Patent GB-693742-A (GB)
Title: Production of diesterified phosphono derivatives of unsaturated mono carboxylic esters, amides or nitriles
IPC: D06M13/288
Filed: 1949-06-03
Abstract: Resinous compositions comprise a synthetic thermoplastic resin, e.g. a vinyl chloride-acetate copolymer, or a cellulosic derivative, and as a plasticizer or modifier a phosphono compound having the general formula <FORM:0693742/IV (a)/1> wherein R represents a saturated aliphatic or cycloaliphatic hydrocarbon radical, an aromatic hydrocarbon radical, or an alkoxyalkyl, aryloxyalkyl or cycloalkoxyalkyl radical, R1 is hydrogen or an alkyl, alkenyl or aryl radical, R2 and R3 represent hydrogen or an alkyl radical and X represents COOR4, CON(R5)2 or a CN group, wherein R4 is an alkyl, alkenyl, cycloalkyl, aralkyl, alkoxyalkyl, aryloxyalkyl or cycloalkoxyalkyl group and R5 is hydrogen or an alkyl or aryl radical, the term "alkoxyalkyl" being used to include saturated heterocyclic radicals containing only ring oxygen in addition to carbon and hydrogen atoms (see Group IV (b)).  Certain of the compounds also have flame-retardant properties.  The Specification as open to inspection under Sect. 91 refers to the same use of phosphorus compounds obtained by reaction of any phosphite di-ester with an a  : b -unsaturated carboxylic acid ester, amide or nitrile. This subject-matter does not appear in the Specification as accepted.ALSO:Phosphono compounds having the general formula <FORM:0693742/IV (b)/1> wherein R represents a saturated aliphatic or alicyclic hydrocarbon radical or an aromatic hydrocarbon radical or an alkoxyalkyl, aryloxyalkyl or cycloalkoxyalkyl group, R1 is hydrogen or an alkyl, alkenyl or aryl radical, R2 and R3 respectively represent a hydrogen atom or an alkyl radical and X represents COOR4, CON (R5)2 or a CN group wherein R4 is an alkyl, alkenyl, cycloalkyl, aralkyl, alkoxyalkyl, aryloxyalkyl or a cycloalkoxyalkyl group and R5 is hydrogen or an alkyl or aryl radical, the term "alkoxyalkyl" being used to include saturated heterocyclic radicals containing only ring oxygen in addition to carbon and hydrogen, are prepared by adding, in the presence of an alkaline non-peroxidic type condensation catalyst incapable of forming free radicals, an ester amide or nitrile of an a : b -ethylenic unsaturated monocarboxylic acid of the general formula CR1R2=CR3X in successive small increments to a phosphite diester of the general formula <FORM:0693742/IV (b)/2> while maintaining the resulting reaction mixture at a temperature within the range from 25 DEG  to 200 DEG  C.  Specified catalysts are alkali metals, their amides, hydrides and alcoholates; sodium naphthalene; secondary and tertiary amines such as di- and tri-ethylamine; the salts of phosphite diesters of the general formula <FORM:0693742/IV (b)/3> where Y represents an alkali metal, magnesium or an alkaline earth metal, and R is as defined above; and benzyl trimethyl ammonium butoxide.  Inert solvents may also be present such as dioxane, aromatic hydrocarbons and ethers, for example, dibutyl ether, diethyl ether and the dimethyl and diethyl ethers of ethylene and diethylene glycols.  The compounds may be used as flame retarding plasticizers for resins (see Group IV (a)).  Examples describe the production of (1) 2-ethylhexyl 3-(dibutylphosphono) propionate from dibutyl phosphite and 2-ethylhexyl acrylate and (2) the corresponding nitrile from acrylonitrile; (3) butyl 3-(dibutylphosphono) butyrate from butyl crotonate and dibutyl phosphite; (4) butyl 2-methyl-3-(dibutyl phosphono) propionate from butyl methacrylate and dibutyl phosphite; (5) ethyl 3-di-(cyclohexylphosphono) propionate from ethyl acrylate and dicyclohexyl phosphite; (6) butyl 3-phenyl-3-(dibutylphosphono) propionate from butyl cinnamate and dibutyl phosphite; (7) butyl 3-(dibutylphosphono) hexen-4-oate from butyl sorbate and dibutyl phosphite; (8) 2-ethylhexyl 3 - (dicyclohexylphosphono) propionate from 2-ethylhexyl acrylate and dicyclohexyl phosphite; (9) 2-methyl-3-dibutylphosphonopropionitrile from a  - methacrylonitrile and dibutylphosphite; (10) 3-(dibutylphosphono) propionamide from acrylamide and dibutyl phosphite; (11) N-methyl 3-(dibutylphosphono) propionamide from dibutyl phosphite and N-methacrylamide; (12) butyl 3-(dimethoxy ethyl phosphono) butyrate from butyl crotonate and di-(methoxyethyl) phosphite; (13) 3-(dibutylphosphono) propionitrile from acrylonitrile and dibutyl phosphite.  The production in like manner of the following compounds is also referred to: 3-di-(phenoxyethyl)-phosphonopropionitrile; phenoxyethyl 2-methyl - 3 - dicyclohexylphosphonobutyrate; hexyl 3 - dibenzylphosphonopropionate; benzyl 2 - methyl - 3 - di - (tetrahydrofuranyl) - phosphonopropionate; butyl 3-methyl-3-dicyclohexylphosphonobutyrate; methoxyethyl 2 - methyl - 3 - di - (ethoxyethyl) - phosphonopropionate; 3 - dihexylphosphonobutyronitrile; 3-dibenzylphosphonobutyramide; 3-diphenylphosphonobutyric anilide.  Many further examples of starting materials are also given.  The Specification as open to inspection under Sect. 91 relates to the production of diesterified phosphono derivatives of aliphatic and aromatic mono-carboxylic esters, amides or nitriles by reacting a phosphite diester with an a : b -unsaturated carboxylic ester, amide or nitrile at 25-200 DEG C.; it includes a further example wherein dibutyl phosphite and butyl crotonate are heated together, in absence of a catalyst, to yield a small amount of butyl 3-dibutyl phosphonobutyrate.  This subject-matter does not appear in the Specification as accepted.