Patent GB-1020620-A (GB)
Title: Ferrated cellulose derivatives and graft copolymers thereof
IPC: D06M14/00
Filed: 1964-04-02
Abstract: A ferrated cellulose derivative is made by reacting alkali cellulose with at least one organic sulphide having in its structure the groups <FORM:1020620/C3/1> and thereafter reacting the resultant cellulose sulphide derivative with a soluble iron salt. Preferably the organic sulphide is a cyclic compound of 5-8 carbon atoms having the thiirane structure or an alkylene sulphide of the formula <FORM:1020620/C3/2> in which the R's are (a) hydrogen, (b) alkyl groups of 1-7 carbon atoms, (c) mono-, di- and trihalo substituted alkyl groups of from 1-7 carbon atoms, provided that when R has a single carbon atom it is singly substituted by a halo atom, (d) alcohols of from 1-7 carbon atoms, (e) ethers of said thiirane alcohols in which the acid moiety is a fatty acid of from 1-7 carbon atoms or an aromatic acid of from 7-15 carbon atoms, of (f) ethers of said thiirane alcohols in which the ether moiety of said alcohol is an aliphatic alcohol of from 1-7 carbon atoms or an aromatic alcohol of from 7-15 carbon atoms, both R's being the same or different. Specified organic sulphides include ethylene sulphide and propylene sulphide. Specified iron salts include ferric and ferrous bromides, chlorides and sulphates, ferric nitrate, ferrous acetate, ferrous ammonium sulphate, ferrous sulphate.  The ferrated cellulose derivative may be reacted with at least one polymerizable or copolymerizable ethylenically unsaturated monomer in the presence of a free radical initiator to produce a copolymer.  Reaction may be effected in an aqueous solution of the ethylenically unsaturated monomer in the presence of an emulsifying agent, and the free radical initiator may be a peroxide compound, e.g. hydrogen peroxide, ammonium persulphate, alkali metal persulphate, t-butyl hydroperoxide, cumene hydroperoxide, or benzoyl peroxide.  Suitable polymerizable or copolymerizable ethylenically unsaturated monomers include (1) alkyl acrylic acids with 0-5 carbon atoms in the alkyl chain (2) alkylacrylic acid esters of 0-5 carbon atoms in the alkyl chain in which the ester is formed from (a) alkyl alcohol of 1-20 carbon atoms, (b) cycloalkyl alcohol of 5-8 carbon atoms, (c) polyhydric alcohol of 2-10 carbon atoms, (d) condensation products of alkylene glycols of 2-6 carbon atoms, (e) nitro alcohols in which the alkyl chain has 2-7 carbon atoms, (f) substituted amino alcohols of 2-7 carbon atoms in the alkylene chain, and 1-7 carbon atoms in the chain on the amino moiety, or (g) cyanoalkyl alcohols in which the alkyl chain is 2-7 carbon atoms, (3) alkylacrylic acid amides of 0-5 carbon atoms in the alkyl chain in which the amide is formed from ammonia, primary and secondary amines, or primary and secondary diamines of 2-16 carbon atoms, (4) alkylene glycol dialkyl acrylates of 0.5 carbon atoms in the alkyl chain in which the alkylene glycol is (a) alkylene glycol of 2-8 carbon atoms, (b) the glycol ether, or (c) the glycol polyether, (5) aliphatic acid esters of 1-olefin alcohols containing from 2-24 carbon atoms in the acid chain and in which the 1-olefin alcohol precursor is of from 2-8 carbon atoms, (b) ethylenically unsaturated aliphatic diacids or their esters or amides of from 4-10 carbon atoms, (7) copolymerizable aliphatic diene compounds, (8) aliphatic 1-olefins of 2-24 carbon atoms, (9) 1-olefin ethers of aliphatic compounds in which the 1-olefin is of 2-8 carbon atoms and the aliphatic moiety is from 1-7 carbon atoms (10) ethylenically unsaturated nitrile compounds, (11) aromatic acid esters of unsaturated alcohols in which the alcohol precursor is of 2-7 carbon atoms and in which the aromatic compound has 1-4 acid groups, (12) ethylenically unsaturated heterocyclic compounds in which the heterocycle has 3-5 carbon atoms and the hetero atom is selected from the group consisting of N, O, or S, or (13) aromatic compounds having ethylenically unsaturated substituents in which the aromatic compound is further substituted by (a) alkyl groups of from 1-7 carbon atoms, (b) halogen or (c) alkyl groups of from 1-7 carbon atoms substituted by halogen and in which the ethylenically unsaturated moieties are of from 2-5 carbon atoms and are further substituted by (a) alkyl groups of 1-3 carbon atoms, or (b) halogen.  Specified ethylenically unsaturated monomers include acrylic acid, acrylamide, acrylonitrile, styrene, 2-ethylhexyl acrylate and/or cyanoethylacrylate.  In a preferred method, the alkali cellulose is reacted with the organic sulphide until about 6-80% of the sulphide has been combined with the alkali cellulose and after reaction of the cellulose sulphide derivative so obtained with the soluble iron salt, the ferrated cellulose sulphide derivative is reacted with the ethylenically unsaturated monomer in a concentration of about 0.05-99.9% based on the concentration of the latter, the concentration of the monomer solution being from 1-100% and the solution is thereafter buffered, the free radical initiator added to the solution, and the reactor allowed to proceed at from 0-100 DEG C. from 5 mins.-96 hrs.