Protected aminofunctionalized polymerization initiators and methods of making and using same
AssigneeFMC Corporation
InventorsThorsten Werner Brockmann, Randy W. Hall
Life of this patent
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Abstract
Anionic polymerization initiators useful in the preparation of polymers having a protected amine functional group. The amine functionality includes a first protecting group, which can be aralkyl, methyl, allyl or tertiary alkyl group. The other of the amine protecting groups can be the same as the first protecting group. Alternatively, the second protecting group can be different from the first protecting group, in which case it is selected to have differential stability to agents used to remove the aralkyl, methyl, allyl or tertiary alkyl protecting group.
Claims31
A compound of the formula:
- wherein:
- M is an alkali metal selected from the group consisting of lithium, sodium and potassium;
- Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- Q is a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M—Z linkage;
- n is from 0 to 5;
- R1 is selected from the group consisting, of aralkyl, allyl, tertiary alkyl and methyl;
- and
- R2 is the same as R1, with the proviso that when R1 is methyl, R2 is not C1-C4 alkyl, or when R1 is aralkyl, R2 is not aralkyl, or R2 is different from R1 and selected from the group consisting of alkyl,substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, and substituted heterocycloalkyl, with the proviso that when R is not the same as R1, then R2 is more stable under conditions used to remove R1,
- or R1 and R2 together with the nitrogen atom to which they are attached form
- wherein y is from 1 to 4 and each R11 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy, substituted alkoxy, heteroaryl, substituted heteroaryl, heterocycloalkyl, and substituted heterocycloalkyl.
A process for making amine functionalized compounds, comprising reacting one or more omega-tertiary-amino-1-haloalkanes of the formula
- wherein:
- X is halide;
- Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- R1 is a protecting group selected from the group consisting of aralkyl, allyl, tertiary alkyl and methyl;
- and
- R2 is the same as R1, with the proviso that when R1 is methyl, R2 is not C1-C4 alkyl, or R2 is different from R1 and selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, and substituted heterocycloalkyl, with the proviso that when R2 is not the same as R1, then R2 is more stable under conditions used to remove R1,
- or R1 and R2 together with the nitrogen atom to which they are attached form
- wherein y is from 1 to 4 and each R11 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy, substituted alkoxy, heteroaryl, substituted heteroaryl, heterocycloalkyl, and substituted heterocycloalkyl,
- with an alkali metal in an alkane, cycloalkane, or aromatic reaction solvent or mixtures of such solvents to form one or more compounds of the formula
- wherein M is an alkali metal and Z, R1, and R2 are the same defined above;
- and
- optionally reacting said amine compound with one or more unsaturated organic compounds to form a compound having a saturated or unsaturated hydrocarbyl group Q between Z and M of the formula
- wherein:
- Q is a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds;
- n is from 0 to 5;
- and
- Z, R1, and R2 are the same defined above.
Dependencies are inferred from the claim text.