Patent GB-971732-A (GB)
Title: New fluorinated methacrylates and polymers thereof
IPC: C08L33/16
Filed: 1962-04-25
Abstract: The invention comprises compounds of the formula <FORM:0971732/C1/1> wherein n is an integer from 3 to 14.  The compounds may be prepared by esterification of alcohols of the formula CnF2n+ 1CH2CH2OH with methacrylic acid or methacrylyl chloride or by transesterification with alkyl methacrylates. They may also be prepared by treatment of the iodides of the formula CnF2n+ 1CH2CH2I with silver methacrylate. The alcohols of the above formula may be prepared by (1) reacting an iodide CnF2n+ 1CH2CH2I with silver acetate to give a compound CnF2n+ 1CH2CH2OCOCH3 which is hydrolyzed to the corresponding alcohol, or (2) reacting an iodide CnF2n+ 1I with vinyl acetate in the presence of a catalyst to produce CnF2n+ 1-CH2-CH(I)-O-CO-CH3 which is reduced by zinc and hydrochloric acid in ethanol to the fluorinated acetate described in (1) above which is then hydrolyzed to the alcohol. Iodides of the formula CnF2n+ 1 CH2CH2I are prepared by reacting CnF2n+ 1I with ethylene.  The compounds of the invention may be polymerized or co-polymerized (see Division C3).ALSO:Compounds of the general formula <FORM:0971732/C3/1> (1) wherein n is an integer from 3-14 (see Division C2) may be polymerized to give polymers comprised of the recurring unit <FORM:0971732/C3/2> wherein n is an integer from 3 to 14 and wherein n may be the same or different in the various recurring units contained in the polymer chain, these polymers being claimed per se.  The polymers of Formula (2) may be used to make compositions comprising 3-25% by weight of such a polymer and from 75-97% by weight of a polymer prepared from at least one polymerizable vinyl compound, this term being defined as a compound free from effective fluorine (i.e. not containing fluorine attached other than directly to a vinyl or vinylidene carbon atom) and chosen from <FORM:0971732/C3/3> 1, 3-butadiene, 2-chloro-1, 3-butadiene, 2, 3-dichloro-1, 3-butadiene and isoprene, wherein R1 is hydrogen or methyl, R2 is a saturated alkyl group containing 1-18 carbon atoms, R3 is phenyl or alkyl-substituted phenyl, R4 is hydrogen or a saturated C1-6 alkyl group and Y is fluorine, chlorine or bromine. The compounds of Formula (1) above may also be copolymerized in an amount of from 25-99% by weight with from 1-75% by weight of at least one polymerizable vinyl compound as defined above, the resultant copolymers being mixed with a polymer prepared from at least one polymerizable vinyl compound as defined above, the proportion of the polymers being such that the mixture contains at least 3% by weight of the component CH2=C(CH3)-CO2CH2CH2CnF2n +1. All the above types of polymer may be prepared by bulk, solution, suspension and emulsion polymerization techniques.  The fluorinated polymers and compositions thereof may be dispersed or dissolved in water or other liquids, the resultant dispersion or solutions being used in rendering porous materials oil- and water-repellent (see Divisions D1 and D2).ALSO:Porous materials are rendered oil- and water-repellent by treatment with (i) a polymer comprised of the recurring unit <FORM:0971732/D1-D2/1> wherein n is an integer from 3-14 and wherein n may be the same or different in the various recurring units contained in the polymer chain, or (ii) a polymer obtained by copolymerizing a compound of the formula <FORM:0971732/D1-D2/2> where n is as defined above, with at least one polymerizable vinyl compound, this term being defined as a compound free from effective fluorine (i.e. not containing fluorine attached other than directly to a vinyl or vinylidene carbon atom) and selected from <FORM:0971732/D1-D2/3> 1, 3-butadiene, 2-chloro-1, 3-butadiene, 2,3-dichloro-1, 3-butadiene and isoprene, wherein R1 is hydrogen or methyl, R2 is a saturated alkyl group containing 1-18 carbon atoms, R3 is phenyl or alkyl-substituted phenyl, R4 is hydrogen or a saturated C1-6 alkyl group and Y is fluorine, chlorine or bromine.  The proofing involves also the application of a polymer of a polymerizable vinyl compound free from effective fluorine as defined above, the "non-fluorinated" and fluorinated polymers being applied simultaneously or successively from solutions or dispersions in water or other liquids.  Specified materials which may be treated are wool, cotton, silk, regenerated cellulose, nylon, fibre-forming linear polyesters, fibre forming polyacrylonitrile, cellulose nitrate, cellulose acetate, ethyl cellulose, paper, fibre glass, wood, pressed or otherwise hardened wood composites, metals, unglazed porcelain and porous concrete, especially suitable materials being dyed and undyed cotton sateen, poplin, broadcloth, jean cloth and gaberdine.  For treating paper it is preferable to add compositions comprising a fluorinated and a "non-fluorinated" polymer to the beater stock, the usual drying step of paper manufacture being sufficient to cure the polymer.  Examples are given.