Polymerisation catalysts

Details Polymerisation catalysts Polymerisation catalysts

2001-12-20

2004-09-14

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S021000, C556S121000, C556S122000, C556S123000, C556S128000, C556S130000, C556S135000, C502S152000, C502S155000, C526S128000, C526S308000

Reexamination Certificate

active

06790972

ABSTRACT:

The present invention relates to new compounds having an element of group 12 and having a tridentate ligand, a process for their preparation and their use in particular as polymerization catalysts.
The use of derivatives having an element of group 12 but having porphyrin type ligands (Inoue, Acc. Chem. Res., (1996) 29, 39) as catalysts for the polymerization of heterocycles is already known.
However, it has been shown that each type of catalyst used for the polymerizations or copolymerizations, produces different polymers or copolymers respectively (Jedlinski et al., Macromolecules, (1990) 191, 2287; Munson et al., Macromolecules, (1996) 29, 8844; Montaudo et al., Macromolecules, (1996) 29, 6461). The problem is therefore to find new catalytic systems in order to obtain new polymers or copolymers, and more particularly block copolymers. The use of catalytic systems allows control of the chain formation of monomers leading to specific copolymers having the appropriate properties. This is particularly useful for biocompatible copolymers, the biodegradation of which is influenced by this chain formation.
Therefore a subject of the invention is the products of general formula I
in which
M represents an element of group 12;
R
M
represents the hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, alkylthio, cycloalkylthio, arylthio, amino, alkylamino, dialkylamino, cycloalkylamino, di(cycloalkyl)amino, alkyl(cycloalkyl)amino, arylamino, diarylamino, alkylarylamino or (cycloalkyl)arylamino radical;
A and B represent, independently, a carbon chain of 2 to 4 carbon atoms, optionally substituted by one or more of the following substituted (by one or more identical or different substituents) or non-substituted alkyl, cycloalkyl or aryl radicals, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical;
L
1
and L
2
represent, independently, a group of formula -E
15
(R
15
)— in which
E
15
is an element of group 15 and
R
15
represents the hydrogen atom; one of the following substituted (by one or more identical or different substituents) or non-substituted alkyl, cycloalkyl or aryl radicals, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical; a radical of formula -E
14
RR′R″ in which E
14
is an element of group 14 and R, R′ and R″ represent, independently, the hydrogen atom or one of the following substituted (by one or more identical or different substituents) or non-substituted alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, alkylthio, cycloalkylthio or arylthio radicals, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical; or a radical of formula —SO
2
Q in which Q represents a halogen atom, an alkyl, haloalkyl or aryl radical optionally substituted by one or more substituents chosen from the alkyl, haloalkyl and halogen radicals.
L
3
indifferently represents a group of formula -E′
15
(R′
15
)(R″
15
) or -E
16
(R
16
) in which
E′
15
is an element of group 15 and
E
16
is an element of group 16 and
R′
15
, R″
15
and R
16
represent, independently, the hydrogen atom; one of the following substituted (by one or more identical or different substituents) or non-substituted alkyl, cycloalkyl or aryl radicals, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical; a radical of formula -E′
14
TTT″ in which E′
14
is an element of group 14 and T, T′ and T″ represent, independently, the hydrogen atom or one of the following substituted (by one or more identical or different substituents) or non-substituted alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, alkylthio, cycloalkylthio or arylthio radicals, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical; or a radical of formula —SO
2
Q′ in which Q′ represents a halogen atom, an alkyl, haloalkyl or aryl radical optionally substituted by one or more substituents chosen from the alkyl, haloalkyl and halogen radicals.
In the definitions indicated above, the expression halogen represents a fluorine, chlorine, bromine or iodine atom, preferably chlorine. The expression alkyl preferably represents a linear or branched alkyl radical having 1 to 6 carbon atoms and in particular an alkyl radical having 1 to 4 carbon atoms such as the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl radicals.
The term haloalkyl preferably designates radicals in which the alkyl radical is as defined above and is substituted by one or more halogen atoms as defined above such as, for example, bromoethyl, trifluoromethyl, trifluoroethyl or also pentafluoroethyl. The alkoxy radicals can correspond to radicals in which the alkyl radical is as defined above. The methoxy, ethoxy, isopropyloxy or tert-butyloxy radicals are preferred. The alkylthio radicals preferably represent radicals in which the alkyl radical is as defined above such as, for example, methylthio or ethylthio. The alkylamino and dialkylamino radicals preferably represent the radicals in which the alkyl radical is as defined above such as, for example, methylamino or dimethylamino.
The cycloalkyl radicals are chosen from saturated or unsaturated monocyclic cycloalkyls. The saturated monocyclic cycloalkyl radicals can be chosen from the radicals having 3 to 7 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals. The unsaturated cycloalkyl radicals can be chosen from cyclobutene, cyclopentene, cyclohexene, cyclopentadiene and cyclohexadiene radicals. The cycloalkoxy radicals can correspond to radicals in which the cycloalkyl radical is as defined above. The cyclopropyloxy, cyclopentyloxy or cyclohexyloxy radicals are preferred. The cycloalkylthio radicals can correspond to radicals in which the cycloalkyl radical is as defined above such as for example cyclohexylthio. The cycloalkylamino and di(cycloalkyl)amino radicals can correspond to radicals in which the cycloalkyl radical is as defined above such as for example cyclohexylamino and di(cyclohexyl)amino.
The aryl radicals can be of mono or polycyclic type. The monocyclic aryl radicals can be chosen from the phenyl radicals optionally substituted by one or more alkyl radicals, such as tolyl, xylyl, mesityl and cumenyl. The polycyclic aryl radicals can be chosen from the naphthyl, anthryl and phenanthryl radicals. The aryloxy radicals can correspond to radicals in which the aryl radical is as defined above. The phenoxy, 2,4,6-tritertiobutylphenoxy, tolyloxy or mesityloxy radicals are preferred. The arylthio radicals preferably designate the radicals in which the aryl radical is as defined above such as for example in phenylthio radicals. The arylamino and diarylamino radicals preferably designate radicals in which the aryl radical is as defined above such as, for example, phenylarnino or diphenylamino radicals.
The alkyl (cycloalkyl)amino radicals can correspond to radicals in which the alkyl and cycloalkyl radicals are as defined above such as, for example methyl(cyclohexyl)amino.
The alkyl arylamino radicals preferably designate radicals in which the alkyl and aryl radicals are as defined above such as, for example methylphenylamino. The (cycloalkyl)arylamino radicals can correspond to the radicals in which the cycloalkyl and aryl radicals are as defined above such as, for example (cyclohexyl)phenylamino.
The compounds of formula 1 can be presented in the form of a monomer or of a dimer and more particularly the compounds of formula 1 in which M represents a zinc atom generally presented in dimer form.
A more particular subject of the invention is the products of general formula I as defined above, characterized in that
R
M
represents an alkyl radical;
A and B represent, independently, a carbon chain with 2 to 4 carbon atoms;
L
1
and L
2
represent, independently, a radical of formula -E
15
(R
15
)— in which E
15
is a nitrogen or phosphorus atom and R
15
, represents a hydrogen atom or a radical of formula -E

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