Patent GB-1063055-A (GB)
Title: Production of laminates resembling linoleum
Inventor: MUELLER HERBERT
IPC: D06N3/10
Filed: 1964-06-26
Abstract: (1,3)-Diene homo-or co-polymers are modified (a) by isomerization, e.g. by heating alone or in solution with transition metals of Group VI to VIII of the Periodic Table and/or compounds which contain these transition metals in zerovalent form, or (b) by heating alone or in solution with a -ethylenically unsaturated carboxylic compounds and/or derivatives of such compounds.  The (1,3)-diene homopolymer may be a homopolymer of a C4- 12 (1,3)-diene, e.g. buta - (1,3) - diene, 2 - methylbuta - (1,3)- diene, cyclopenta - (1,3) - diene, or cyclohexa - (1,3) - diene. The (1,3) - diene copolymer may be derived from a (1,3)-diene and ethylene, propylene, 2-methyl-1-butene, an ester of an acrylic or methacrylic acid with a C1- 6 alkanol, acrylonitrile, styrene, a -, o-, m-, or p-methylstyrene, or a mixture thereof.  Specified transition metals and compounds thereof are Fe, Co, Ni, Mn, Cr, Mo, W, Pd, Pt, Ni(CO)4, Fe (CO)5, HCo(CO4, [Co(CO)4]2, H2Fe(CO)4, Fe2(CO)9, Fe3(CO)12, nickel-(o)-bis-cycloocta-(1,5)-diene, and Mn2(CO)2. Specified a -ethylenically unsaturated carboxylic compounds and derivatives thereof are maleic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid, and esters of the acids with C1- 6 alkanols. The (1,3)-diene polymers, and their modified derivatives, are oxidized by treatment either alone or in solution with an oxygen transferring agent, e.g. oxygen, organic peroxides, or conventional driers, e.g. Fe, Co, Pb, Mn naphthenates, caprylates, or oleates, to form polymers having peroxidic oxygen atoms.  The treated polymers may be mixed with wood flour, cork powder, or powdered fillers.ALSO:Coated sheet material which may be used as floor, table, or wall covering is prepared by applying a mixture of 15 to 60% by wt, of an oxidised (1,3)-diene polymer and 40 to 85% by wt. of wood, flour, cork powder and/or stone powder to a woven or non-woven web of natural and/or artificial fibres, and pressing the coated web at a temperature of from 50 -200 DEG C.  The (1,3)-diene polymer may be a homopolymer e.g. of buta-(1,3)-diene, 2-methyl buta-(1,3)-diene, cyclopenta-(1,3)-diene, cyclohexa-(1,3)-diene, or a co-polymer of a -(1,3)-diene with, for example, ethylene, propylene, 2-methyl-1-butene, an ester of acrylic or methacrylic acid with a C1-6 alkanol, acrylonitrile, styrene, a -methylstyrene, o, m, or pmethylstyrene, or a mixture thereof.  The homo- or copolymer may be modified, prior to oxidation either by isomerisation e.g. by heating alone or in solution in the presence of Group VI to Group VIII transition metals and/or compounds which contain these transition metals in zerovalent form; or by reaction with a -ethylenically unsaturated carboxylic compounds and/or derivatives of such compounds e.g. mallic anhydride, mallic acid, fumaric acid, acrylic acid, methacrylic acid, and esters thereof with C1-6 alkanols.  Oxidation may be carried out using oxygen and/or oxygen donors e.g. organic peroxides and driers e.g. Co, Fe, Pb, and Mn naphthenates, caprylates and oleates.  The organic peroxides and/or driers may be added to the oxidised polymers or mixtures thereof with wood flour, cork powder and/or stone powder, optionally with natural or synthetic resinse.g. linoxyn, linseed oil varnish, colophony, kauri gum, wood oil, and other conventional auxiliaries e.g. pigments.  The web is preferably made of jute but may also be of wool, hemp, sisal, cellulose, acetylcellulose, polyamide, polyester, polyacrylonitrile, polyethylene, polypropylene, glass or mineral fibres.