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
1998-11-19
2002-03-26
Lipman, Bernard (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...
C525S328900, C525S331100, C525S332200, C525S333300, C525S333500, C525S333600, C525S343000, C525S344000, C525S379000, C525S385000, C525S387000
Reexamination Certificate
active
06362284
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to functionalized polymers and processes for preparing the same. More particularly, the invention relates to heterotelechelic functionalized polymers.
BACKGROUND OF THE INVENTION
Telechelic polymers (i.e., polymers having terminal functional groups) can be used in a variety of applications, such as the manufacture of adhesives, sealants, coatings, films, fibers, and the like. These polymers have typically been prepared using dilithium initiators. See U.S. Pat. Nos. 5,393,843 and 5,405,911. For example, reaction of two equivalents of an alkyllithium reagent, such as sec-butyllithium, with a compound having at least two independently polymerized vinyl groups, such as isomeric divinylbenzenes or isomeric diisopropenylbenzenes, generates a dilithium initiator. Addition of an anionically polymerizable monomer, such as 1,3-butadiene, isoprene, or styrene, affords a polymer chain with living anions on each of the two termini (a “dianion”). This dianion can then be quenched with various functionalizing agents to afford a telechelic polymer.
These functionalization reactions, however, are often inefficient, due to the formation of physical gelation phenomena that produce severe mixing problems. See L. Weber, Makromol. Chem., Macromol. Symp., 3,317 (1986) and U.S. Pat. Nos. 5,393,843 and 5,478,899. In addition, polymers prepared from dilithium initiators necessarily have the same functional group on each termini (are “homotelechelic”).
Electrophiles that contain protected functional groups have been employed to functionalize polystyryl lithium and polyisoprenyl lithium. For example, Deffieux and co-workers reported that chloroacetals afforded high yields of functionalized polystyrene. See Polymer International 41, 453 (1996). Additional references to the use of protected functionalized electrophiles include: M. Tokyamo, A. Hirao, S. Nakahama and K. Takenaka, Macromol. Chem. Phys., 197, 3135 (1996); A. Hirao, H. Nagahama, T. Ishizone, and S. Nakahama, Macromolecules, 26, 2145 (1993), and K. Ueda, A. Hirao, and S. Nakahama, Macromolecules, 23, 939 (1990). The polymers produced in each of these syntheses, however, are monofunctional.
SUMMARY OF THE INVENTION
The present invention provides novel protected, functionalized heterotelechelic polymers (polymers having different functional groups on opposing termini), as well as hydrogenated and/or deprotected analogues thereof. In contrast to telechelic polymers of the prior art, the molecular architecture of compounds of the present invention can be precisely controlled. High functionalization of the living polymer anions can be achieved, as the functionalizing agents of the current invention do not cause gelation when added to a living polymer. The nature of the functional group on each terminus, and its protecting group, can also be varied simply by changing the functionalized initiator or the functionalizing agent.
The invention also provides processes for preparing these compounds. The processes of the invention can provide efficient functionalization of the living polymer anions.
DETAILED DESCRIPTION OF THE INVENTION
The protected heterotelechelic polymers of the present invention can be generally described by the following formula:
(R
1
R
2
R
3
—A)
m
—T—Z—Q
n
—C—Y—W—(B—R
4
R
5
R
6
)
k
wherein:
C represents a hydrogenated or unsaturated block derived by anionic polymerization of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic hydrocarbons, or mixtures thereof;
Y and Z are independently branched or straight chain hydrocarbon connecting groups which contains 3-25 carbon atoms optionally substituted with aryl or substituted aryl containing lower alkyl, lower alkylthio, or lower dialkylamino groups;
Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic hydrocarbons, or mixtures thereof;
T and W are each independently selected from oxygen, sulfur, and nitrogen;
(A—R
1
R
2
R
3
)
m
and (B—R
4
R
5
R
6
)
k
are each protecting groups in which A and B are elements independently selected from Group IVa of the Periodic Table of the Elements; and R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms; and k and m are 1 when T or W is oxygen or sulfur, and 2 when T or W is nitrogen; and
n is an integer from 0 to 5,
with the proviso that —T—(A—R
1
R
2
R
3
)
m
and W—(B—R
4
R
5
R
6
)
k
are not the same.
As used herein the term “with the proviso that T—(A—R
1
R
2
R
3
)
m
and W—(B—R
4
R
5
R
6
)
k
are not the same” refers to polymers in which the protected functional groups T and W differ and in which the respective protecting groups are the same or different; or in which T and W are the same and the respective protecting groups differ.
In one preferred embodiment of the invention, each C block is hydrogenated 1,3-butadiene having a peak molecular weight from 500 to 350,000. Still further, preferably the 1,2-polymerization of the hydrogenated butadiene is between 40% and 60%. In another preferred embodiment of the invention, each C block is hydrogenated isoprene having a peak molecular weight from 500 to 350,000.
To prepare the telechelic polymers of the present invention, living polymer anions are prepared by anionically polymerizing at least one monomer in an inert solvent at a temperature from −30° C. to 150° C. for a period of at least one hour with a protected functionalized initiator having the formula:
M—Q
n
—Z—T—(A—R
1
R
2
R
3
)
m
(I)
wherein:
M is an alkali metal selected from the group consisting of lithium, sodium and potassium;
and each of Q, n, Z, T, A, R
1
, R
2
, R
3
and m are the same as defined above.
The protected functional initiators of formula (I) include omega-(tert-alkoxy)-1-alkyllithiums; omega-(tert-alkoxy)-1-alkyllithiums chain extended with conjugated alkadiene hydrocarbons, alkenylsubstituted aromatic hydrocarbons and mixtures thereof; omega-(tert-alkylthio)-1-alkyllithiums; omega-(tert-alkylthio)-1-alkyllithiums chain extended with conjugated alkadiene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums; omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums chain extended with conjugated alkadiene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; omega-(tert-butyldimethylsilylthio)-1-alkyllithiums; omega-(tert-butyldimethylsilylthio)-1-alkyllithiums chain extended with conjugated alkadiene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; omega-(dialkylamino)-1-alkyllithiums; omega-(dialkylamino)-1-alkyllithiums chain-extended with conjugated alkadiene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; omega-(bis-tert-alkylsilylamino)alkyllithiums; and omega-(bis-tert-alkylsilylamino)alkyllithiums chain extended with conjugated alkadiene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof.
Examples of protected functionalized organolithium initiators (I) include, but are not limited to, tert-alkoxy-alkyllithiums such as 3-(1,1-dimethylethoxy)-1-propyllithium and its more hydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2 in formula (I) above), 3-(tert-butyldimethylsilyloxy)-1-propyllithium (n=0), tert-alkylthio-alkyllithiums such as 3-(1,1-dimethylethylthio)-1-propyllithium and its more hydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2), 3-(dimethylamino)-1-propyllithium and its more hydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2) and 3-[di-(tert-butyldimethylsilyl)amino]-1-propyllithium, and mixtures thereof. Further examples of protected functionalized initiators
Kamienski Conrad William
Kamienski Diane Buschke
Quirk Roderic Paul
Schwindeman James Anthony
Alston & Bind LLP
FMC Corporation
Kamienski Diane Buschke
Lipman Bernard
LandOfFree
Protected functionalized heterotelechelic polymers and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Protected functionalized heterotelechelic polymers and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Protected functionalized heterotelechelic polymers and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2843310