Multifunctional alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinones and their use as polymerization regulators/initiators

A polymerizable composition, comprising

• a) at least one ethylenically unsaturated monomer or oligomer, and
• b) a compound of formula Ia, Ib, Ic or Id or a mixture thereof
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• wherein
• R1 and R2 are independently of each other hydrogen, C1-C18alkyl or phenyl;
• R3 is hydrogen, C1-C18alkyl, C1-C18alkyl which is substituted by OH, or phenyl which is unsubstituted or substituted by OH, halogen, C1-C8alkoxy or C1-C8alkyl;
• X is O, S, NR4 or, if Z is —O—CH2—, X is additionally a direct bond;
• R4 is hydrogen or C1-C18alkyl;
• Z is a direct bond and if R1 is hydrogen and R2 phenyl, Z is additionally —O—CH2—;
• Y is a radical derived from a polyol, a polyamine, a polyaminoalcohol, a polyaminothiol, a polyhydroxytiol, a polyaminohydroxythiol or a polythiol having 2 to 20 —OH, SH and/or —NR5H groups, wherein R5 is hydrogen, C1-C18alkyl or phenyl;
• or if X is a direct bond and Z is —O—CH2—, Y is a radical derived from a polycarboxylic acid having 2-20 carboxylic functions;
• A and A′ together are ═O;
• or
• A′ is hydrogen;
• and
• A is hydrogen, —O—R100, wherein R100 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, NHR100, NR100R103 or cyanoethyl;
• or a group
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• R101 is hydrogen, —COOH, —COO(C1-C4alkyl), —COO-phenyl, —COObenzyl, C1-C8alkoxy, C1-C18alkyl, C2-C4alkenyl, C1-C18alkyl or C2-C4alkenyl substituted by OH, —COOH, —COO(C1-C4)alkyl, C2-C18alkyl which may be interrupted by one or more oxygen atom, unsubstituted cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl;
• or cyclopentyl, cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted by C1-C4alkyl, —COOH or —COO—(C1-C4alkyl)
• R102 is hydrogen, C1-C18alkyl or R101 and R102 together with the nitrogen atom form a 5-membered ring which may have an unsaturated bond or be fused to a benzene ring;
• R103 is hydrogen or C1-C18alky;
• or
• A and A′ together are a group
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• wherein
• Z1 is O, NR202 or when R201 represents alkyl or aryl Z1 is additionally a direct bond;
• R202 is H, C1-C18alkyl or phenyl;
• R201 is H, straight or branched C1-C18alkyl or C3-C18alkenyl, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl, C5-C12cycloalkyl or C5C12cycloalkenyl;
• phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
• or
• —C(O)—C1-C18alkyl, or an acyl moiety of a α,β-unsaturated carboxylic acid having 3 to 9 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
• —SO3−Me+, —PO(O−Me+)2, —P(O)(OR2)2, —SO2R2, —CO—NH—R2, —CONH2, COOR2, or Si(Me)3, wherein Me+ is ═H+, ammonium or an alkali metal cation;
• or
• A is O—Y1 and A′ is O—Y2 forming a ketale structure in the 4 position;
• wherein
• Y1 and Y2 are independently C1-C12alkyl, C3-C12alkenyl, C3-C12alkinyl, C5-C8cycloalkyl, phenyl, naphthyl, C7C9phenylalkyl;
• or
• Y1 and Y2 together form one of the bivalent groups —C(R301)(R302)—CH(R303)—, —CH(R301)—CH2—C(R302)(R303)—, —CH(R302)—CH2—C(R301)(R303)—, —CH2—C(R301)(R302)—CH(R303)—, o-phenylene, 1,2-cyclohexyliden,
• —CH2—CH═CH—CH2— or
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• wherein
• R301 is hydrogen, C1-C12alkyl, COOH, COO—(C1-C12)alkyl or CH2OR304;
• R302 and R303 are independently hydrogen, methyl, ethyl, COOH or COO-(C1-C12)alkyl;
• R304 is hydrogen, C1-C12alkyl, benzyl, or a monovalent acyl residue derived from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid having up to 18 carbon atoms.