Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1998-10-28
2001-08-28
Dawson, Robert (Department: 1712)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S152000, C502S167000, C502S200000, C502S202000, C546S002000, C546S006000, C546S010000, C546S013000, C549S206000, C549S210000, C549S213000, C556S172000, C556S173000, C556S174000, C556S175000, C526S204000, C526S217000, C526S266000, C526S270000, C526S273000, C528S092000, C528S094000, C528S354000, C528S359000, C528S416000, C528S417000, C528S421000
Reexamination Certificate
active
06281154
ABSTRACT:
This application is a 371 of PCT/FR97/00773 filed Apr. 30, 1997.
Certain mono- and di-anionic tridentate ligands are known as ligands for transition metals.
Thus, the (Ph
2
PCH
2
SiMe
2
)
2
N
−
derivative was used to prepare iridium complexes (Fryzuk et al., Angew. Chem. Ed. Engl. (1990), 29, 73) and the [(Me
3
SiNCH
2
CH
2
)
2
NSiMe
3
]
2−
derivative was used to prepare zirconium dichloride complexes (Cloke et al., J. Chem. Soc., Dalton Trans. (1995), 25). Boron derivatives having the [(O
2
CCH
2
)
2
NCH
3
]
2−
ligand are also known (Contrepas et al., J. Organomet. Chem. (1986), 307,1). Moreover, aluminium derivatives having the [NH(CH
2
CH
2
O)
2
]
2−
ligand have also been described (Mehrotra et al., J. Indian Chem. Soc. (1962), 39, 677-82).
The use of Lewis acids having an element of group 13 in organic synthesis is also known (Yamamoto, H. in Organometallics in Synthesis; Schlosser, M., Ed.; John Wiley and Sons Ltd.: West Sussex, England, 1994, Chapter 7) as well as catalysts for the polymerization of heterocycles (Inoue, Acc. Chem. Res. (1996) 29,39). Inoue et al. demonstrated that the catalysts having ligands of porphyrine type were capable of producing polymers having a polymolecularity index close to one (J. Chem. Soc., Chem. Commun. (1985), 1148; Chem.
Lett. (1987), 991; Makromol. Chem. (1981) 182, 1073). Moreover, these catalysts can be used to prepared alternating or block copolymers (Inoue et al., J. Am. Chem. Soc. (1983) 105, 1304; J. Am. Chem. Soc. (1985) 107, 1358; Macromolecules (1984) 17, 2217). These two properties are due to the fact that a living polymer is generated.
However, these catalytic systems use porphyrine ligands which are expensive and difficult to access, resulting in an increased cost. Furthermore, in order to increase the activity, it is necessary to add Lewis acids, which increases the complexity of the catalytic systems (Inoue et al., Macromolecules (1994) 27, 2013; Macromolecules (1995) 28, 651).
The problem was therefore to find catalytic systems which were more efficient, easier to synthesize and more economical than those previously recommended.
The present invention relates to new compounds having an element of group 13 linked to a mono- or di-anionic tridentate ligand, a process for their preparation and their use in particular as polymerization catalysts.
A subject of the invention is thus the products of general formula 1 and 2
in which
M represents an element of group 13;
R
M
represents the hydrogen atom, a halogen atom or one of the following radicals, substituted (by one or more identical or different substituents) or non-substituted: alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, alkylthio, cycloalkylthio or arylthio, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical;
A and B represent, independently, a carbonated 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 radicals: alkyl, cycloalkyl or aryl, 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 radicals: alkyl, cycloalkyl or aryl, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical; a radical of formula RR′R″E
14
— 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 radicals: alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, alkylthio, cycloalkylthio or arylthio, 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 radicals and halogen;
X
1
−
represents a non-coordinating anion with respect to element M;
R
1
represents a hydrogen atom, a radical of formula RR′R″E
14
— in which E
14
, R, R′ and R″ have the same definitions as above, or one of the following radicals, substituted (by one or more identical or different substituents) or non-substituted: alkyl, cycloalkyl or aryl, in which said substituent is a halogen atom, the alkyl, nitro or cyano radical.
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 from 1 to 6 carbon atoms and in particular an alkyl radical having from 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 the 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 may correspond to the 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 the radicals in which the alkyl radical is as defined above such as, for example, methylthio or ethylthio.
The cycloalkyl radicals are chosen from the saturated or unsaturated monocyclic cycloalkyls. The saturated monocyclic cycloalkyl radicals can be chosen from the radicals having from 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, cyclopentanediene, 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 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 the radicals in which the aryl radical is as defined above such as for example in phenylthio.
The X
1
−
anion can be chosen from non-coordinating anions with respect to element M such as the tetrafluoroborate, tetraphenylborate, tetrachloroaluminate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulphonate or perchlorate anions.
A more particular subject of the invention is the products of general formula 1 and 2 as defined above, characterized in that
M represents a boron, aluminium or gallium atom;
R
M
represents the hydrogen atom, a halogen atom and in particular chlorine, or the methyl radical;
A and B represent, independently, a carbonated chain with 2 to 4 carbon atoms, and in particular a carbonated chain with 2 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 radical of formula RR′R″E
14
— in which E
14
represents a carbon or silicon atom and R, R′ and R″ represent, independently, the hydrogen atom or an alkyl radical; R
15
represents in particular
Bertrand Guy
Cazaux Jean Bernard
Emig Norbert
Reau Régis
Bierman, Muserlian and Lucas
Dawson Robert
Robertson Jeffrey B.
Societe de Conseils de Recherches et d'Applications Scienti
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