New allylic unsatd. cpds. - useful as antioxidants for stabilisation of polymers

摘要

Allylic unsatd. antioxidants of formulae (Ic) and (Ib) are new: ((Z)a(A)b(X')c(B)d(O)e(D)f (COg(E)h(CO)i(G')l)wQv (Ia) ((Z)a(A)b(X')(B)d(O)e(D)f (CO-X2)i(F)j(X3)k(G')l)wQv (Ib) Q= (U'(CO)m(L0n(CO)o(X4)p(M)q'(C))r (COOH)s(Y)t(-CH2-C(R34)=VH2)u); Z = 1-20C alkyl or a gp. of formula (i)-(viii)Z' = R15, NHR18, COOR19, or COR20; Q1Q2 = CH2NCH2, C(O)NCH2 or C(O)NC(O); R = H, 1-20C alkyl, 1-20C acyl, benzyl, or opt. alkyl-substd. cycloalkyl; one of R1,R3 = OH and the other is H; R2 = 4-12C t-alkyl, cyclohexyl, 1-methyl-cyclohex-1-yl or 9-12C t-aralkyl; R4 = H, 1-12C n-alkyl, 3-12C sec-alkyl, 4-12C t-alkyl, cyclohexyl, 1-methyl-cyclohex-1-yl or 4-12C t-aralkyl; R5 = H or Me; R6 = 1-18C alkyl; or OR13; R13 = 1-18C alkyl; R7 = H or Me; R8 = 4-8C t-alkyl, 1-methyl-cyclohex-1-yl or 9-12C t-aralkyl, T = S or CR4R10; R9 = H or Me; R10 = H, 1-12C aklyl, 5-8C cycloalkyl, benzyl, phenyl, COR11, CH2COR11, CH2CH2COR11, or CH2CH2COR11; R11 = 1-20C alkoxy, NH2, NHR12 or N(R12)2; R12 = 1-20C alkyl; R14 = as R; R15 = H, 1-20C akoxy, cyclohexyloxy (opt. alkyl substd.), benzyloxy, NRR12, N(R)benzyl, N(R12)2, N(benzyl)2, N(R) (opt. alkyl substd. cyclohexyl), N(opt. alkyl substd. cyclohexyl)2 or NH (1-20C acyl); R16 = H or 1-4C alkyl; or C(Me)(CH2R16) = spiro-cyclohexane or spiro-cyclopentane; R18 = 1-20C alkyl, benzyl or opt. alkyl substd. cyclohexyl; R19 = H or R18; R20 = NH2, N(R33) (1-20C alkyl, N(R33) (opt. alkyl substd. cyclohexyl) or N(R33) (benzyl); R33 = as R but not acyl; R21, R22, R23 = H, or 1-5C alkyl; R24,R25,R26,R27 = H, 1-5C alkyl, OH, 1-20C akloxy, arylamino, NHR33 or N(R33)2; or R25+R26 or R26+R27 = benzo; R28 = H; R29 = 1-20C aklyl, benzyl or opt. alkyl substd. cyclohexyl; R30 = H or Me; R31 = 7-20C aralkyl; R32 = H or 7-20C aralkyl, R34 = H or Me; a,b,c,d,e,f,g or h = 0,1 or 2; A = H, or 1-20C hydrocarbodiyl, -triyl or tetryl; X1,X2,X3 = O,S,N,NR, NHNH or NH-N=; B = 1-8C alkdiyl or 5-9C cycloalkdiyl; D = 1-6C alkydiyl; E = 1-20C alkdily; F = 1-20C alkdiyl; i,j,k = 0,1,2,3 or 4; G' = OCH2CH(OH)CH2, NHNHCH2CH(OH)CH2 or NHN(CH2CH(OH)CH2-)2; G2 = CH2CH(OH)CH2; l = 0-8; w = 1,2 or 3; u' = O,NH, NR, N, NHNH, =NNH or =N-N=; m = 0 or 1; l = 1-20C alkdiyl; n,o = 0 or 1; X4 = ), NH or N; p = 0 or 1; m = 1-10C akdiyl, -triyl or tetryl, all opt. substd. by OH; q' = 0,1 or 2; r = 0,1,2 or 3;s = 0 or 1; y = as X4; t = 1,2 or 3; R34 = H or Me; u = 1,2,3,4 or 5; v = 1,2 or 3. Prepn. of the antioxidants are also claimed. USE/ADVANTAGE - The cpds. (I) are useful as antioxidants for stabilisation of polymers. They may be incorporated into the polymers by (a) copolymerisation of one or more monomers with one or more cpds. (I), or (b) grafting one or more cpds. (I) onto a polymer chain with opt. simultaneous cross-linking of the polymer chain. Polymers incorporating (I) are suitable for, e.g. food and drug application. (I) contain an olefinic double bond of low reactivity which makes them more suitable than prior art antioxidants for certain applications.