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US 2002/0173607 A1Published application
Protected aminofunctionalized polymerization initiators and methods of making and using same
AssigneeFMC Corporation
InventorThorsten Werner Brockmann
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 is part of a heterocyclic radical and includes a protecting group.
Claims128
A compound of the formula:
- 48
- 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;
- n is from 0 to 5;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- PG is a protecting group,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
8 more elements
A process for making amine functionalized compounds, comprising reacting one or more omega-tertiary-amino-1-haloalkanes of the formula
- 51
- 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;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- with the proviso that when A is —CR, then Z can be absent,
- 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
- 52
- wherein M is an alkali metal and Z, A, PG and R1 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 of the formula
- 53
- 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
- A, Z, PG, and R1 are the same defined above.
16 more elements
A polymer of the formula:
- 56
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- PG is a protecting group;
- and
- FG is hydrogen or a protected or unprotected functional group or FG represents a polymer segment derived by reaction of at least one functional group with a comonomer, with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
10 more elements
A polymer of the formula:
- 66
- wherein:
- 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;
- n is from 0 to 5;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- FG is hydrogen or a protected or unprotected functional group or FG represents a polymer segment derived by reaction of at least one functional group with a comonomer,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
9 more elements
A polymer of the formula
- 69
- wherein:
- each Z is independently a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds;
- each n is independently from 0 to 5;
- each P is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- each m is independently from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- each PG is independently a protecting group;
- and
- L is a residue of a difunctional linking agent,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
10 more elements
A polymer of the formula
- 70
- wherein:
- each Z is independently a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M—Z linkage;
- each n is independently from 0 to 5;
- each P is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- each m is independently from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- each PG is independently a protecting group;
- each B is independently a residue of an alkyllithium initiator or the residue of a protected functionalized initiator, in which the protecting group is intact or removed;
- L′ is a residue of a multifunctional linking agent;
- and
- v is from 3 to 30,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
12 more elements
A process for the anionic polymerization of anionically polymerizable compounds comprising the steps of:
- initiating polymerization of one or more compounds capable of anionic polymerization in a hydrocarbon or mixed hydrocarbon-polar solvent medium with one or more compounds having the formula:
- 71
- 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;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- PG is a protecting group,
- with the proviso that when A is -CR, then Z, Qn, or both, can be absent, to produce an intermediate living polymer;
- reacting the intermediate living polymer with a terminating, functionalizing, or coupling agent;
- optionally removing at least one protecting group to liberate at least one functional group;
- and
- optionally reacting said at least one liberated functional group with one or more comonomers to form a polymer segment.
13 more elements
An amine functionalized polymer comprising one or more compounds of the formula
- 74
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- PG is a protecting group;
- and
- Y is a branched or straight chain hydrocarbon connecting group which contains 1-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- T is selected from the group consisting of oxygen, sulfur, and nitrogen and mixtures thereof;
- A′ is an element selected from Group IVa of the Periodic Table of the Elements;
- R4, R5, and R6 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl, or R6 is optionally a —(CR7R8)1— group linking two A′ when k is 2, wherein R7 and R8 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl, and 1 is an integer from 1 to 7;
- and
- 1 is an integer from 1 to 7;
- and
- k is 1 when T is oxygen or sulfur, and 2 when T is nitrogen,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
17 more elements
A polymer of the formula
- 77
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- PG is a protecting group;
- and
- each R10 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, substituted heterocycloalkyl, and alkylsilyl.
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
10 more elements
A polymer having the formula
- 79
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- PG is a protecting group;
- Ph is phenyl;
- and
- Me is methy,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
11 more elements
A polymer of the formula
- 80
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- PG is a protecting group;
- Ph is phenyl;
- and
- TMS is trimethylsilyl,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
11 more elements
A polymer of the formula
- 81
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- TMS is trimethylsilyl,
- with the proviso that when A is P, CR or SiR, then Z, Qn, or both, can be absent.
9 more elements
A polymer of the formula:
- 82
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- PG is a protecting group;
- each R10 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, substituted heterocycloalkyl, and alkylsilyl;
- and
- X is a polymer segment or functional group,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
11 more elements
A polymer of the formula
- 83
- wherein:
- each Z is independently a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M—Z linkage;
- each n is independently from 0 to 5;
- each P is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- each m is independently from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- and
- L is a residue of a difunctional linking agent,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
9 more elements
A polymer of the formula
- 84
- wherein:
- each Z is independently a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M—Z linkage;
- each n is independently from 0 to 5;
- each P is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- each m is independently from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- each B is independently a residue of an alkyllithium initiator or the residue of a protected functionalized initiator, in which the protecting group is intact or removed;
- L′ is a residue of a multifunctional linking agent;
- and
- v is from 3 to 30,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
11 more elements
A polymer of the formula:
- 85
- wherein:
- each Z is independently a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M—Z linkage;
- each n is independently from 0 to 5;
- each P is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- each m is independently from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- each X comprises a polymer segment derived by reaction of one or more comonomers;
- and
- L is a residue of a difunctional linking agent,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
10 more elements
A polymer of the formula
- 86
- wherein:
- each Z is independently a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M—Z linkage;
- each n is independently from 0 to 5;
- each P is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- each m is independently from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- each B is independently a residue of an alkyllithium initiator or the residue of a protected functionalized initiator, in which the protecting group is intact or removed;
- each X comprises a polymer segment derived by reaction of one or more comonomers;
- and
- L′ is a residue of a multifunctional linking agent;
- and
- v is from 3 to 30,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
13 more elements
A polymer having the formula
- 87
- wherein:
- 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;
- P is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more anionically polymerizable compounds;
- m is from 2 to 20,000;
- A is N, P, CR or SiR, wherein R is selected from the group consisting of H and saturated or unsaturated aliphatic and aromatic radicals;
- each R1 is independently selected from the group consisting of alkylene and substituted alkylene;
- X comprises a polymer segment derived by reaction of one or more comonomers;
- and
- FG is hydrogen or a protected or unprotected functional group or FG represents a polymer segment derived by reaction of at least one functional group with a comonomer,
- with the proviso that when A is —CR, then Z, Qn, or both, can be absent.
10 more elements
Dependencies are inferred from the claim text.