Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-06-30
2001-04-24
Teskin, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S173000, C526S178000, C526S180000, C526S181000, C526S328000, C526S329700, C526S341000, C525S088000, C525S093000, C525S094000, C525S100000, C525S102000, C525S123000, C525S178000, C525S183000, C525S272000, C525S288000, C525S292000, C525S305000, C525S329100, C525S329400, C525S330300, C525S330400, C525S330500, C525S338000, C525S342000, C525S343000, C525S354000, C525S356000, C525S359200, C525S359600, C525S383000, C525S385000
Reexamination Certificate
active
06221991
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to novel functionalized polar polymers and processes for producing the same. More particularly, the invention relates novel functionalized methacrylate and acrylate polymers and processes for the anionic polymerization of the same.
BACKGROUND OF THE INVENTION
Living polymerizations can provide advantages over other polymerization techniques, such as well-defined polymer structures and low degree of compositional heterogeneity. Many of the variables that affect polymer properties can be controlled, including molecular weight, molecular weight distribution, copolymer composition and microstructure, stereochemistry, branching and chain end functionality.
Living anionic polymerization of styrene and diene monomers were first described by Szwarc and his coworkers. See M. Szwarc,
Nature
178, 1169 (1956) and M. Szwarc, et al.,
J. Am. Chem. Soc.
78, 2656 (1956). While living anionic polymerization can be effective for the controlled polymerization of non-polar monomers, anionic polymerization of polar monomers, such as methacrylates and acrylates, is more problematic. The presence of a carbonyl group in acrylate monomers complicates anionic polymerization of polar monomers. For example, nucleophilic attack at the carbonyl group can lead to no initiation or polymerization termination.
Various techniques have been proposed to address the problem of anionic polymerization of methacrylate and acrylate monomers. Proposals include low polymerization temperatures (−78° C.), the use of sterically hindered initiators, bulky alkyl ester groups, and the addition of complexing agents, such as crown ethers, lithium chloride and lithium alkoxides. Other techniques include metal-free anionic polymerization using delocalized carbanion initiators with nonmetallic tetrabutylammonium salts (see, e.g., M. T. Reetz,
Angew. Chem. Int. Ed. Eng.
27, 994 (1988)); group transfer polymerization, using a silicon-based initiator (O. W. Webster, et al., European Patent 0 068 887 (1986)); and immortal polymerization using aluminum porphyrins as initiators (M. Kuroki et al.,
J. Am. Chem. Soc.
109, 4739 (1987); Y. Hosokawa, et al.,
Macromolecules
24, 824 (1991)). See also, T. P Davis, et al.,
Rev. Macromol. Chem. Phys.,
C34(2), 243-324 (1994) and H. Hsieh and R. Quirk,
Anionic Polymerization
(Marcel Dekker, Inc., New York 1996) for a more complete review.
Although useful, these and other techniques of anionic polymerization of methacrylate and acrylate monomers can suffer from drawbacks, such as ineffectiveness at higher temperatures, slow reaction rates, broad molecular weight distributions, poor copolymerization with polar and non-polar comonomers, and the like. Further, these processes can be expensive, thus limiting their commercial applicability. These problems can be compounded when polymerizing acrylate monomers, which are more reactive than methacrylate monomers.
SUMMARY OF THE INVENTION
The present invention provides novel polar polymers, including functionalized, telechelic, heterotelechelic, and multi-branched or star methacrylate and acrylate polymers, and processes for preparing the same. The novel polymers have applications in a variety of areas, including use in low VOC coatings, adhesives, and as viscosity index (V.I.) improvers for lubricants.
The present invention also provides processes for anionic polymerization of polar monomers to produce the polymers of the invention. These polymers are prepared from protected functionalized initiators which are reacted with an appropriate diaryl alkenyl group, such as 1,1-diphenylethylene, to provide a stabilized carbanion. A polar monomer, preferably methyl methacrylate, is polymerized in the presence of the initiator to provide a living anion.
The resultant living anion can be quenched, for example with acidic methanol, to afford a protected, mono-functional polar polymer, and removal of the protecting group results in a functionalized polar polymer.
Alternatively, the resultant living anion can be quenched with various functionalizing agents, such as ethylene oxide, carbon dioxide, epichlorohydrin, and the like, to afford a mono-protected telechelic polar polymer. The functional groups on the termini of the polymer can be the same (such as two hydroxyl groups) or different (such as one hydroxyl group and one amino group).
Protected, functionalized polar star polymers can also prepared by linking the living anion with suitable linking agents, such as ethylene glycol dimethylacrylate, glycerol trimethacrylate, &agr;,&agr;′-dibromo-p-xylene, &agr;,&agr;′,&agr;″-tribromo-mesitylene, and the like. Subsequent deprotection affords functionalized polar stars.
In contrast to star polymers of the prior art, the molecular architecture of compounds of the present invention can be precisely controlled. For example, each arm of the multi-arm polymer can contain a functional group (protected or non-protected), and the functional groups (and/or protecting groups) can be the same or different. The star polymers can also include both functional and non-functional ends. The nature of the functional group, and/or protecting group, and/or non-functional group can be varied simply by changing the initiator, and the ratio of one functional group to another functional group, or of one functional group to a non-functional group, can be adjusted by simply varying the ratio of initiators to one another. Further, monomer identity, monomer composition and molecular weight of both functional and non-functional arms can be independently manipulated by varying the monomer charged by each initiator. Still further, 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 polar polymers of the present invention have the following formula:
FG-(Q)
d
-R
n
-Z-J-[A(R
1
R
2
R
3
)]
x
(I)
or
L[(Q)
d
R
n
-Z-J-[A(R
1
R
2
R
3
)]
x
]
m
(II)
wherein FG is H or a protected or non-protected functional group; Q is a hydrocarbyl group derived by incorporation of a polar monomer selected from group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof with one another and/or with other polar monomers; d is an integer from 10 to 2000; R 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; n is an integer from 0 to 5; 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. L in formula II is a linking agent selected from the group consisting of reactive halogen compounds and multifunctional acrylates, as described below.
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 polyfunctional comonomers and/or linking or cou
Kamienski Conrad W.
Letchford Robert J.
Quirk Roderic P.
Schwindeman James A.
Alston & Bird LLP
FMC Corporation
Teskin Fred
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