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US 6,720,391 B2Granted
Functionalized initiators for anionic polymerization, protected functionalized polymers, deprotected analogues thereof, and methods of making the same
AssigneeFMC Corporation
InventorsJames Anthony Schwindeman, Robert J. Letchford, Eric John Granger, Roderic P. Quirk
Life of this patent
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Abstract
The present invention provides functionalized electrophiles, their analogous initiators, and processes for preparing these compounds. The present invention also relates to homotelechelic, heterotelechelic, and radial functional polydiene polymers, polyarylene polymers and polydiene/polyarylene copolymers, their optionally hydrogenated analogues, their optionally deprotected analogues, and processes for preparing these functionalized polymers.
Claims17
A polymer of the formula
- wherein
- each FG is independently hydrogen, a protected functional group, a non-protected functional group, the residue of a difunctional coupling agent, or the residue of a multifunctional coupling agent, with the proviso that when each T is oxygen, then FG is not hydrogen;
- each Q is independently 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 conjugated diene hydrocarbons with one or more alkenylsubstituted aromatic compounds;
- each x is independently the number of units of conjugated diene hydrocarbons, alkenylsubstituted aromatic compounds, or mixture thereof and ranges from about 10 to about 2000;
- 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 T is independently selected from the group consisting of oxygen, sulfur, nitrogen, and mixtures thereof;
- (A—R1R2R3) is a protecting group, in which each A is independently an element selected from Group IVa of the Periodic Table of the Elements;
- and R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
- R, R4, and R5 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;
- h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen;
- l is an integer from 1 to 7;
- m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;
- n is 2 or 3;
- w is 0 or 1;
- and
- y is 1.
13 more elements
A polymer of the formula
- FG—(Q)x—Z—C—(O)—R
- or
- FG—(Q)x—Z—C—(O)—OH
- wherein
- each FG is independently a protected functional group or a non-protected functional group;
- each Q is independently 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 conjugated diene hydrocarbons with one or more alkenylsubstituted aromatic compounds;
- each x is independently the number of units of conjugated diene hydrocarbon, alkenylsubstituted aromatic compound, or mixture thereof and ranges from about 10 to about 2000;
- 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;
- and
- each R is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl.
7 more elements
A polymer of the formula
- FG—[(Q)x—Z—C—(O)—R]y
- or
- FG—[(Q)x—Z—C—(O)—OH]y
- wherein
- each FG is independently the residue of a difunctional coupling agent or the residue of a multifunctional coupling agent;
- each Q is independently 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 conjugated diene hydrocarbons with one or more alkenylsubstituted aromatic compounds;
- each x is independently the number of units of conjugated diene hydrocarbons, alkenylsubstituted aromatic compounds, or mixture thereof and ranges from about 10 to about 2000;
- 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 R is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;
- and
- each y is independently 2 to 30.
8 more elements
A process for preparing polymers having a protected terminal carbonyl or carboxyl group of the formula
- 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 T is independently selected from the group consisting of oxygen, sulfur, nitrogen, and mixtures thereof;
- (A—R1R2R3) is a protecting group, in which each A is independently an element selected from Group IVa of the Periodic Table of the Elements;
- and R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;
- R, R4, and R5 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;
- h is 0 when T is oxygen or sulfur, and 1 when T is nitrogen;
- l is an integer from 1 to 7;
- m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;
- n is 2 or 3;
- and
- w is 0 or 1,
- the process comprising:
- initiating anionic polymerization of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or a mixture of one or more conjugated diene hydrocarbons with one or more alkenylsubstituted aromatic compounds with one or more protected functional initiators of the formula
- wherein:
- each M is independently an alkali metal;
- each Q is independently a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more compounds selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic compounds, and mixtures thereof;
- each v independently ranges from 0 to 5;
- and
- Z, T, A, R1, R2, R3, R, R4, R5, h, l, m, n, and w are the same as defined above, to produce one or more living polymer anions;
- and
- reacting one or more of said living polymer anions with at least one of a quenching agent, functionalizing reagent, or coupling agent, with the proviso that when each T is oxygen, then the living polymer anions are not reacted with a quenching agent.
19 more elements
Dependencies are inferred from the claim text.