Patent GB-1028616-A (GB)
Title: Stabilized polymer compositions, phosphorus containing carboxylic acid amides for use therein and process for their preparation
IPC: C08L77/00
Filed: 1964-10-28
Abstract: Lubricating oils or motor fuels contain as stabilizing additive a phosphorus-containing carboxylic acid amide of the formula:- <FORM:1028616/C4-C5/1> wherein R1 is a monovalent hydrocarbon group or an OR2 group, R3 is a monovalent hydrocarbon group or an OR4 group, R2, R4 and R5 are similar or dissimilar monovalent hydrocarbon groups and R6 is H or a monovalent hydrocarbon group, or R5 and R6 together with the N atom form a heterocyclic ring which may contain other hetero-atoms; and R7 is a divalent polymethylene group, consisting of a chain of at least 3 methylene groups (see Division C2).ALSO:The invention comprises phosphorus-containing carboxylic acid amides of the formula <FORM:1028616/C2/1> in which R1 is a monovalent hydrocarbon group or an OR2 group, R3 is a monovalent hydrocarbon group or an OR4 group, R2, R4 and R5 are similar or dissimilar monovalent hydrocarbon groups, R6 is H or a monovalent hydrocarbon group, or R5 and R6 together with the N atom form a heterocyclic ring which may contain other hereto atoms, R7 is a divalent polymethylene group, consisting of a chain of at least 3 methylene groups.  They may be obtained by reacting a halo-carboxylic acid amide of the formula <FORM:1028616/C2/2> with a phosphite, phosphonite or phosphinite of the formula <FORM:1028616/C2/3> wherein X represents halogen and R8 a monovalent, substituted or unsubstituted hydrocarbon group.  Temperatures of 120-220 DEG  C. are used in phosphite reactions, and temperatures of 20-160 DEG  C. are used in phosphonite and phosphinite reactions. The hydrocarbon groups may be aliphatic or aromatic or may be of aliphatic-aromatic character.  The aliphatic groups may be branched or unbranched or cyclic, saturated or unsaturated.  The aromatic groups may be single or condensed nuclei.  Preferred aliphatic groups are methyl ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, n-hexyl, cyclohexyl and alkyl.  A preferred aromatic group is phenyl.  The products may be incorporated as stabilizers in polymer and/or copolymer compositions (see Division C3) and are also useful as stabilizers for lubricating oils and as additives for motor fuels.  The halocarboxylic acid amide used as starting material may be prepared from lactones such as g -butyrolactone, d -valerolactone, g -valerolactone or e -caprolactone by reacting with thionyl chloride or PCl5; the resulting chloro-carboxylic acid chloride being reacted with a primary or secondary amine.ALSO:A stabilized composition comprises a polymer and/or a copolymer of an olefinically unsaturated hydrocarbon and as a stabilizing additive a phosphorus-containing carboxylic acid amide of the formula <FORM:1028616/C3/1> wherein R1 is a monovalent hydrocarbon group or an OR2 group, R3 is a monovalent hydrocarbon group or an OR4 group, R2, R4 and R5 are similar ot dissimilar monovalent hydrocarbon groups and R6 is H or a monovalent hydrocarbon group, or R5 and R6 together with the N atom form a heterocyclic ring which may contain further hetero-atoms; and R7 is a divalent polymethylene group, consisting of a chain of at least 3 methylene groups (see Division C2).  The stabilizing effect of the above additives may be improved by the addition of one or more phenols having secondary and/or tertiary hydrocarbon group substituents in one or more ortho-positions. Specified phenols include those of the formula <FORM:1028616/C3/2> where Ar is an aryl nucleus which may be substituted, preferably a benzene nucleus, R9 is a similar or dissimilar secondary and/or tertiary hydrocarbon groups; and R10 represents hydrogen atoms which may be replaced by similar or dissimilar hydrocarbon groups; and n is a whole number from 1 to 3; Ar may also contain a phenolic hydroxyl group.  Other suitable phenols are those of the formula <FORM:1028616/C3/3> where X is O, S, NH group or a group CmH2n where m is at least 2, and wherein the hydrogen atom of the NH group may be replaced by <FORM:1028616/C3/4> Useful phenols are those which contain two arylol nuclei linked by an O or S atom, an imino group or a methylene group, and having in the ortho-position relative to the HO groups present in the aryl nuclei one or more alkyl groups which are branched in the a -position. In addition to the said phenols the stabilized compositions may also contain organic sulphur compounds such as dilauryl thiodipropionate and/or dialkyl sulphides.  An example is given where polypropylene prepared with the aid of a catalyst system composed of TiCl3 and Al(C2H5)2Cl is stabilized by the addition of various stabilizers of the above general formula.