Patent GB-798399-A (GB)
Title: Vinyl ether derivatives and polymers thereof
IPC: C07D295/215
Filed: 1955-09-26
Abstract: The invention comprises vinyl ether derivatives of formula: (CH2 = CHOANRCONR1)nB I wherein n is 2 or 3; A is a divalent hydrocarbon group of not more than 18 carbon atoms providing at least two carbon atoms between ether oxygen and nitrogen or such a group the chain of which is interrupted by one or more of the hetero atoms oxygen, nitrogen, and sulphur, with the proviso that in the group -OAN there are at least two carbon atoms between each hetero atom and the hetero atom nearest thereto; R is hydrogen or a monovalent hydrocarbon group of not more than 18 carbon atoms which may be substituted by halogen atoms or hydroxy, nitro, cyano, heterocyclic, or tertiary amino groups; R1 is hydrogen or a hydrocarbon group of not more than 24 carbon atoms which may be substituted in the same way as R, with the exception of heterocyclic groups and with the proviso that, when n is 2 and the two R groups are hydrocarbon or substituted hydrocarbon, such R1 groups may be joined to form a chain between their adjacent nitrogen atoms; and B is a di- or tri-valent hydrocarbon group.  In formula I the group A is preferably an alkylene group, i.e. -CmH2mwhere m is 2 to 18, R and R1 are preferably hydrogen or saturated aliphatic or alicyclic hydrocarbon groups and B is preferably a di- or tri-valent saturated aliphatic or alicyclic group, particularly C2-C18 alkylene or cycloalkylene or a residue of benzene, naphthalene, diphenyl, a diphenylalkane or a triphenylalkane.  The monomeric compounds of formula I may form homopolymers and copolymers (see Group IV (a)).  The compounds of formula I may be divided into sub-groups of various general formul , i.e. (CH2 = CHOANRCONH)nB II wherein A, R, n and B are as defined above, (CH2 = CHOANR2CONR1)nB III wherein A, B, n and R1 are as defined above and R2 is a monovalent hydrocarbon group of 1-18 carbon atoms which may be substituted by halogen atoms or hydroxyl, nitro, cyano or tertiary amino groups: (CH2 = CHOYC(R3)(R4)NHCONR1)nB IV wherein R1, n and B are as defined above, Y is an alkylene group of 1-7 carbon atoms and R3 and R4 are alkyl groups of 1-4 carbon atoms; and (CH2=CHOZNHCONR1)nB V wherein R1, n and B are as defined above and Z is a saturated cycloaliphatic group or an alkylene group of 4-18 carbon atoms giving a chain of at least four carbon atoms between the oxygen and nitrogen atoms. Compounds of formula II are prepared by reacting one mol. of an isocyanate of formula B(NCO)n wherein n=2 or 3 with two or three mols. of an aminoalkyl vinyl ether of formula: CH2=CHOANHR VI Specified compounds of formula B(NCO)n include hexamethylene diisocyanate, p-phenylene diisocyanate, 2 : 4-diisocyanato-1-chlorobenzene, 2 : 6 - diisocyanato - naphthalene, 4 : 41 - diisocyanato - diphenylmethane, 1 : 4-cyclohexylene - diisocyanate and 1 : 2 : 4-benzene-triisocyanate.  