Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2002-06-21
2004-03-09
Teskin, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S102000, C525S105000, C525S106000, C525S123000, C525S131000, C525S165000, C525S177000, C525S182000, C525S184000, C525S280000, C525S291000, C525S292000, C525S354000, C525S356000, C525S375000, C525S385000, C525S386000, C525S388000, C526S176000, C526S178000, C526S180000
Reexamination Certificate
active
06703446
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to novel polymers and processes for producing the same. More particularly, the invention relates novel hetero-telechelic polymers, and to processes for the anionic polymerization of olefinic-containing monomers to produce the same.
BACKGROUND OF THE INVENTION
Telechelic polymers are polymers that contain two functional groups per molecule at the termini of the polymer. Such polymers have found wide utility in many applications. For instance, telechelic polymers have been employed as rocket fuel binders, in coatings and sealants and in adhesives. In addition, polymers that contain two hydroxyl groups per molecule can be co-polymerized with appropriate materials to form polyesters, polycarbonates, and polyamides (see U.S. Pat. No. 4,994,526).
A variety of polymerization techniques, such as cationic and free radical polymerizations, have been employed to prepare telechelic polymers. However, functionality can be best controlled with anionic polymerization. An early approach to the preparation of telechelic polymers is described in D. N. Schulz, et al,
J. Polym. Sci., Polym. Chem.Ed.
12, 153 (1974), which describes the reaction of a protected hydroxy initiator with butadiene. The resultant living anion was quenched with ethylene oxide to afford mono-protected di-hydroxy polybutadiene. While excellent functionality (f=1.87-2.02) was achieved by this process, the protected initiator was insoluble in hydrocarbon solution. Therefore, the reaction was conducted in diethyl ether, and as a result, relatively high 1,2 microstructure (31-54%) was obtained.
Another approach that has been employed to prepare telechelic polymers is the generation and subsequent functionalization of a “dilithium initiator”. A dilithium initiator is prepared by the addition of two equivalents of secondary butyllithium to meta-diisopropenylbenzene. The dilithium initiator is then reacted with a conjugated diene, such as butadiene or isoprene, to form a polymer chain with two anionic sites. The resultant polymer chain is then reacted with two equivalents of a functionalizing agent, such as ethylene oxide. While useful, gelation is frequently observed during the functionalization step. This leads to lower capping efficiency (see, for example, U.S. Pat. No. 5,393,843, Example 1, wherein the capping efficiency was only 82%). Additional details of this gelation phenomenon are described in U.S. Pat. No. 5,478,899. Further, this dilithium approach can only afford telechelic polymers with the same functional group on each end of the polymer chain.
Great Britain published patent application 2,241,239, published Aug. 28, 1991, describes a novel approach for producing telechelic polymers in hydrocarbon solution. Telechelic polymers were prepared using monofunctional silyl ether initiators containing alkali metal end groups that were soluble in hydrocarbon solutions. These monofunctional silyl ether initiators were demonstrated to be useful in producing dihydroxy (telechelic) polybutadienes having desirable characteristics, such as a molecular weight of typically 1,000 to 10,000, a 1,4 microstructure content of typically 90%, and the like.
SUMMARY OF THE INVENTION
The present invention provides novel hetero-telechelic polymers and processes for preparing the same. The novel hetero-telechelic polymers of the invention can be generally described as having different functionalities at opposite ends of the polymer chain. The presence of different functionalities can provide unique properties to the polymers. Further, the hetero-telechelic polymers of the invention can be copolymerized with other monomers to provide novel copolymers possessing a wide range of useful physical properties.
Preferred hetero-telechelic polymers have the formula:
FG—(Q)
d
—Z—J—[A(R
1
R
2
R
3
)]
x
(I)
wherein FG is a protected or non-protected functional group; Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; d is an integer from 10 to 200; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; J is oxygen, sulfur, or nitrogen; [A(R
1
R
2
R
3
)]
x
is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of Elements; R
1
, R
2
, and R
3
are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, with the proviso J and FG are not the same.
The present invention also provides for the preparation of the novel hetero-telechelic polymers described above. The process of the invention includes polymerizing a monomer, including conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof, with a protected functional organometallic initiator of the formula
M—Q
n
—Z—J—[A(R
1
R
2
R
3
)]
x
(II)
wherein M is an alkali metal, preferably lithium, n is an integer from 0 to 5, and Q, Z, J, A, R
1
, R
2
, R
3
and x are the same as defined above, to form a mono-protected, mono-functionalized living polymer. The resultant living polymer is then functionalized by reaction with a reactive or functionalizing group capable of terminating or end-capping a living polymer to provide a mono-protected or di-protected, di-functional polymer, with the proviso that the initiator and the reactive group contain different functional groups. The resultant hetero-telechelic polymer can be further reacted with other comonomers.
DETAILED DESCRIPTION OF THE INVENTION
The novel hetero-telechelic polymers of the invention can be generally described as having different functionalities at opposite ends of the polymer chain. This is represented schematically by the formula A-------B, wherein A and B are different functional groups.
Preferred hetero-telechelic polymers of the present invention have the following formula:
FG—(Q)
d
—Z—J—[A(R
1
R
2
R
3
)]
x
(I)
wherein FG is a protected or non-protected functional group; Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; d is an integer from 10 to 200; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; J is oxygen, sulfur, or nitrogen; [A(R
1
R
2
R
3
)]
x
is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of Elements; R
1
, R
2
, and R
3
are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, with the proviso J and FG are not the same.
Removal of the protecting group (deprotection) produces polymers with oxygen, sulfur or nitrogen functional groups on the ends of the polymers. The residual aliphatic unsaturation can be optionally removed by hydrogenation before or after removal of the protecting groups. These functional groups can then participate in various copolymerization reactions by reaction of the functional groups on the ends of the polymer with selected difunctional or polyfun
Kamienski Conrad W.
Letchford Robert J.
Quirk Roderic P.
Schwindeman James A.
FMC Corporation Lithium Division
Myers Bigel Sibley & Sajovec P.A.
Teskin Fred
LandOfFree
Hetero-telechelic polymers and processes for making same does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Hetero-telechelic polymers and processes for making same, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Hetero-telechelic polymers and processes for making same will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3211323