Patent GB-757043-A (GB)
Title: Improvements in polymeric materials and methods of preparing them
Inventor: CUPERY MARTIN ELI
IPC: C08G59/32
Filed: 1954-02-10
Abstract: Polymeric phosphates are obtained by reacting a copolymer containing 98 to 35 per cent of styrene or methyl styrene and 2 to 65 per cent of a polymerized ethylenically unsaturated epoxy monomer such as allyl glycidyl ether, myrcene monoepoxide, glycidyl acrylate and methacrylate, 4-vinylcyclohexene, 1,3-butadiene monoepoxide, vinyl and allyl glycidyl phthalates, allyl glycidyl maleate, methallyl glycidyl ether and allyl a ,b -epoxyisovalerate with at least 0.5 mol. of phosphoric acid or partially esterified phosphoric acid per oxicane oxygen atom in the molecule.  Up to 25 per cent of vinylidene compounds such as vinyl fluoride and chloride, vinylidene chloride, vinyl acetate and propionate, acrylic and methacrylic acids, methyl methacrylate, ethyl acrylate, acrylo- and methacrylonitriles, methacrylamide, ethylene, isobutylene, allyl alcohol and methyl vinyl ketone may also be present in the copolymer.  In examples the copolymer is prepared, using as catalyst benzoyl or di-t-butyl peroxide, or azodiisobutyronitrile, which is dissolved in the epoxy monomer and added gradually to the heated mixture and the viscoxity reduced by di-(2-ethoxyethyl) ether or as an alternative a mixture of styrene, glycidyl methacrylate and di-t-butyl peroxide is added to xylene over a period and refluxed.  O-, m- or p-phosphoric acid or the methyl or butyl acid phosphates, which may be in aqueous solution, may be added to a solution of the polymer in benzene, toluene, xylenes, acetone, methyl ethyl ketone, cyclobutanone, acetophenone, di-n-butyl ether, dioxone, tetrahydrofurane, diphenylene oxide, ethanol, n-butanol, or isopropanol, and heated. The product is precipitated by water or salt solution and washed. The polymeric esters are soluble in water and alkalies such as sodium or potassium hydroxide, ammonia, methylamine, n-butylamine, di- and triethylamines, mono-and diethanolamines and cyclohexamine and form salts with metals such as copper, silver, zinc, aluminium, iron, nickel, cobalt, chromium and manganese.  Solutions of the polymers in acetone, methyl isobutyl ketone or n-butyl alcohol may be used as coating compositions with addition of pigments such as titanium dioxide, carbon black, iron blues, phthalocyanin blues and greens, metal oxides and chromates and organic maroons, extenders such as talc, barytes, and china-clay, and other film-formers such as urea-formaldehyde, melamine-formaldehyde, and alkyd resins.  The coatings may be heat-cured to an infusible, insoluble state.  The alkali-soluble polyphosphates may be used to size fibres and treat leather, and the copper and nickel salts in aqueous solution may be applied to substrates of paper, textiles, wood, leather, or ceramics and after-treated with ammonia or alkali-metal polyphosphates. Copper and mercury salts with bacterical and fungicidal properties may be used in insecticides, insect repellants, herbicidal compositions and wood and textile preservatives.  The phosphates are compatible with colloidal silica sols and are useful as adhesives, finishes and in wax dispersions.  Aqueous solutions of low molecular weight polyphosphates are surface active and may be used in emulsion, polymerizations, pigment dispersions, lime requestering agents or as detergents.  The Specification refers also to rendering styrene-unsaturated epoxy copolymers insoluble and infuzible by heating with polyamines such as m-phenylenediamine, p,p1-diaminodiphenylmethane, diacetone, diamine, bis-(p-aminocyclohexyl) methane, p-xylylenediamine, tripropylene tetramine, tetraethylene pentamine and 3,31-diaminodipropyl ether.ALSO:Myrcene monoepoxide (2-methyl-2,3-epoxy-6-methylene-7-octene) <FORM:0757043/IV(a)/1> is prepared by treating a mixture of 2 moles commercial myrcene and 4.8 moles of peracetic acid in 2.85 moles of acetic acid at 0 DEG -5 DEG C.