Polymerisation catalyst

Details Polymerisation catalyst Polymerisation catalyst

2001-12-18

2004-04-06

Sellers, Robert (Department: 1712)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C534S015000, C556S012000, C556S018000, C556S020000, C556S021000, C556S022000, C556S023000, C556S404000, C556S410000, C502S152000, C502S153000

Reexamination Certificate

active

06716787

ABSTRACT:

The present invention relates to new compounds having a lanthanide and a tridentate ligand, a process for their preparation and their use in particular as polymerization catalysts.
The use of the lanthanide derivatives as catalysts for polymerization and copolymerization of olefines (Gibson et al., Angew. Chem., Int. Ed. Engl., (1999) 38, 428) and heterocycles (Yao et al., J. Polymer. Sci. Part A: Polymer Chem., (1996) 34, 1799) is known.
However, it has been shown that each type of catalyst used for polymerizations or copolymerizations produces respectively different polymers or copolymers in particular because of transesterification reactions which lead to inversions of the stereogenic centres (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 making it possible to obtain block copolymers, allows control of the chain formation of the monomers in order to obtain 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 1
in which
M represents a lanthanide;
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 with 2 to 4 carbon atoms, optionally substituted by 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;
L
1
, L
2
and L
3
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
R′
15
in which R′
15
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 radicals in which the alkyl radical is as defined above such as, for example, methylamino or dimethylamino.
The cycloalkyl radicals are chosen from the saturated or unsaturated monocyclic cycloalkyls. The saturated monocyclic cycloalkyl radicals can be chosen from radicals having 3 to 7 carbon atoms such as the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals. The unsaturated cycloalkyl radicals can be chosen from the cyclobutene, cyclopentene, cyclohexene, cyclopentadiene or 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, cumenyl. The polycyclic aryl radicals can be chosen from the naphthyl, anthryl, 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 radicals in which the aryl radical is as defined above such as for example in phenylthio. The arylamino and diarylamino radicals preferably designate radicals in which the aryl radical is as defined above such as, for example, phenylamino or diphenylamino.
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 alkylarylamino 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 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 samarium atom are generally presented in the form of a dimer.
A more particular subject of the invention is the products of general formula 1 as defined above, characterized in that R
M
represents a halogen atom; A and B represent, independently, a carbon chain with 2 to 4 carbon atoms; L
1
, L
2
and L
3
represent, independently, a radical of formula —E
15
(R
15
)— in which E
15
is a nitrogen or phosphorus atom and R
15
represents an alkyl radical or a radical of formula —E
14
RR′R″ in which E
14
represents a carbon or silicon atom and R, R′ and R″ represent, independently, the hydrogen atom or an alkyl radical.
Preferably, M represents a samarium atom. Preferably also, R
M
represents a chlorine atom; A and B represent, independently, a carbon chain with 2 carbon atoms; L
1
, L
2
and L
3
represent, independently, a radical of formula —E
15
(R
15
)— in which E
15
is a nitrogen atom and R
15
represents a methyl, ethyl, propyl, isopropyl radical or a radical of formula —E
14
RR′R″ in which E
14
represents a silicon atom and R, R′ and R″ represent, independently, the hydrogen atom or a methyl, ethyl, propyl or isopropyl radical.
A more particular subject of the invention is the product described hereafter in the examples, in particular the product corresponding to the following formula:
—[(Me
3
SiNCH
2
CH
2
)
2
NMe]SmCl.
A subject of the invention is also a process for

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