Patent GB-968847-A (GB)
Title: Modified textile and industrial fibers and fabrics and process for making them
IPC: D06M11/55
Filed: 1960-10-14
Abstract: Fibrous products formed from a mass of linear polymer molecules which are at least partially orientated longitudinally of the axis of the fibre comprising at least one polymerized monoethylenically unsaturated aromatic compound (A) and at least one polymerized linear aliphatic polyene and/or alkenyl halide (B) the polymeric mass having an apparent second order transition temperature of at least 20 DEG C., are alkylated in the presence of an alkylation catalyst under conditions such that aromatic nuclei of the polymeric mass are alkylated by polymerized polyene and/or alkenyl halide units for a period of time at least sufficient to render the fibrous product resistant to solvents by crosslinking. A blend of A and B, or a copolymer of the A and B monomers may be used. Preferably, A is a monovinyl aromatic compound of formula CH2=C(R)Z where R is hydrogen or an alkyl group, advantageously of less than three carbon atoms, and Z is an aryl group which has positions on an aromatic nucleus available for substitution. Specified compounds include vinyl aryls, e.g. styrene, vinyl naphthalene, vinyl diphenyl, and vinyl fluorene, and their nuclear-substituted derivatives, e.g. alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkoxy, aryloxy, chloro, fluoro, chloromethyl, fluoromethyl and trifluoromethyl nuclear derivatives, e.g. o-, m-, and p-methylstyrenes, o-, m-, and p-ethyl styrenes, isopropyl styrenes, tolyl-styrenes, benzyl-styrenes, cyclohexylstyrenes, methoxystyrenes, phenoxystyrenes, o-, m- and p-chlorostyrenes, o-, m- and p-fluorostyrenes, chloromethyl styrenes, fluoromethyl styrenes, trifluoromethylstyrenes, vinyl methyl naphthalenes, vinyl ethyl naphthalenes, vinyl chloronaphthalenes and vinyl methyl chloronaphthalenes. Also suitable are aromatic compounds having a vinyl group containing an alkyl group in its a -position, e.g. isopropenyl or a -methyl vinyl, a -ethyl vinyl, a -propyl vinyl &c. Such a -alkyl vinyl groups may be substituted on e.g. benzene, naphthalene, diphenyl or fluorene nuclei and may have other substituents on the aromatic nuclei as illustrated for the vinyl aryl compounds. The A polymer may be a homopolymer or copolymer of one or more of the specified monovinyl aromatic compounds, and may comprise up to 15% of a non-aromatic compound copolymerized therein (C) e.g. isobutylene, ethylene, vinyl acetate, acrylonitrile, methyl methacrylate, ethyl acrylate, or other acrylic esters.  Specified B compounds include the following alkenyl halides:-methallyl chloride, allyl chloride, 2,3-dichloro-propene-1, crotyl chloride, vinyl chloride, vinylidene chloride, 1-chloro-fluoro-ethylene, 4-chlorobutene-1 and pentenyl-chlorides; and the following linear polyenes:-butadiene-1,3; isoprene or 2-methyl butadiene-1,3; natural rubber; 2,3-dimethylbutadiene-1, 3; 2 methyl-pentadiene-1,3; hexatriene-1,3,5; myrcene; ocimene; allo-ocimene and substituted aliphatic polyenes, e.g. the chloro, fluoro and aryl derivatives e.g. chloroprene or 2 chloro-butadiene-1,3; fluoroprene or 2-fluorobutadiene-1,3; and 1-phenyl-butadiene-1,3. The B polymer may comprise copolymers of an alkenyl halide or of a linear polyene or of both with up to 90% by weight of one of the aromatic compounds specified or it may include up to 15% of any other type of comonomer, e.g. those specified at (C).  The polymers or copolymers may be made by bulk, solution, suspension or emulsion polymerization, and the blends may be made by mixing melts, solutions or aqueous dispersions of the two polymer components. The proportion of polymerized alkenyl halide and/or linear aliphatic polyene units in the polymeric mass is desirably 2-30%, especially 5-20%.  Fibres may be made from the mass by melt, dry, or wet spinning. An example describes the wet-spinning of an aqueous dispersion containing 40% polymer solids, consisting of 85:15 styrene and butadiene, with 5% toluene, into a coagulating bath consisting of 30% aqueous hydrochloric acid with 0.5% p-diisobutyl phenoxyethoxy ethyl dimethyl benzyl ammonium chloride and held at 85 DEG C. The filaments formed may be stretched, desirably at least 50%, to effect longitudinal orientation, suitably at 40-120 DEG C. Alkylation may be effected on a tow or yarn of the stretched filaments, and on textile and "non-woven" fabrics made therefrom. Alkylation catalysts may be Lewis acids or Friedel-Crafts catalysts e.g. aluminium chloride, ferric chloride, stannic chloride, titanium chloride, the corresponding bromides and boron trifluoride, especially its complexes e.g. with ethyl ether, or concentrated solutions of strong acids, e.g. sulphuric and phosphoric acids, chlorosulphonic acid, alkyl or aryl sulphonic acids, e.g. o- or p-toluene sulphonic acid, methanesulphonic acid, or polyphosphoric acid.  Treatment with solid Lewis acid catalysts may be effected in solvents, e.g. in nitromethane, but with liquid catalysts, e.g. the boron trifluoride ethyl ether complex, solvents are unnecessary. Alkylation in the presence of Lewis acid catalysts may be effected at from 0-100 DEG C., the time of treatment varying from 1-72 hours at 0 DEG C. to 1 min.-2 hours at 100 DEG C.  With strong acid catalysts, e.g. 70-103% sulphuric acid, alkylation may be effected at from 0-35 DEG C., treatment times at 20 DEG C. varying from 1 minute to 3 days. Alkylation may be terminated by rinsing with water, and may be accompanied or followed by sulphonation of the aromatic nuclei of the fibrous product. Where a Lewis acid catalyst or a strong acid other than sulphuric or a sulphonic acid is used for alkylation, a sulphonating agent, optionally with a catalyst, e.g. silver sulphate may be added to the alkylation bath.  Where sulphuric acid or one of the strong sulphonic acids mentioned is used in the alkylation, the treatment period may be extended, or a more strongly acting sulphonating agent, e.g. oleum, may be added to the alkylation bath. The fibrous product is finally rinsed with water, and may be neutralized in an aqueous alkaline solution. The extent of sulphonation is desirably up to 0.03 sulphonic acid groups per aromatic nucleus where the fibrous product is intended for normal textile uses, and from 0.1 to 3, preferably about 1, sulphonic acid groups per aromatic nucleus where the fibrous product is to be used as an ion-exchange medium. Fibrous products so made are stabilized against shrinkage on heating and against excessive swelling or shrinking in aqueous media, and may be used in the filtration of gases and liquids at elevated temperatures. The sulphonated fibrous products, especially in the form of pile fabrics, may be used as "endless-belt" ion-exchange fabrics in continuous ion-exchange systems, e.g. in water-softening.