Patent GB-815229-A (GB)
Title: Aminoorgano vinyl ethers and derivatives thereof
IPC: A01N33/08
Filed: 1955-09-20
Abstract: The compound: <FORM:0815229/III/1> and homopolymerized 2-(N-2-ethylhexylamino) isobutyl vinyl ether are employed at 0.1 to 5 per cent concentrations in cutting oils and mineral lubricating oils as corrosion inhibitors, antioxidants and dispersants. Specifications 369,297, 427,036, [both in Group IV], 641,436 and 765,792, [both in Group IV (b)], are referred to.ALSO:Vinyloxyorganoamino compounds of the formulae CH2:CHOZC(R)(R1)NHR2 and CH2:CHOANHC(R)(R1)(R4), in which Z is a divalent hydrocarbon group (preferably a C1-7 alkylene group), R and R1 are C1-4 alkyl groups, R2 is hydrogen, a C1-18 hydrocarbon group (e.g. an alkyl, benzyl or cyclohexylmethyl group), a heterocyclic group (e.g. a 2-thienyl group) or a heterocyclic-substituted hydrocarbon group (e.g. a 2-thenyl or 2-tetrahydrofurfurylmethyl group), R4 is a C1-21 alkyl group (preferably a C1-4 alkyl group) and A is a C2-18 hydrocarbon group with a chain of at least 2 carbon atoms between the ether oxygen and nitrogen (preferably a C2-6 alkylene or cyclohexylene-1:2 group), alone, or admixed with one or more other polymerizable ethylenically unsaturated monomers are polymerized in bulk, or as suspensions in aqueous or organic solvents in the presence of a polymerization catalyst. Exemplified co-monomers are acrylic and methacrylic esters such as ethylene diacrylate, methyl, ethyl, butyl, dodecyl and octadecyl acrylates and methacrylates, vinyl esters such as vinyl acetate, propionate, butyrate, laurate and stearate, acrylonitrile, methacrylonitrile, hydrocarbons such as ethylene, styrene, vinyltoluene and divinyl benzene, N-vinyl compounds such as N-vinyl-N-methylacetamide, N-vinyl-pyrrolidone, N-vinyl-carbazole and N-vinyl-sulphonamide, vinyl ethers such as butyl vinyl ether, ethylene glycol-bis-vinyl ether, ethanedithio-bis-vinyl ether and N:N-bis-vinyloxyethylurea, and other vinyl or vinylidene compounds such as methylene-bis-acrylamide.  Specified solvents are water, benzene, toluene and b -ethoxyethyl acetate.  Specified polymerization catalysts are azoisobutyronitrile and dimethyl azoisobutyronitrile. Exemplified vinyloxyorganoamino monomers are CH2:CHOCH2C(CH3)2NHCH2Ph <FORM:0815229/IV (a)/1> <FORM:0815229/IV (a)/2> <FORM:0815229/IV (a)/3> CH2:CHOCH2C(CH3)NHC2H5, CH2:CHOCH2C(CH3)NHCH2CH(CH3)2, <FORM:0815229/IV (a)/4> <FORM:0815229/IV (a)/5> <FORM:0815229/IV (a)/6> <FORM:0815229/IV (a)/7> CH2:CHOCH2C(CH3)2NHCH3, CH2:CHOCH2C(CH3)2NH2, CH2:CHOCH2C(CH3)(C4H9)NH2, CH2:CHOCH2C(CH3)(C4H9)NHCH2Ph, <FORM:0815229/IV (a)/8> <FORM:0815229/IV (a)/9> <FORM:0815229/IV (a)/100> CH2:CHO(CH2)2NHC(CH3)3, CH2:CHOCH(C10H21)CH2NHC(CH3)3, CH2:CHOCH(C16H33)CH2NHC(CH3)3, CH2:CHOCH(Ph)CH2NHC(CH3)3, CH2:CHOCH(CH:CH2)CH2NHC(CH3)3, 2 - tert. - butylaminocyclohexanol - 1 vinyl ether, 2 - N - tert. - tetracoxylaminoethyl vinyl ether, N-tert.-butylaminodecyl vinyl ether and also those derived by reacting acetylene with aminoalcohols such as 4-amino-4-methylpentanol, 4 - amino - 4 - methyl - 2 - pentanol, 2 - amino - 2 - ethylpropanol, 2 - N - butylamino - 2 - methylpropanol, 2 - N - dodecylamino - 2 - methylpropanol, 2 - N - allylamino-2 - methylpropanol, 2 - N - cyclohexylamino - 2-methylpropanol, 2 - amino - 2 - methylbutanol, 2 - N - methylamino - 2 - methylbutanol, 2 - N-benzylamino - 2 - methylbutanol, 2 - N - cyclohexylamino - 2 - methylbutanol, 2 - N - tert.