Patent GB-812140-A (GB)
Title: Improvements in linear copolymers
IPC: C08F8/44
Filed: 1955-06-27
Abstract: Linear quaternary ammonium polymers or copolymers are prepared by aminolyzing a polymer of at least 20 mol. per cent of an alkyl acrylate, methacrylate, ethacrylate or propacrylate, and if desired, at least one other monoethylenically unsaturated monomer, with an amine of the formula <FORM:0812140/IV (a)/1> or <FORM:0812140/IV (a)/2> in which R1 is hydrogen or a C1-C4 alkyl group, A is a C2-C10 alkylene group or a divalent saturated aliphatic group consisting of a plurality of C2-C10 alkylene groups each pair of which is connected by an ether oxygen atom, R2 and R3 are (1) separate individually selected C1-C12 alkyl, hydroxyalkyl, alkoxyalkyl or (polyalkoxy) alkyl groups; or (2) a single saturated group which together with the N atom forms a heterocyclic group containing 5 of 6 atoms in the rin of which 4 or 5 are carbon atoms and 1 or 2 are O, N or S atoms, of which one is the N atom of the group -NR2R3 of the formula, the second, if nitrogen, being substituted by a C1-C18 alkyl group, R4 is a saturated or unsaturated C1-C18 linear hydrocarbon group, a C2-C18 (polyalkoxy) alkyl group, a C1-C18\t hydroxyalkyl group or a C7-C24 aralkyl, substituted aralkyl or phenoxyalkyl group, X is OH or a negative salt-forming atom or radical and n is 1 or 2, and when an amine of the first mentioned formula is used, subsequently quaternizing at least 20 mol. per cent of the units in the aminolyzed polymer with an alkylating agent R4X, R4 and X being as above.  The starting polymers may be derived from the esters alone or in admixture with one another or with other monomers such as vinyl aromatic hydrocarbons, ethylene, acrylonitrile and substituted acrylonitriles, acrylamide and substituted acrylamides, vinyl esters, vinyl ethers, fluorinated vinyl compounds and N-vinyl compounds, numerous examples of monomers of the above types being provided. Preferred amines for use in the aminolysis reaction are dimethylaminopropylamine, N - dimethylaminoethyl - N - butylamine, di(butoxyethyl)aminoethylamine, aminopropylmorpholine, dimethylaminoethylamine, dimethylaminodecylamine, dimethylaminoethoxyethylamine and bis - (dimethylaminoethyl) amine. Preferred alkylating agents are an alkylene oxide, styrene oxide and inorganic esters of (1) C1-C18 saturated and unsaturated aliphatic alcohols; (2) C7-C24 aralkyl and substituted aralkyl alcohols, and (3) C7-C24 phenoxyalkyl alcohols.  The use of alkylene oxides as alkylating agents gives rise to quaternary ammonium hydroxides which may be neutralized with an acid.  The quaternary ammonium polymers may be used as bactericides, fungicides, antistatic agents, acid ion absorbers, dispersants, flocculating agents, softening agents for cellulosic materials, battery separators, permselective membrances, anchoring agents for paper and cellulosic pulps, soil conditioners, as additions to film-forming materials to improve the dyeing characteristics thereof, as solvents for cellulosic materials and in the isolation of protein fractions by forming an insoluble complex and regenerating the protein.  The above applications are exemplified by a fungicidal composition comprising a quaternary ammonium copolymer in admixture with talc or clay, a permselective membrane made by extruding an aqueous acetone solution of quaternary ammonium copolymer and cellulose acetate into water and a polyacrylonitrile fibre of improved dye-receptivity from a solution made by dissolving a small amount of quaternary ammonium polymer in a dimethylformamide solution of polyacrylonitrile.  In addition the copolymers may be modified by after-treatment, e.g. a methyl acrylate/N-vinyl - 2 - pyrrolidone copolymer is aminolysed with bis-(dimethylaminoethyl) amine, alkylated with propylene oxide and then treated with ethylene oxide to give a polyethylene oxide quaternary copolymer effective as an anti-static agent on synthetic films and fibres.ALSO:The accumulation of static charges on fibres, filaments and fabrics, made from cellulose esters, nylon, polyesters and acrylonitrile polymers, is prevented or reduced by applying thereto a quaternary ammonium polymer or copolymer obtained by the aminolysis of polymers or copolymers of alkyl acrylates, methacrylates, ethacrylates or propacrylates (see Group IV (a)). In Example (15) fibres made from synthetic materials are treated with a solution in dimethyl formamide of a copolymer obtained by the aminolysis of a methyl acrylate (N-vinyl-2-pyrrolidone copolymer with bis-(dimethylaminoethyl) amine followed by quaternization with propylene oxide.  In addition the thus formed quaternary copolymer may be treated with ethylene oxide to yield a polyethylene oxide quaternary copolymer which is also effective as an antistatic agent.ALSO:Water-supplies may be purified or the filtration of acid-leached ores may be improved by the addition thereto of flocculating and aggregating agents which are quaternary ammonium copolymers obtained by the aminolysis of polymers of alkyl acrylates, methacrylates, ethacrylates or propacrylates (see Group IV(a)).  In an example (8), a quaternary ammonium copolymer obtained by the aminolysis of polymethylacrylate with dimethyl-amino-propylene followed by quaternization with dimethyl sulphate is stated to be useful for the above purposes.ALSO:Sugar-cane extracts are clarified with quaternary ammonium copolymers obtained by the aminolysis of polymers of alkyl acrylates, methacrylates, ethacrylates or propacrylates (see Group IV (a).  According to an Example (8), sugar-cane extracts may be clarified with a copolymer obtained by the aminolysis of polymethylacrylate with dimethylaminopropylamine followed by quaternization with dimethyl sulphate.  Fungicidal compositions comprise a quaternary ammonium copolymer of the above type and a diluent such as talc or clay.  A specified copolymer is one obtained by the aminolysis of polymethyl acrylate with dimethylaminopropylamine, followed by quaternization with octyl benzyl chloride.