Anionic polymerization initiators containing tertiary amine functionality, their chain extended analogues, and processes for using the same

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.

If you were to search for Anionic polymerization initiators containing tertiary amine functionality, their chain extended analogues, and processes for using the same using relaxed search criteria, these patents would come up:

That which is claimed is:

1. A hydrocarbon solution comprising at least one tertiary amino anionic polymerization initiator of the formula: ##STR14##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl; and

R.sup.3 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-C25alkyl 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 nitrogenatom and the alkali metal are separated by three or more carbon atoms.

2. A process for the preparation of hydrocarbon solutions of monofunctional tertiary amine initiators comprising a compound of the structure: ##STR15##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl; and

R.sup.3 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-C25alkyl 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 nitrogenatom 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.degree. C. in an alkane, cycloalkane oraromatic solvent or a mixture thereof to form said alkali metal-containing monofunctional tertiary amine initiator.

3. A hydrocarbon solution comprising at least one tertiary amino anionic polymerization initiator of the formula: ##STR16##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl; and

R.sup.3 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-C25alkyl 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 nitrogenatom 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 alkenylsubstitutedaromatic compounds into the M--R.sup.3 linkage; and

n is an integer from 1 to 5.

4. A process for the preparation of hydrocarbon solutions of monofunctional tertiary amine initiators comprising a compound of the structure: ##STR17##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.3 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-C25alkyl 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 nitrogenatom 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 alkenylsubstitutedaromatic compounds into the M--R.sup.3 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.degree. C. in an alkene, cycloalkane or aromatic solvent to form analkali metal-containing monofunctional tertiary amine product of the formula ##STR18##

wherein

M, R.sup.1, R.sup.2 and R.sup.3 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 Q.sub.n between Mand R.sup.3, wherein Q and n are as defined above.

5. 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 dienehydrocarbons and one or more alkenylsubstituted aromatic compounds in a hydrocarbon or mixed hydrocarbon-polar solvent medium at a temperature of 10.degree. C. to 150.degree. C. with at least one initiator having the formula: ##STR19##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.3 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-C25alkyl 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 nitrogenatom 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 alkenylsubstitutedaromatic compounds into the

M.quadrature.R.sup.3 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.

6. The process of claim 5, wherein said living polymer is reacted with a functionalizing agent to form a polymer of the structure: ##STR20##

wherein:

R.sup.1, R.sup.2, R.sup.3, Q, and n are as defined above;

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; and

FG is a protected or unprotected functional group.

7. The process of claim 6, wherein said functionalizing agent is selected from the group consisting of alkylene oxides, oxygen, sulfur, carbon dioxide, halogens, haloalkyltrialkoxysilanes, halotrialkylsilanes, alkenylhalosilanes,omegaalkenylarylhalosilanes, sulfonated compounds, silicon acetals, 1,5-diazabicyclo[3.1.0]hexane, allyl halides, methacryloyl chloride, amines, epihalohydrins, 1-(3chloropropyl)-hexamethyleneimine, and mixtures thereof.

8. The process of claim 6, wherein said functionalizing agent comprises a compound of the formula

X--Z--T--(A--R.sup.1 R.sup.2 R.sup.3).sub.m

wherein:

X is halogen selected from the group consisting of chloride, bromide and iodide;

Z 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;

R.sup.4, R.sup.5, and R.sup.6 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl, or R.sup.6 is optionally a --(CR.sup.7 R.sup.8).sub.l-- group linking two A when m is 2, wherein R.sup.7 and R.sup.8 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl and l is an integer from 1 to7; and

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen, to form a polymer of the formula ##STR21##

wherein

R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, Q, Z, T, A, n and m have the meanings ascribed above.

9. The process of claim 8, further comprising the steps of:

removing said protecting group --(A--R.sup.4 R.sup.5 R.sup.6).sub.m to liberate the functional group T; and

optionally reacting said liberated functional group T with one or more comonomers to produce a polymer segment.