-butylaminopropanol, 3 - N - tert. - butylaminopropanol, 2 - N - 11:11:51 - trimethylheptylaminoethanol, HO(CH2)2NHC(CH3)2C15H31, HO(CH2)2NHC(CH3)2C21H43, HO(CH2)4NHC (CH3)3 and HOCH(C6H13)CH2NHC(CH3)3.  The polymers may be modified by reaction with monofunctional reactants such as anhydrides, alkylene oxides, alkyl isocyanates, acid chlorides and ketenes.  Thus poly-2(N-tert.-butylamino) ethyl vinyl ether is reacted with ethyl isocyanate to yield a poly (N-ethylurea).  The polymers may also be insolubilized by reaction with reagents having two functional groups reactive with the amino groups in the polymer, e.g. diisocyanates, bis - chloroformates and bis - acid chlorides.  Thus poly-2-aminoisobutyl vinyl ether is modified with 2:4-diisocyanatotoluene; a copolymer of methyl methacrylate and 2-aminoisobutyl vinyl ether is modified with p:p1-diisocyanatophenylmethane or 1:8-paramenthane diisocyanate. Uses: the above products may be used as coating and impregnating compositions, for making films and fibres, for treating textiles, as oil additives, as corrosion inhibitors, as acid acceptors, as emulsifiers, as adhesives, as ion-exchange resins which are also capable of removing metals, aldehydes, epoxides, isocyanates and ketones from solution, and as gasfade inhibitors and dye-receptivity improvers for cellulose acetate and polyacrylonitrile films and fibres; thus 2 to 5 per cent of polymerized 2-aminoisobutyl vinyl ether (based on fibre-forming polymer) may be added to a dimethylformamide solution of polyacrylonitrile and films and fibres having increased dye-receptivity formed therefrom.  The vinyloxy monomers of formulae (1) and (2) may also be added to cellulose acetate dopes to inhibit gas-fading of cellulose acetate dyes; thus the compounds CH2:CHOCH2C(CH3)(C4H9)NH2 and CH2: CHOCH2C(CH3)3NHCH2CH(CH3)2 may be added to cellulose acetate dopes in proportions of 5 per cent and 2-10 per cent by weight of acetate solids, respectively, and films and fibres formed from such dopes. Specifications 369,297, 427,036, [both in Group IV], 641,436, [Group IV (b)], and 765,792 are referred to.ALSO:The invention comprises vinyl ethers of the formul  (1) CH2 : CHOZC(R)(R1)NHR2 wherein Z is a divalent saturated hydrocarbon group (preferably a C1-7 alkylene group), R and R1 are C1-4 alkyl groups and R2 is hydrogen, a C1-C18 hydrocarbon group (e.g. an alkyl, benzyl or cyclohexylmethyl group), a hetero-cyclic group (e.g. a 2-thienyl group) or a hetero-cyclic-substituted hydrocarbon group (e.g. a 2-thenyl or 2-tetrahydrofurfurylmethyl group) and (2) CH2 : CHOANHC(R)(R1)(R4) wherein A is a C2-18 hydrocarbon group with a chain of at least 2 carbon atoms between the ether oxygen and nitrogen (preferably a C2-C6 alkylene or cyclohexylene-1 : 2 group), R and R1 are C1-4 alkyl groups and R4 is a C1-21 alkyl group (preferably a C1-4 alkyl group). The compohnds are prepared by reacting amino compounds of the formula HOZC(R)(R1)NHR2 or HOANH C(R)(R1)(R4) with acetylene in the presence of a strongly basic alkali metal compound at a temperature of 100 DEG to 180 DEG  C. and under a pressure of 200 to 500 p.p.s.i.g.  The basic catalyst may be an alkali metal hydroxide or an alkali metal salt of the aminoalcohol reactant.  