Back to results
US 6,664,353 B2Granted
Heterocyclic alkoxyamines as regulators in controlled radical polymerization processes
AssigneeCiba Specialty Chemicals Corporation
InventorsPeter Nesvadba, Andreas Kramer, Marie-Odile Zink
Life of this patent
Estimating the term…
Abstract
The present invention is aimed at a process for controlled polymerization of ethylenically unsaturated monomers in the presence of heterocyclic sterically hindered alkoxyamine compounds. 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. Still further subjects of the invention are novel amine precursors and a novel process for manufacturing 5-ring heterocyclic amines.
Claims21
A compound of formula (IIa) or (IIb)
- R1, R2, R3 and R4 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R5, C2-C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl or R1 and R2 and/or R3 and R4 together with the linking carbon atom form a C3-C12cycloalkyl radical;
- with the proviso that if Q in formula (IIa) is —CH2— or CO, at least one of R1, R2, R3 or R4 is different from methyl;
- R5, R6 and R7 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
- X is selected from the group consisting of
- —CH(aryl)2, —CH2-aryl,
- —CH2—CH2-aryl,
- (C5-C6cycloalkyl)2CCN, C5-C6cycloalkylidene-CCN, (C1-C12alkyl)2CCN, —CH2CH═CH2, (C1C12)alkyl-CR30—C(O)—(C1-C12)alkyl, (C1-C12)alkyl-CR30—C(O)—(C6-C10)aryl, (C1-C12)alkyl-CR30—C(O)—(C1C12)alkoxy, (C1-C12)alkyl-CR30—C(O)phenoxy, (C1-C12)alkyl-CR30—C(O)—N-di(C1-C12)alkyl, (C1-C12)alkyl-CR30—CO—NH(C1-C12)alkyl, (C1-C12)alkyl-CR30—CO—NH2, —CH2CH═CH—CH3, —CH2—C(CH3)═CH2, —CH2—CH═CH-phenyl,
- —O—C(O)—C1-C12alkyl, —O—C(O)—(C6-C10)aryl, (C1-C12)alkyl-CR30-CN,
- wherein
- R30 is hydrogen or C1-C12alkyl;
- Z1 is O or NR8;
- R8 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R5, C2-C18alkyl which is interrupted by least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10alkyl, C7-C9phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
- Q is a divalent radical CR9R10, CR9R10—CR11R12, CR9R10CR11R12CR13R14, C(O) or CR9R10C(O), wherein R9, R10, R11, R12, R13 and R14 are independently hydrogen, phenyl or C1-C18alkyl, 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 —COOC1-C12alkyl.
11 more elements
A compound of formula (IIIa) or (IIIb)
- wherein R1, R2, R3 and R4 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R5, C2C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or
- C6-C10aryl or R1 and R2 and/or R3 and R4 together with the linking carbon atom form a C3-C12cycloalkyl radical;
- R5, R6 and R7 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
- Z1 is O or NR8;
- R8 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R5, C2C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl, C7C9phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
- Q is a divalent radical CR9R10, CR9R10—CR11R12, CR9R10CR11R12CR13R14, C(O) or CR9R10C(O), wherein R9, R10, R11, R12, R13 and R14 are independently hydrogen, phenyl or C1-C18alkyl;
- with the proviso that in formula (IIIa)
- if Q is CH2 and Z1 is O, at least one of R1, R2, R3 or R4 is higher alkyl than methyl;
- or if Q is CH2 or C(O) and Z1 is NR8 at least two of R1, R2, R3 or R4 are higher alkyl than methyl or one is higher alkyl than methyl and R1 and R2 or R3 and R4 form a C3-C12cycloalkyl radical together with the linking carbon atom.
6 more elements
A compound of formula (IVa) or (IVb)
- wherein R1, R2, R3 and R4 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R5, C2C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl;
- R5, R6 and R7 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
- Z1 is O or NR8;
- R8 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R5, C2C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl, C7C9phenylalkyl, C5C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
- Q is a divalent radical CR9R10, CR9R10—CR11R12, CR9R10CR11R12CR13R14, C(O) or CR9R10C(O), wherein R9, R10, R11, R12, R13 and R14 are independently hydrogen, phenyl or C1-C18alkyl;
- with the proviso that if the compounds of formula (IVa) or (IVb) represent a 6 or 7 membered ring at least two of R1, R2, R3 and R4 are different from methyl and the substitution patterns R1, R2, R3, R4 being;
- methyl, methyl, butyl, butyl or methyl, ethyl, methyl, ethyl are excluded.
4 more elements
Dependencies are inferred from the claim text.