Thermal- and photoinitiated radical polymerization in the presence of an addition fragmentation agent
AssigneeCiba Specialty Chemicals Corporation
InventorsVincent Desobry, Peter Murer, Anne Schuwey
Life of this patent
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Abstract
Disclosed are compositions from which radically initiated oligomers/polymers having a controlled molecular weight, low polydispersity and a vinyl or dienyl end group are prepared. Further subjects of the invention are a process for controlled radical polymerization, oligomers/polymers obtainable by said process and the use of specific addition fragmentation agents for the polymerization process. The addition fragmentation agents are new in part and these are also subject of the present invention. The addition fragmentation agents are of the formula (Ia), (Ib) or (Ic) where Y is a group which activates the double bond towards Michael addition.
Claims20
A composition comprising
- a) at least one ethylenically unsaturated monomer or oligomer
- b) a radical initiator which forms a radical upon heating or upon irradiation with (UV) light from 305 nm to 450 nm and
- c) a compound of formula (Ia), (Ib) or (Ic)
- wherein
- Y is a group which activates the double bond towards Michael addition;
- X is halogen or the anion of a mono carboxylic acid from 1-12 carbon atoms, a monovalent oxo acid or complex acid;
- n is 0 or 1;
- R1, R2 R3 are independently of each other hydrogen, unsubstituted C1-C18alkyl, C3-C18alkyl, interrupted by at least one nitrogen or oxygen atom, C3-C18alkenyl, C3-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom;
- or
- C1-C18alkyl or C3-C18alkyl interrupted by at least one nitrogen or oxygen atom, C3-C18alkenyl, C3-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino, C1-C4alkylamino, di(C1-C4alkyl)amino or by a group —O—C(O)—C1-C8alkyl;
- or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino;
- or
- R1 and R2, together with the linking hetero atom, form a C3-C12 heterocycloalkyl radical;
- or
- R1 and R2 form a group
- or
- R1, R2 and R3 form a group
A compound of formula (Ia), (Ib) or (Ic)
- wherein
- Y is CN, C(O)halogen, COOR4, C(O)R4, CONR5R6, phenyl or naphthyl which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen, nitro, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino;
- and
- R4, R5 and R6 are hydrogen or C1-C18alkyl;
- X is Cl−, Br−, —I−, ClO4−, CF3SO3−, CH3SO3−, CF3COO−, p-toluene sulfonate, HSO4−, BF4−, B(Phenyl)4−, PF6−, SbCl6−, AsF6−, SbF6− or a mono carboxylic acid from 1-12 carbon atoms;
- n is 0 or 1;
- R1, R2 R3 are independently of each other hydrogen, unsubstituted C1-C18alkyl, C3-C18alkyl, interrupted by at least one nitrogen or oxygen atom, C3-C18alkenyl, C3-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom;
- or
- C1-C18alkyl, C3-C18alkyl, interrupted by at least one nitrogen or oxygen atom, C3-C18alkenyl, C3-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino, di(C1-C4alkyl)amino or by a group —O—C(O)—C1-C18alkyl;
- or
- phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino;
- or
- R1 and R2, together with the linking hetero atom, form a C3-C12heterocycloalkyl radical;
- R10 and R20 are independently of each other C3-C18alkyl which is unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino;
- and
- R30 is hydrogen or methyl.
Dependencies are inferred from the claim text.