US 2004/0176553 A1Published application

4-Imino-n-alkoxy or oxy-polyalkyl-piperidine compounds and their use as polymerization regulators

AssigneeCiba Specialty Chemicals Corporation

InventorsPeter Nesvadba, Tobias Hintermann, Andreas Kramer, Marie-Odile Zink, Lucienne Bugnon

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Abstract

The present invention relates to selected 4-imino-N-alkoxy-polyalkyl-peperidine compounds preparation, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a 4-imino-N-alkoxy-polyalkyl-piperidine compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of 4-imino-N-alkoxy-polyalkyl-piperidine compounds for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for polymerization are also subjects of the present invention. 1

Claims22

Dependent claims

A compound of formula (I)

44
G1, G2, G3 and G4 are independently C1-C4alkyl or G1 and G2 together and G3 and G4 together, or G1 and G2 together or G3 and G4 together are pentamethylene;
wherein, when
G1, G2, G3 and G4 are C1-C4alkyl, at least one is higher alkyl than methyl;
G5 and G6 are each independently of the other hydrogen or C1-C4alkyl;
n is 1, 2, 3, or 4
Y is O, NR2 or when n is 1 and R1 represents alkyl or aryl Y is additionally a direct bond;
R2 is H, C1-C18alkyl or phenyl;
if n is 1
R1 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
—C(O)—C1-C38alkyl, or an acyl moiety of a α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OR2)2,—SO2—R2, —CO—NH—R2, —CONH2, COOR2, or Si(Me)3, wherein Q+ is H+, ammnonium or an alkali metal cation;
if n is 2
R1 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
or xylylene;
or
R1 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if n is 3,
R1 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid;
if n is 4, R1 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
and
X is selected from the group consisting of —CH2-aryl,
45
—CH2—CH2-aryl,
46
(C5-C6cycloalkyl)2CCN, (C1-C12alkyl)2CCN, —CH2CH═CH2, (C1-C12)alkyl-CR20—C(O)—(C1-C12)alkyl, (C1-C12)alkyl-CR20—C(O)—(C6-C10)aryl, (C1-C12)alkyl-CR20—C(O)—(C1-C12)alkoxy, (C1-C12)alkyl-CR20—C(O)-phenoxy, (C1-C12)alkyl-CR20—C(O)—N-di(C1-C12)alkyl, (C1-C12)alkyl-CR20—CO—NH(C1-C12)alkyl, (C1-C12)alkyl-CR20—CO—NH2, —CH2CH═CH—CH3, —CH2—C(CH3)═CH2, —CH2—CH═CH-phenyl,
47
3-cyclohexenyl, 3-cyclopentenyl,
48
wherein
R20 is hydrogen or C1-C12alkyl;
the alkyl groups are unsubstituted or substituted with one or more —OH, —COOH or —C(O)R20 groups;
and
the aryl groups are phenyl or naphthyl which are unsubstituted or substituted with C1-C12alkyl, halogen, C1-C12alkoxy, C1-C12alkylcarbonyl, glycidyloxy, OH, —COOH or —COO(C1-C12)alkyl.

33 more elements

A polymerizable composition, comprising

a) at least one ethylenically unsaturated monomer or oligomer, and
b) a compound according to formula (I)
52
G1, G2, G3 and G4 are independently C1-C4alkyl or G1 and G2 together and G3 and G4 together, or G1 and G2 together or G3 and G4 together are pentamethylene;
G5 and G6 are each independently of the other hydrogen or C1-C4alkyl;
and
X represents a group such that the free radical X. derived from X is capable of initiating polymerization of ethylenically unsaturated monomers;
n is 1, 2, 3, or 4
Y is O, NR2 or when n is 1 and R1 represents alkyl or aryl Y is additionally a direct bond;
R2 is H, C1-C18alkyl or phenyl;
if n is 1
R1 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
—C(O)—C1-C36alkyl, or an acyl moiety of a α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OR2)2,—SO2—R2, —CO—NH—R2, —CONH2, COOR2, or Si(Me)3, wherein Q+ is H+, ammnonium or an alkali metal cation;
if n is 2
R1 is C1-C18alkylene, C3-C18alkenylene or C3-C,8alkinylene, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
or xylylene;
or
R1 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if n is 3,
R1 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid;
and
if n is 4, R1 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

22 more elements

A polymerizable composition, comprising

a) at least one ethylenically unsaturated monomer or oligomer, and
b) a compound according to formula (II)
54
G1, G2, G3 and G4 are independently C1-C4alkyl or G1 and G2 together and G3 and G4 together, or G1 and G2 together or G3 and G4 together are pentamethylene;
G5 and G6 are each independently of the other hydrogen or C1-C4alkyl;
n is 1, 2, 3, or 4
Y is O, NR2 or when n is 1 and R1 represents alkyl or aryl Y is additionally a direct bond;
R2 is H, C1-C18alkyl or phenyl;
if n is 1
R1 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
—C(O)—C1-C36alkyl, or an acyl moiety of a α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OR2)2,—SO2—R2, —CO—NH—R2, —CONH2, COOR2, or Si(Me)3, wherein Q+ is H+, ammnonium or an alkali metal cation;
if n is 2
R1 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substitued, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
or xylylene;
or
R1 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if n is 3,
R1 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid;
and
if n is 4, R1 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
and
c) a source of free radicals.

22 more elements

Dependencies are inferred from the claim text.