Patent GB-826945-A (GB)
Title: Polymeric aminoorgano vinyl ethers, and process for producing them
IPC: C08F28/00
Filed: 1955-12-07
Abstract: Polymers and copolymers of amino-organo vinyl ethers may be prepared by polymerizing amido-organo vinyl ethers of the form:-CH2=CHOANRCONH2 or CH2=CHOANRCOR1 where A is a saturated hydrocarbon group which provides at least two carbon atoms separating the oxygen and nitrogen atoms, and R and R1 are hydrogen or saturated hydrocarbon groups, preferably alkyl groups with 1 to 4 carbon atoms, and hydrolysing the product. Specified ethers are:-CH2=CHOCH2CH2NHCONH2, CH2=CHOCH2CH2N(CH3)CONH2, CH2=CHOCH2CH2CH2NHCONH2, CH2=CHOCH2CH2CH2N(CH3)CONH2, CH2=CHOCH(CH3)CH2NHCONH2, CH2=CHOCH(CH3)CH2N(CH3)CONH2, CH2=CHOCH2CH(CH3)NHCONH2, CH2=CHOCH2CH(CH3)N(CH3)CONH2, CH2=CHOCH2CH2NHCOH, CH2=CHOCH2CH2NHCOCH3, CH2=CHOCH2CH2NHCOC2H5, CH2=CHOCH2CH2NHCOC4H9, CH2=CHO(CH2)3NHCOH, CH2=CHO(CH2)3NHCOCH3, CH2=CHOCH(CH3)CH2NHCOH and CH2=CHOCH(CH3)CH2NHCOCH3. Specified comonomers are 1,3-butadiene, 2-fluoro - 1,3 - butadiene, 2 - chloro - 1,3 - butadiene, 2,3 - dichloro - 1,3 - butadiene, vinyl formate, vinyl acetate, vinyl chloracetate, vinyl butyrate, vinyl laurate, diallyl phthalate, acrolein, methacrolein, methyl vinyl ketone, vinyl ethyl ether, bis - (vinyloxyethyl)urea, isobutylene, styrene, divinyl benzene, divinyl toluene, divinyl naphthalene, trivinyl benzene, ethyl acrylate, methyl methacrylate, butyl methacrylate, methoxymethyl methacrylate, chlorethyl methacrylate, beta - diethylaminoethyl methacrylate, diethylene glycol dimethacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diethyl fumarate, dimethyl maleate, vinyl chloride, vinyl bromide, vinyl iodide, vinylidene fluoride, vinylidene chloride, tetrafluoroethylene, N - vinylphthalimide, N - vinylsuccinimide, vinylpyridine and N-vinylcaprolactam.  Specified catalysts are azodiisobutyronitrile, azodiisobutyramide, dimethyl, diethyl or dibutyl azodiisobutyrate, azobis-(a ,g -dimethylvaleronitrile), azobis (a -methylbutyronitrile), azobis(a -methylvaleronitrile) and dimethyl azobismethylvalerate.  The polymerization may be conducted in bulk, solution, e.g. in water, methanol, ethanol, isopropanol, butanol, dimethylformamide, benzene, toluene or ethyl acetate, or emulsion, e.g. in the presence of alkylaryl polyethoxyethanols in which the alkyl group has 8 to 18 carbon atoms and the molecule contains 6 or more ethylene oxide units, preferably in an inert atmosphere, such as nitrogen.  Partial or complete hydrolysis may be effected by acids, e.g. hydrochloric, sulphuric or oxalic acid, or alkalis, e.g. sodium, potassium, ammonium or titanium hydroxide or carbonate, in water or aqueous alcohol mixtures, preferably at 80 DEG to 100 DEG  C.  The hydrolysed polymers may be reacted with chlorocarbonate esters in water or aqueous alcohol, with disubstituted carbamyl chlorides, sulphonyl chlorides or iso-cyanates under anhydrous conditions or in the presence of inert solvents, in the presence of sodium carbonate, potassium carbonate or polyamines. The products may be used as additives to paper, fungicides, bactericides, and incorporated in regenerated cellulose, cellulose acetate or polyvinyl alcohol films to form perm-selective membranes. They may be used as plasticizers for vinyl resins, e.g. polyvinyl chloride and copolymers of vinyl chloride with vinyl acetate, vinylidene chloride or acrylonitrile, and cellulose derivatives. Products derived from polyunsaturated comonomers or cross-linked by reacting with polychlorocarbonates or polyisocyanates may be used as ion-exchange resins.  Cellulose derivative compositions.-Polycarbamates, polyureides and polysulphonamides prepared by reacting amino-organo vinyl ether polymers with chlorocarbonic acid esters, disubstituted carbamyl chlorides and sulphonyl chlorides are plasticizers for cellulose derivatives. Example 4(d) describes the use as plasticizers for cellulose acetate and cellulose butyrate of the product obtained by hydrolysing and reacting with dimethyl carbamyl chloride a copolymer of 97 mol. per cent of acetamidoethyl vinyl ether and 3 mol. per cent of N,N1-bis-vinyloxyethyl urea.  Specifications 747,184, 786,927, 822,266 and U.S.A. Specification 2,647,886 are referred to.