trihalide to the perfluoroalkene is generally from 2 : 1 to 20 : 1 preferably 2 : 1 to 10 : 1, and the reaction may be carried out in an inert solvent. The products are useful for the production of oleophobic finishes on porous and non-porous substances, e.g. leather, paper, textile materials, metals, plastics and glass. A perfluoroheptylbutene isomer mixture is obtained by addition of perfluoroheptyl iodide to isobutylene and alkaline elimination of HI. A perfluoroheptyl octene isomer is obtained analogously using n-octene-(1).</p> |
