Patent GB-1108294-A (GB)
Title: Process for producing formaldehyde copolymer having amino groups or substituted amino groups which are highly dyeable
IPC: C08G2/00
Filed: 1965-08-13
Abstract: A dyeable formaldehyde copolymer is prepared by reacting a formaldehyde copolymer comprising oxymethylene units and from 0.1 to 10 molar per cent side chain halogenated comonomer units with an amount of ammonia or of an amine which is in molar excess of the amount of halogen present.  The copolymer may also comprise oxyalkylene units.  Specified copolymers are those prepared by copolymerizing a mixture of (a) formaldehyde, trioxane or tetraoxane and (b) a halogen-containing alkylene oxide, a halogen containing cyclic ether or acetal, a halogen-containing cyclic vinyl ether or a halogen-containing aldehyde, e.g. formaldehyde-epichlorhydrin copolymer. Terpolymers &c. such as trioxane/monochloro-acetaldehyde / ethylene oxide, trioxane / parachlorobenzaldehyde / monochloroacetaldehyde / 1,3-dioxolane; formaldehyde/acetaldehyde/epichlorohydrin, and formaldehyde/chloral/chloroethyl-vinyl ether may be used as may also the copolymer prepared by grafting a halogen containing vinyl monomer, e.g. dichlorostyrene, or halogen containing dienic monomer on to a formaldehyde homopolymer or a formaldehyde/alkylene oxide copolymer.  Amines include diisopropylamine, dibutylamine, cyclohexylamine, diphenylamine, monomethylaniline, mono- and di-ethanolamine, metaxylenediamine, phenyl alpha or beta-naphthylamine or triethylenetetramine. The reaction with ammonia or amine may be carried out at below 200 DEG  C. in a polar solvent, e.g. water, an alcohol or dimethyl formamide; the reaction may be carried out so as to leave a portion of halogen atoms unreacted. The aminated copolymers may contain anti-oxidants, light stabilizers and heat stabilizers. Examples are given of the dyeing of the copolymers.ALSO:Fibres of aminated copolymers prepared by reacting a formaldehyde copolymer comprising oxymethylene units and from 0.1 to 10 molar per cent side chain halogenated comonomer units with an amount of ammonia or of an amine which is in molar excess of the amount of halogen present are dyed.  The fibres may be hot drawn to form filaments before dyeing.  Specified copolymers are those prepared by copolymerising a mixture of (a) formaldehyde trioxane or tetraoxane and (b) a halogen-containing alkylene oxide, a halogen-containing cyclic ether or acetal, a halogen-containing cyclic vinyl ether or a halogen-containing aldehyde e.g. formaldehyde-epichlorhydrin copolymers.  Ter acid higher polymers such as trioxane/monochloroacetaldehyde/ethylene oxide, trioxane/parachlorobenzaldehyde/monochloroacetaldehyde/1, 3-dioxolane; formaldehyde/acetaldehyde/epichlorohydrin and formaldehyde/chloral/chloroethyl vinyl ether may be used as may also the copolymer prepared by grafting a halogen-containing vinyl monomer e.g. dichlorostyrene or a halogen containing dienic monomer on to a formaldehyde homopolymer or a formaldehyde/alkylene oxide copolymer. These copolymers may also contain antioxidants and heat and light stabilisers.  In Examples (b) a formaldehyde/4-chloromethyl-1, 3-dioxolane copolymer which has been aminated using tributylamine is mixed with 0.5% 4, 4\sv-butylidene bis (3-methyl-6-tert-butylphenol) and 1% of a polyurethane as stabilisers and melt-spun at 190 DEG C the fibre being then hot drawn by 300% at 140 DEG C to form a 2-denier filament.  Five parts of this filament are dipped in an aqueous solution containing 0.5 part ethylene diamine and heated at 90 DEG C for 3 hours.  The fibre is cooled, water washed, dried and dipped in 100 ml. of an aqueous solution containing 0.49/lit. Congo Red and 20g/lit sodium sulphate and dyed at 100 DEG C for 2 hours and (7). A similar procedure is used using 2-chloromethyl, 1-3-dioxolane and dyeing with Acid Brilliant Scarlet 3R.