Patent GB-1034495-A (GB)
Title: Process for the production of dioxolanes and related polymers
IPC: C08G65/26
Filed: 1965-03-09
Abstract: Dioxolanes of formula:-  <FORM:1034495/C2/1> and/or polymers of formula:-  <FORM:1034495/C2/2> wherein X and X1 are hydrogen, fluorine, chlorine or bromine atoms or polyfluoro alkyl groups of up to 18 carbon atoms, or together form a polyfluoroalkylene group of up to 3 carbon atoms, and R, R1 and R11 are hydrogen atoms, or cyano, carboxyl or alkyl groups, alkyl groups substituted with hydroxy or alkoxy groups or fluorine, chlorine or bromine atoms and containing up to 18 carbon atoms, or with aryloxy groups and containing up to 14 carbon atoms or alkoxy carbonyl, carbacyl or carbocyclooxy-, carboxy- or alkoxycarbonylalkylenyl groups containing up to 18 carbon atoms, or where R and R11 together form an alkylene group of up to 6 carbon atoms and n and a are at least 1 and 3 respectively, are prepared by a reaction between at least one polyfluoroketone of formula X-CF2-CO-CF2-X1 with at least one epoxide of general formula <FORM:1034495/C2/3> in the presence of a catalyst which is anionic or a tertiary amine.  The dioxolanes are preferentially prepared at temperatures of 100-200 DEG  C. and the polymers below 100 DEG  C. (see also Division C3).  Suitable catalysts include alkyl sulphoxides, alkalimetal fluorides, cyanates, thiocyanates, alkoxides and acylates; tetraalkyl, trialkylaryl-, and trialkylaralkyl ammonium chlorides and tertiary lower alkyl amines; phosphine oxides may also be used. Lists of suitable reagents for the reaction are given and the examples describe the preparation of 2,2-bis-(trifluoromethyl)-1,3-dioxolane from ethylene oxide and hexafluoroacetone.  Hexafluoroacetone is prepared by converting commercial hexafluoroacetone to the 1.6 H2O hydrate, adding sodium silicate solution until the pH is from 2-2.3 and distilling the hydrate under vacuum.  The ketone is liberated by adding it to a mixture of concentrated sulphuric acid and phosphorous pentoxide.ALSO:Polymers of formula <FORM:1034495/C3/1> together with dioxolanes (see Division C2) wherein X and X1 are hydrogen, fluorine, chlorine or bromine atoms or polyfluoroalkyl groups of up to 18 C atoms, or together form a polyfluoroalkylene group of up to 3 C atoms, and R, R1 and R11 are hydrogen atoms, or cyano, carboxyl or alkyl groups, alkyl groups substituted with hydroxy or alkoxy groups or with fluorine, chlorine or bromine atoms and containing up to 18 carbon atoms or with aryloxy groups and containing up to 14 carbon atoms or alkoxy-carbonyl, carbacyl or carbocyclooxy-, carboxy-, or alkoxycarbonyl-alkylenyl groups containing up to 18 carbon atoms, or where R and R11 together form an alkylene group of up to 6 carbon atoms and n is at least 1 and a is at least 3, are prepared by a reaction between at least one polyfluoroketone of formula <FORM:1034495/C3/2> with at least one epoxide of formula <FORM:1034495/C3/3> in the presence of a catalyst which may either be anionic or a tertiary amine.  Preferred temperatures are below 100 DEG  C. Suitable catalysts include alkyl sulphoxides, alkali metal fluorides, cyanates, thiocyanates, and alkoxides and acylates; tetraalkyl-, trialkylary- and trialkylaralkyl ammonium chlorides and tertiary lower-alkyl amines; phosphine oxides may also be used.  The polymers can be converted into polymers with different end groups. Ester end groups may be obtained by reaction with an alkanoic acid, acid anhydride, acid halide or ketone; halide end groups by reaction with a phosphorus halide; ether end groups by reaction with an orthoester, acetal or an alkyl ester of a strong inorganic acid. Long lists of suitable reagents for the reaction are given and the examples describe the preparation of a polymer from ethylene oxide and hexafluoroacetone, 1,2-epoxycyclohexane and hexafluoroacetone, ethylene oxide and chloropentafluoroacetone, 1,2-epoxypropane and hexafluoroacetone, 3-phenoxy-1,2-epoxypropane and hexafluoroacetone, 3,4-epoxybutane- 1 and hexafluoroacetone, 2-methyl-1,2-epoxypropane and hexafluoroacetone.ALSO:Water-repellancy may be imported to flexible and rigid substrates by coating with a copolymer of formula:-  <FORM:1034495/B1-B2/1> wherein X and X1 are hydrogen, fluorine, chlorine or bromine atoms or polyfluoroalkyl groups and R, R1 and R11 are hydrogen atoms, alkyl groups or other functionally substituted organic groups; n and a are at least 1 and 3 respectively. Suitable substrates are paper or cloth and example 1c describes the process of waterproofing paper by sprinkling powdered untreated copolymer on it and then heating the coated paper to 150 DEG C. under 3000 lb/sq in pressure.