Procedure for the controlled radical polymerisation of...

C - Chemistry – Metallurgy – 08 – F

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C08F 110/02 (2006.01) C08F 4/00 (2006.01) C08F 10/02 (2006.01) C08F 210/02 (2006.01) C08F 218/08 (2006.01) C08F 220/10 (2006.01) C08F 293/00 (2006.01) C08F 299/00 (2006.01) C08L 23/04 (2006.01) C08L 53/00 (2006.01)

Patent

CA 2332493

Process for the radical polymerization or copolymerization of ethylene under high pressure and in the presence of at least one initiating free radical (Z.cndot.) and of at least one controlling stable free radical (SFR.cndot.) which comprises the indoline nitroxide backbone represented by the formula (I), For example, radicals (SFR.cndot.) of formula (II). (see formula I) (see formula 2). : A is a hydrocarbonaceous chain forming an aromatic ring with the two carbon atoms to which it is attached, this ring being able to carry substituents or being able to carry one or more rings placed side by side, which rings are aromatic or aliphatic and optionally substituted, the carbon atoms forming the nitrogenous ring and in the alpha- and beta-position with respect to the nitrogen atom being able to carry hydrogen atoms or substituents; R1, R2, R3 and R4, which can be identical or different, each independently represent hydrogen; alkyl; alkenyl; aryl; aralkyl; -COOH; -COOR6 with R6 remain alkyl, alkenyl, aryl or aralkyl residue; or CN; it being possible for R3 and R4 to merge together into =X, X representing O or =NR7 with R7 representing an alkyl, alkenyl, aryl or aralkyl residue; and it being possible for the alkyl, alkenyl, aryl or aralkyl residues coming within the definition of R1 to R6 to carry substituents.

On conduit une (co)polymérisation radicalaire de l'éthylène sous haute pression en présence d'au moins un radical libre amorceur (Z~) et d'au moins un radical libre stable contrôleur (SFR~) qui comporte le squelette nitroxyde indolinique représenté par la formule (I). A titre d'exemples, on peut citer les radicaux (SFR~) de formule (II). (voir formule I)(voir formule II) A est une chaîne hydrocarbonée formant un cycle aromatique avec les deux atomes de carbone auxquels elle se rattache, ce cycle pouvant porter des substituants ou pouvant porter un ou plusieurs cycles accolés, aromatiques ou aliphatiques, éventuellement substitués, les atomes de carbone formant le cycle azoté et en position alpha et bêta par rapport à l'atome d'azote, pouvant porter des atomes d'hydrogène ou des substituants ; R1, R2, R3 et R4, pouvant être identiques ou différents, représentent chacun indépendamment H ; alkyle ; alcényle ; aryle ; aralkyle ; OH ; -OR5, R5 = reste alkyle, alcényle, aryle ou aralkyle ; -COOH ; -COOR6, R6 = reste alkyle, alcényle, aryle ou aralkyle ; ou CN ; R3 et R4 pouvant se confondre en =X, X représentant O ou =NR7, R7= reste alkyle, alcényle, aryle ou aralkyle; et les restes alkyle, alcényle, aryle ou aralkyle entrant dans la définition de R1 à R6 pouvant porter des substituants.

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