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US 6,184,338 B2Granted
Anionic polymerization initiators containing tertiary amine functionality, their chain extended analogues, and processes for using the same
AssigneeFMC Corporation
InventorsJames A. Schwindeman, Robert J. Letchford
Life of this patent
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Abstract
The present invention provides novel anionic polymerization amine initiators having a tertiary amine group pendant to the polymer chain and processes for making the same. The initiators can be useful in the preparation of tertiary amine containing polymers, including linear, homotelechelic, heterotelechelic and radial polymers.
Claims32
A hydrocarbon solution comprising at least one tertiary amino anionic polymerization initiator of the formula:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms.
10 more elements
A process for the preparation of hydrocarbon solutions of monofunctional tertiary amine initiators comprising a compound of the structure:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms,
- the process comprising reacting at least one tertiary amino halide with an alkali metal having a particle size between 10 and 300 microns in size at a temperature ranging from about 35 to about 130° C. in an alkane, cycloalkane or aromatic solvent or a mixture thereof to form said alkali metal-containing monofunctional tertiary amine initiator.
11 more elements
A hydrocarbon solution comprising at least one tertiary amino anionic polymerization initiator of the formula:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
- Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M—R3 linkage;
- and
- n is an integer from 1 to 5.
13 more elements
A process for the preparation of hydrocarbon solutions of monofunctional tertiary amine initiators comprising a compound of the structure:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
- Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M—R3 linkage;
- and
- n is an integer from 1 to 5,
- the process comprising:
- reacting at least one tertiary amino halide with an alkali metal having a particle size between 10 and 300 microns in size at a temperature ranging from about 3 to about 130° C. in an alkene, cycloalkane or aromatic solvent to form an alkali metal-containing monofunctional tertiary amine product of the formula
- wherein
- M, R1, R2 and R3 are the same as defined above;
- and
- adding one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or a mixture of one or more dienes with one or more alkenylsubstituted aromatic compounds to form an extended hydrocarbon chain Qn between M and R3, wherein Q and n are as defined above.
18 more elements
A process for the anionic polymerization of anionically polymerizable monomers comprising the steps of:
- initiating polymerization of a conjugated diene hydrocarbon monomer, a mixture of conjugated diene monomers, an alkenylsubstituted aromatic compound, a mixture of alkenylsubstituted aromatic compounds, or a mixture of one or more conjugated diene hydrocarbons and one or more alkenylsubstituted aromatic compounds in a hydrocarbon or mixed hydrocarbon-polar solvent medium at a temperature of 10° C. to 150° C. with at least one initiator having the formula:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
- Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the
- M□R3 linkage;
- and
- n is an integer from 1 to 5, to produce an intermediate living polymer;
- and
- reacting the intermediate living polymer with a terminating, functionalizing, or coupling agent.
16 more elements
A polymer having the formula
- wherein:
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
- Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M—R3 linkage;
- n is an integer from 0 to 5;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more compounds selected from the group consisting of conjugated dienes, alkenylsubstituted aromatic hydrocarbons and mixtures thereof;
- z is an integer from 2 to 10,000;
- FG is hydrogen or a protected or unprotected functional group.
13 more elements
A polymer of the formula
- wherein:
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
- Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M—R3 linkage;
- n is an integer from 0 to 5;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more compounds selected from the group consisting of conjugated dienes, alkenylsubstituted aromatic hydrocarbons and mixtures thereof;
- z is an integer from 2 to 10,000;
- L is a residue of a multifunctional linking agent;
- and
- v is from 3 to 30.
15 more elements
A functionalized polymer which contains at least one tertiary amine functionality pendant to the polymer backbone.
A tertiary amino anionic polymerization initiator of the formula:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms.
10 more elements
A tertiary amino anionic polymerization initiator of the formula:
- wherein:
- M is an alkali metal;
- R1 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C3-C16 alkyl;
- and saturated and unsaturated, linear and branched, C3-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- R2 is chiral or achiral and is selected from the group consisting of saturated and unsaturated, linear and branched, optionally silyl-, amino-, or oxy-substituted, C1-C16 alkyl;
- saturated and unsaturated, optionally silyl-, amino-, or oxy-substituted, C3-C16 cycloalkyl;
- saturated and unsaturated, linear and branched, substituted C1-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C16 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and
- R3 is a hydrocarbon connecting group or tether selected from the group consisting of saturated and unsaturated, linear and branched C1-C25 alkyl;
- saturated and unsaturated C3-C25 cycloalkyl;
- saturated and unsaturated substituted C1-C25 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
- and saturated and unsaturated substituted C3-C25 cycloalkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl, with the proviso that the nitrogen atom and the alkali metal are separated by three or more carbon atoms;
- Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M—R3 linkage;
- and
- n is an integer from 1 to 5.
13 more elements
Dependencies are inferred from the claim text.