The products may be reacted with one or more moles. of an alkylene oxide (e.g. ethylene or propylene oxide) to produce the corresponding N-hydroxyalkyl- or N-hydroxyalkyleneoxyalkyl-derivatives.  The products and their N-hydroxyalkyl derivatives may be quaternated with benzyl chloride or dimethyl sulphate.  With anhydrides and acid chlorides the corresponding amides are formed.  Alkyl isocyanates react to give N-alkyl-N1-vinyloxy-organo - N1 - R2- or -C(R)(R1)(R4) - substituted ureas; thus N-tert.-butylaminoethyl vinyl ether reacts with ethyl isocyanate to give the urea <FORM:0815229/IV (b)/1> and N-tert.-octylaminoethyl vinyl ether reacts with butyl isocyanate to give the urea <FORM:0815229/IV (b)/2> Halocarbonates of the formula XCOOR DEG  (X being chlorine or bromine and R DEG  being an aliphatic hydrocarbon group) react with the amino-organo-vinyl ethers in presence of an acid-binding agent to give the corresponding carbamate derivatives; thus CH2 : CHOCH2C(CH3)2NH2 reacts with methyl chlorocarbonate to give the carbamate CH2 : CHOCH2C(CH3)2NHCOOCH3 These carbamate derivatives may be heated to 170 DEG  to 300 DEG  C. in presence of a base to yield the corresponding isocyanates; thus the carbamate CH2 : CHOCH2C(CH3)2NHCOOCH3 yields the isocyanate CH2 : CHOCH2C(CH3)2NCO on heating.  With cyanogen chloride (CNCl) the amino-organo vinyl ethers yield the corresponding cyanamides; thus the compound CH2 : CHOCH2C(CH3)2NH2 reacts with CNCl to give the cyanamide CH2 : CHOCH2C(CH3)2NHCN Exemplified amino-organo vinyl ethers are CH2 : CHOCH2C(CH3)2NHCH2Ph, <FORM:0815229/IV (b)/3> <FORM:0815229/IV (b)/4> <FORM:0815229/IV (b)/5> <FORM:0815229/IV (b)/6> 2 - tert - butylaminocyclohexanol - 1 vinyl ether, 2 - N - tert - tetracosylaminoethyl vinyl ether, N-tert-butylaminodecyl vinyl ether and also those derived from aminoalcohols such as 4 - amino - 4 - methylpentanol, 4 - amino - 4 - methyl - 2 - pentanol, 2 - amino - 2 - ethylpropanol, 2 - N - butylamino - 2 - methylpropanol, 2 - N - dodecylamino - 2 - methylpropanol, 2 - N - allylamino - 2 - methylpropanol, 2 - N - cyclohexylamino - 2 - methylpropanol, 2-amino-2 - methylbutanol, 2 - N - methylamino - 2 - methylbutanol, 2 - N - benzylamino - 2 - methylbutanol, 2 - N - cyclohexylamino - 2 - methyl - butanol, 2 - N - tert - butylaminopropanol, 3-N-tert - butylaminopropanol, 2 - N - 11 : 11 : 51-trimethylheptylaminoethanol, HO(CH2)2NHC(CH3)2C15H31, HO(CH2)2NHC(CH3)2C21H43, HO(CH2)4NHC(CH3)3 and HOCH(C6H13)CH2NHC(CH3)3 The vinyl ethers of formul  (1) and (2) may be polymerized or copolymerized with other ethylenically unsaturated compounds. Some of these polymers function as ion-exchange resins and are also capable of removing metals, aldehydes, epoxides, isocyanates and ketenes from solution. Aminoalcohols of the formula HOZC(R)(R1)NHR2 and HOANHC(R)(R1)(R4) are prepared (1) by reacting suitably unsaturated alcohol (e.g. 3 : 7-dimethyl- D 6 : 7-octenol) with hydrogen cyanide in presence of sulphuric acid monohydrate and hydrolysing the resultant formamide, e.g. of the formula <FORM:0815229/IV (b)/7> (2) by reacting formaldehyde and nitroalkanes (e.g. 2-nitrobutane and 2-nitropentane) and reducing the product (e.g. 2-nitro-2-methylolbutane and 2 - nitro - 2 - methylolpentane respectively); (3) by reacting a tertiary-alk