Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymer of an ethylenically unsaturated reactant with a...
Reexamination Certificate
1998-08-24
2001-02-06
Hampton-Hightower, P. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymer of an ethylenically unsaturated reactant with a...
C528S423000, C526S173000, C526S180000, C526S335000, C526S336000, C525S280000, C525S332800, C525S332900, C525S333100, C525S333200, C525S366000, C502S131000, C502S157000, C502S167000
Reexamination Certificate
active
06184338
ABSTRACT:
FIELD OF THE INVENTION
This invention concerns novel anionic polymerization initiators which contain tertiary amine functionality, their chain extended analogues, processes for preparing these initiators, polymers containing tertiary amine functionality, and processes for preparing these polymers.
BACKGROUND OF THE INVENTION
Monofunctional anionic initiators possessing amine functionalities are useful in preparing amino-terminated styrene-butadiene rubbers (SBR). See, for example, European Patent Application 593049A1 and U.S. Pat. No. 5,496,940 to Bridgestone Corporation. These elastomers have been shown to possess increased rebound, decreased rolling resistance, and lower heat build-up (reduced hysteresis). They are useful in forming improved, energy efficient tires, power belts, and mechanical goods.
Typically, the tertiary amino functionality is connected to the alkali metal via a connecting group. Exemplary tertiary amino initiators are illustrated, for example, in FIG. 1 below. Thus, the tertiary amine functionality of the resultant polymer is attached directly on the polymer backbone.
wherein:
M is an alkali metal, preferably lithium;
R
1
and R
2
are alkyl, cycloalkyl or aralkyl having from 1 to 12 carbon atoms;
R
3
is a linear-, branched-, or cyclo-alkylene having from 2 to 20 carbon; and
R
4
is a divalent alkylene, oxy- or amino-alkylene, or substituted alkylene having 6 to 20 carbon atoms. See U.S. Pat. Nos. 5,332,810 and 5,496,940.
Recently, a method of incorporating tertiary amine functionality was described in U.S. Pat. No. 5,736,617, to Bridgestone Corporation. This patent is directed to use of an electrophile, described generically in FIG. 2, to quench a living polymer anion.
wherein:
Z is a halogen atom;
R
1
is selected from the group consisting of organic groups containing from 1 to about 12 carbon atoms and a bridging bond;
each R
2
is independently selected from the group consisting of hydrogen, organic groups containing from 1 to about 12 carbon atoms and a bridging bond;
each R
3
is independently selected from the group consisting of hydrogen, organic groups containing from 1 to about 12 carbon atoms;
a is an integer from 4 to about 16; and
b is an integer from 0 to about 12. These materials, however, were not very efficient electrophiles, as relatively low incorporation of tertiary amine functionality was obtained (11-73%).
SUMMARY OF THE INVENTION
The present invention provides tertiary amino anionic polymerization initiators of the formula:
wherein:
M is an alkali metal;
R
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 -C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
R
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-, 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;
R
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-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—R
3
linkage; and
n is an integer from 1 to 5.
The present invention also provides processes for making the tertiary amino initiators of the invention. In this aspect of the invention, the tertiary amino initiators of this invention are prepared by reaction of selected tertiary amino halides with an alkali metal at a temperature ranging from about 35 to 130° C. in a hydrocarbon solvent to form an alkylorganometallic compound containing a tertiary amine. The resultant compound can be further reacted with one or more conjugated dienes or one or more alkenylsubstituted aromatic compounds, or a mixture thereof, to form an extended hydrocarbon chain between M and R
3
(designated as Q
n
above). Such compounds can have increased solubility in hydrocarbon solvents.
In another aspect of the invention, the tertiary amino initiators of the invention are used to initiate and polymerize anionically polymerizable monomers (such as one or more conjugated dienes, one or more alkenylsubstituted aromatic compounds, or mixtures thereof) to form a living polymer having a pendant tertiary amine functionality. The living tertiary amine containing polymers can be further reacted with a suitable terminating, end capping or coupling agent as known in the art to form linear homotelechelic or heterotelechelic polymers and/or radial polymers. The resultant polymers can further be optionally hydrogenated.
The present invention also provides novel polymers, in which, in contrast to the polymers of the prior art, the tertiary amine functionality is pendant to the polymer backbone. High tertiary amino functionality can be achieved because each polymer chain has a contains an amino functionality derived from the initiator. Further, the tertiary amino funtionalized polymers have improved utility as materials with reduced hysteresis. In addition, the molecular architecture of compounds of the present invention can be precisely controlled. The degree of functionality can be adjusted by simply varying the ratio of tertiary amino functional initiator to coupling agent. Further, the monomer identity, the monomer composition and molecular weight can be independently manipulated by varying the monomer charged. Finally, the number of polymer arms can be adjusted by varying the nature of the coupling agent, and the ratio of living polymer to the coupling agent.
DETAILED DESCRIPTION OF THE INVENTION
The novel, tertiary amino anionic polymerization initiators of the invention can be described as illustrated in FIG. 3 below.
wherein:
M is an alkali metal;
R
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-C16 alkyl containing saturated or unsaturated lower alkyl, aryl, or substituted aryl;
R
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-, 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
R
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-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 alk
Letchford Robert J.
Schwindeman James A.
Alston & Bird LLP
FMC Corporation
Hampton-Hightower P.
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