Many amines of formula VI (which are obtained by the vinylation of hydroxy-organoamines with acetylene) are specified such as: CH2=CHOCH2CH2NH2, CH2=CHOCH2CH(CH3)NHCH3, CH2=CHOCH2CH2NHC6H5, CH2=CHOCH(CH3)CH2NHC2H5, CH2=CHOCH2CH2NH-cyclo-C6H11, CH2=CHOCH2CH2NHCH2CH=CHCH3, CH2=CHOCH2CH2NHCH2CH2C­CCH3, CH2=CHOC6H10NH2, CH2=CHOCH(C6H5)CH2NH2, CH2=CHOCH2CH2OCH2CH2NH2, and CH2=CHOCH2CH2SCH2CH2NH2. Compounds of formula III, IV and V may be prepared by reacting a carbamyl chloride of formula: B(NR1COCl)n VII and an amine of one of the following formul : CH2=CHOANHR2 VIII CH2=CHOYC(R3)(R4)NH2 IX and CH2=CHOZNH2 X Specified carbamyl chlorides of formula VIII include: <FORM:0798399/IV (b)/1> and <FORM:0798399/IV (b)/2> The amines of formula VIII are all those of formula VI wherein R is other than hydrogen.  Specified amines of formula IX include: H2NC(CH3)2CH2OCH=CH2 and <FORM:0798399/IV (b)/3> Specified amines of formula X include 1-amino-cyclohexane-4-vinyl ether and H2(CH2)-OCH=CH2.  A further method by which certain of the compounds of formula II and those of formula IV may be obtained is the reaction of vinyloxyalkylisocyanates of formula CH2=CHOYC(R3)(R4)NCO XI with amines of formula B(NHR1)n XII.  The ethers of formula XI are disclosed in Specification 763,635. Specified amines of formula XII include ethylene diamine, phenylene diamine, piperazine, 1 : 2 : 6-triaminohexene and N - N1 - dibenzyl - p - phenylenediamine.  In examples: (1) the following pairs of compounds are reacted to give compounds of formula I: 1 : 8-diisocyanato - paramenthane or 1 : 6-hexamethylene diisocyanate and 2-aminoethyl vinyl ether, 1 : 6-hexamethylene diisocyanate and 2-methylaminoethyl vinyl ether, decamethylene diisocyanate and 5-aminopentyl vinyl ether, 4 : 41-diisocyanato-diphenylmethane and 2 - amino - 1 - cetyl - ethyl vinyl ether, 2 : 4-diisocyanato-1-chlorobenzene and divinyloxyethylamine, 2 : 6-diisocyanato - naphthalene and 2 - (21 : 41 - dichlorophenyl) - aminoethyl vinyl ether 4 : 41 : 411 - triisocyanato - triphenylmethane and 2-methylaminoethyl vinyl ether; (2) the following pairs of compounds are reacted to give compounds of formula I: the N : N1-bis-carbamyl chloride of piperazine and 2-methylaminoethyl vinyl ether or 3-dimethylaminopropylaminoethyl vinyl ether or 4-aminohexyl vinyl ether or 2-(N-tert.-octylamino)-ethyl vinyl ether or 2-(N-p-chlorophenylamino)-ethyl vinyl ether, the bis-carbamyl chloride of N : N1-dilauryl - hexamethylenediamine and b  - hydroxyethylaminoethyl vinyl ether, the bis-carbamyl chloride of N : N1-di-(p-chlorophenyl)-hexamethylenediamine and b -cyanoethylaminoethyl vinyl ether, the bis-carbamyl chloride of N : N1 - dibenzyl - 4 : 41 - diaminodiphenyl and octadecyl-aminoethyl vinyl ether, the bis-carbamyl chloride of N : N1-di-(p-nitrophenyl)-hexamethylene diamine and benzylaminoethyl vinyl ether, the bis-carbamyl chloride of N : N1-diethylphenylenediamine and 2-aminoisobutyl vinyl ether; (3) 2-isocyanato-isobutyl ether is reacted with the following amines to give symmetrical and asymmetrical products of formula I: trimethylenediamine, ethylenediamine, tetramethylenediamine, decamethylenediamine, phenylenediamines, 1 : 2 : 6-triaminohexane, piperazine, N : N1-dibutyl- or dibenzyl - ethylenediamine, N - benzyl - or -phenyl- or -dodecyl- or -allyl-ethylenediamine.  