10. The process of claim 9, wherein said removing step and said reacting step occur simultaneously.

11. The process of claim 8, further comprising:

removing said protecting group (A--R.sup.4 R.sup.5 R.sup.6).sub.m to liberate the functional group T; and

optionally reacting said liberated functional group T under conditions sufficient to modify the functionality of T to incorporate a reactive olefinic bond.

12. The process of claim 5, wherein:

said coupling agent is selected from the group consisting of isomeric dialkenylaryls, isomeric di- and trivinylaryls, and mixtures thereof; and

said polymer has the formula ##STR22##

wherein:

R.sup.1, R.sup.2, R.sup.3, Q, P, n, and z have the meanings ascribed above;

L is a residue of a multifunctional linking agent; and

v is from 3to 30.

13. The process claim 5, wherein said initiator has the formula ##STR23##

14. The process of claim 13, wherein Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated dienes or a mixture of one or more conjugated dienes with one or more alkenylsubstituted aromatic hydrocarbons.

15. The process of claim 13, wherein Q is a saturated hydrocarbyl group derived by incorporation of one or more alkenylsubstituted aromatic hydrocarbons.

16. The process of claim 5, further comprising:

recovering said polymer; and

optionally hydrogenating the recovered polymer.

17. A polymer having the formula ##STR24##

wherein:

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.3 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-C25alkyl 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 nitrogenatom 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 alkenylsubstitutedaromatic compounds into the M--R.sup.3 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.

18. The polymer of claim 17, wherein n is an integer from 1 to 5.

19. The polymer of claim 18, wherein Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated dienes or a mixture of one or more conjugated dienes with one or more alkenylsubstituted aromatic hydrocarbons.

20. The polymer of claim 18, wherein Q is a saturated hydrocarbyl group derived by incorporation of one or more alkenylsubstituted aromatic compounds.

21. The polymer of claim 17, wherein FG is --Z--T--(A--R.sup.1 R.sup.2 R.sup.3).sub.m, wherein:

Z 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;

R.sup.4, R.sup.5, and R.sup.6 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl, or R.sup.6 is optionally a --(CR.sup.7 R.sup.8).sub.l-- group linking two A when m is 2, wherein R.sup.7 and R.sup.8 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl and l is an integer from 1 to7; and

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.

22. The polymer of claim 17, wherein FG is --Z--T--(H).sub.m, wherein:

Z 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; and

m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.

23. The polymer of claim 17, wherein FG is --Z--T--X, wherein:

Z 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; and

X is a polymer segments derived by incorporation of at least one comonomer reacted with T.

24. A polymer of the formula ##STR25##

wherein:

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.3 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-C25alkyl 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 nitrogenatom 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 alkenylsubstitutedaromatic compounds into the M--R.sup.3 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.

25. The polymer of claim 24, wherein L is a residue of one or more coupling agents selected from the group consisting of isomeric dialkenylaryls, isomeric di- and trivinyl aryls, and mixtures thereof.

26. A functionalized polymer which contains at least one tertiary amine functionality pendant to the polymer backbone.

27. The polymer of claim 26, wherein said polymer is a homotelechelic functionalized polymer.

28. The polymer of claim 26, wherein said polymer is a heterotelechelic functionalized polymer.

29. The polymer of claim 26, wherein said polymer is a functionalized radial polymer.

30. The polymer of claim 26, wherein said polymer is hydrogenated.

31. A tertiary amino anionic polymerization initiator of the formula: ##STR26##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl; and

R.sup.3 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-C25alkyl 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 nitrogenatom and the alkali metal are separated by three or more carbon atoms.

32. A tertiary amino anionic polymerization initiator of the formula: ##STR27##

wherein:

M is an alkali metal;

R.sup.1 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-C16alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;

R.sup.2 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-, oroxy-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 cycloalkylcontaining saturated or unsaturated lower alkyl, aryl, or substituted aryl; and

R.sup.3 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-C25alkyl 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 nitrogenatom 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 alkenylsubstitutedaromatic compounds into the M--R.sup.3 linkage; and

n is an integer from 1 to 5.