The compound CH2=CHOCH2CH2NHCH2CH2C­CH3 is prepared by reacting methylacetylene and ethylene oxide to give CH3C­CCH2CH2OH which is converted to the chloride with thionyl chloride and reacted with ethanolamine to form CH3C­CCH2CH2NH2CH2CH2OH which is finally reacted with acetylene to give the vinyl ether.ALSO:Vinyl ether derivatives of formula (CH2=CHOANRCONR1)nB I wherein n is 2 or 3; A is a divalent hydrocarbon group of not more than 18 carbon atoms providing at least two carbon atoms between ether oxygen and nitrogen or such a group, the chain of which is interrupted by one or more of the hetero atoms oxygen, nitrogen and sulphur, with the proviso that in the group -OAN-there are at least two carbon atoms between each hetero atom and the hetero atom nearest thereto; R is hydrogen or a monovalent hydrocarbon group of not more than 18 carbon atoms which may be substituted by halogen atoms or hydroxy, nitro, cyano, heterocyclic or tertiary amino groups; R1 is hydrogen or a hydrocarbon group of not more than 24 carbon atoms which may be substituted in the same way as R, with the exception of heterocyclic groups and with the proviso that, when n is 2 and the two R1 groups are hydrocarbon or substituted hydrocarbon, such R1 groups may be joined to form a chain between their adjacent nitrogen atoms; and B is a divalent or trivalent hydrocarbon group (see Group IV (b)) may be polymerized or copolymerized with other olefinically unsaturated compounds.  The polymerization is effected by mixing the monomer and an acyclic azo catalyst directly or in the presence of an inert solvent and warming, preferably in an atmosphere of nitrogen.  Specified azo catalysts are azodiisobutyronitrile, azodiisobutyramide, dimethyl or diethyl or dibutyl azodiisobutyrate, azobis (a , g -dimethylvaleronitrile), azobis (a -methylbutyronitrile), azobis (a -methylvaleronitrile) and dimethyl azobismethylvalerate.  Specified inert solvents are water, methanol, ethanol, isopropanol, butanol, dimethylformamide, benzene, toluene and ethylacetate.  Olefinically unsaturated compounds which may be copolymerized with the compounds of formula I are acrylamide, methacrylamide, N-methylacrylamide, N:N-dipropyl - methacrylamide, N - vinylpyrrolidone, N - vinylcaprolactam, N - vinyl - N - methylacetamide, N - vinylethyleneurea, N-vinylcarbazole, N - vinylbenzenesulphonamide, hydroxyethyl vinyl ether, ethyl N-vinyloxyethyl carbamate, N - vinyloxyethyl - ethyleneurea, butyl vinyl ether, dimethylaminoethyl vinyl ether, the methyl, ethyl, butyl and dodecyl esters of acrylic and methacrylic acids, fumaric, maleic and itaconic acids and esters and polyesters thereof, vinyl acetate, vinyl chloracetate, vinyl stearate, acrylonitrile, methacrylonitrile, a  - alkylacrylonitriles, tert.-butyl vinyl sulphide, hydroxyethyl vinyl sulphide, vinyl chloride, vinylidene chloride, 2- or 4-vinylpyridine, styrene and vinyltoluene.  In Examples: (1) 1:6-bis-(2-vinyloxyethylureido) hexane is polymerized under nitrogen in dimethylformamide solution and in the presence of dimethyl azoisobutyrate; (2) a mixture, the monomer of formula I, prepared by reacting 1 mol. of the bis-carbamyl chloride of piperazine and 2 mols. of 2-N-methylaminoethyl vinyl ether, with N-vinyloxyethyl-N:N1-ethyleneurea is copolymerized under the conditions described in (1); (3) the monomer described in (2) is copolymerized with methylmethacrylate by heating under pressure in the presence of benzoyl peroxide; (4) the monomer described in (2) is copolymerized with 4-vinylpyridine in aqueous suspension in the presence of a polyethylene oxide condensate of nonylphenol and azoisobutyronitrile.  The monomer described in (2) may also be copolymerized with vinyl acetate, acrylonitrile, aminoethyl vi