Vinyl-phenyl pyridine monomers and polymers prepared therefrom

Details Vinyl-phenyl pyridine monomers and polymers prepared therefrom Vinyl-phenyl pyridine monomers and polymers prepared therefrom

2001-08-10

2003-04-08

Rotman, Alan L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S350000

Reexamination Certificate

active

06545159

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to vinyl-phenyl monomers and polymers prepared therefrom. More particularly, the present invention is to provide the vinyl-phenyl monomers expressed by formula (1) which are capable of various polymerization such as radical polymerization, cationic polymerization, anion polymerization and metallocene catalyzed polymerization due to the resonance effect of phenyl group and changing characteristics variously and thus, suitable in the synthesis of polymers which can be used in photo-functional materials by forming a polymer complex with a metal component having an optical characteristic.
Continuous polymerization can be divided to ionic polymerization and radical polymerization depending on an initiator. It is difficult to do a controlled polymerization due to side reaction with the radical chain ends in radical polymerization, and reaction termination for the repulsion between the functional groups chain ends in ionic polymerization. Reactivity of radical polymerization varies with resonance stability of vinyl group and that of ionic polymerization varies with the polarity.
Monomers used in continuous polymerization can be polymerized by means of radical, cationic or anionic polymerization depending on Q-e value shown in the following table. Especially, either cationic or anionic polymerization can be expected with e value representing the degree of polarity.
Cationic
Anionic
Monomer
◯
e
Polymerization
Polymerization
0.02
−1.8
⊚
X

0.98
−1.27
⊚
◯

1.00
−0.80
◯
◯

0.42
0.62
X
◯

0.60
1.20
X
⊚
The polarity of a monomer is important in anionic polymerization because reactivity is highly dependent on the polarity of the monomer. That is, a selection of monomers plays an essential role in the synthesis of block copolymers. A monomer having an electron-withdrawing character in vinyl group is preferable for anionic polymerization. Representative anionic monomers are styrene, &agr;-methylstyrene, butadiene and isoprene which undergo the polymerization with a carbanion having strong reactivity because they have −e values. The order of polymerization is &agr;-methylstyrene, isoprene and styrene.
Polymers having functional groups can be widely used for photo-functional materials. In order to polymerize styrene, butadiene and methacrylate having a variety of functional groups through anionic polymerization, it is required to protect the functional groups during the polymerization to prevent from the termination reaction between carbanion and the functional groups. S. Nakahama et. al have reported that styrene monomer having amine, hydroxy, carbonyl, carboxyl, or mercapto group can be protected with an appropriate protecting group such as trimethyl silyl, t-butyldimethyl silyl, oxazoline and ester groups during the polymerization and the protected functionality is then deprotected to regenerate the original functional group after the polymerization [S. Nakahama,
Prog. Polym. Sci.,
15, 299 (1990);
Makromol, Chem.,
186, 1157 (1985);
Polymer,
28, 303(1987);
Macromolecules,
19, 2307 (1986); ibid. 26, 4995 (1993); ibid. 26, 35 (1993);
Macromolecules,
20, 2968 (1987); ibid. 24, 1449 (1991); ibid. 26, 6976 (1993);
Macromolecules,
19, 2307 (1986); ibid. 21, 561 (1988); ibid. 22, 2602 (1989)]. And further, the research and development of photo conductive and organic light emitting devices using phenylpyridines have been actively studied and some examples have been reported [Alistair J. Lee,
Chem. Rev.
1987, 87, 711~743; M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, S. R. Forrest,
Appl. Phys. Lett.,
75, 4, (1999); Raymond C. Kwong, Sergey Lamansky, and Mark E. Thompson,
Adv. Mater.,
2000, 12, No. 15, 1134; Catherine E. Housecroft,
Coordination Chemistry Reviews,
152, (1996), 141~156; K. Dedeian, P. I. Djurovich, F. O. Garces, G. Carlson, R. J. Watts,
Inorg. Chem.,
1991, 30, 1687~1688; King, K. A, Spellane, P. J., Watts, R. J.,
J. Am. Chem. Soc.,
1985, 107, 1431].
However, the study of phenylpyridines is limited to only organic molecule and there is no report in the synthesis of the corresponding polymers using phenylpyridine monomers.
The present invention is to provide 2-(4-vinyl-phenyl)pyridine monomers and polymers with controllable molecular weight and molecular structure which can be widely useful for photo-functional materials since said polymers of such monomers is reliable to form a complex of a metal component (iridium, ruthenium and the like).
SUMMARY OF THE INVENTION
Vinyl-phenyl monomers of formula (1) of the present invention are capable of various polymerization such as radical polymerization, cation polymerization, anion polymerization and metallocene catalyzed polymerization due to the resonance effect of the phenyl group.
The molecular weight and molecular structure of polymers can be controlled during the polymerization and the prepared polymers can further form a complex with various metal components such as iridium, ruthenium and the like to be useful for photo-functional materials.
Therefore, an object of the present invention is to provide vinyl-phenyl pyridine monomers and the preparation method thereof which can be easily introduced to synthesize polymers with the controlled functional groups and thus, such polymers can be applied in the preparation of thin film or fiber depending on the purpose.
Another object of the present invention is to provide the polymers prepared by using the monomers of formula (1).
Further objection of the present invention is to provide a complex of the polymers and iridium, ruthenium or platinum having optical character.


REFERENCES:
English Abstract, Polymeric Copper Complexes in oxidative coupling reactions, Challa G. et al 1978, vol. 183, pp. 185-193.*
T. Ishizone et al., Anionic Polymerization of Monomers Containing Functional Groups. 7. Anionic Polymerizations of N-Alkyl-N-(4-vinylbenzylidene) amines, Macromolecules, vol. 26, No. 25, pp. 6976-6984. (1993).
Y. Ishino et al., Protection and Polymerization of Functional Monomers. 7. Anionic Living Polymerization of 2-(4-vinylphenyl)-4,4-dimethyl-2-oxazoline; Macromolecules, vol. 19, pp. 2307-2309 (1986).
A. Hirao et al., Protection and Polymerization of Functional Monomers. 18. Synthesis of Well-Defined Poly(vinylphenol), Poly[vinylphenyl) methanol], and Poly [2-(vinlyphenyl) ethanol] by Means of Anionic Living Polymerization of Styrene Derivatives Containing tert-Butyldimethylsily Ethers, Macromolecules, vol. 26, pp. 4995-5003, (1993).
A. Hirao et al., Protection and Polymerization of Functional Monomers. 11. Syntheses of Well-Defined Poly (4-vinylbenzoic acid) by Means of Anionic Living Polymerization of 2-(4-Vinylphenyl)-4, 4-dimethyl-2-oxazoline, Macromolecules, vol. 21, pp. 561-565, (1988).
M.A. Baldo et al., Very high-efficiency green organic light-emitting devices based on electrophosphorescence.
C. Landry, et al., Novel Miscible Blends of Etheric Polyphosphazense with Acidic Polymers, Macromolecules, vol. 26, pp. 35-46 (1993).
T. Ishizone et la., Protection and Polymerization of Functional Monomers. 15. Anionic Living Polymerization of 2-(3-Vinylpheny)-1,3-dioxolane and Related Monomers, Macromolecules, vol. 24, pp. 1449-1454 (1991).
A. Hirao., Protection and Polymerization of Functional Monomers. 103. Syntheses of Well-Defined Poly(4-vinlybenzaldehyde) by the Anionic Living Polymerization of N-[4-Ethenylphenyl) methylene] cyclohexamine, Macromolecules, vol. 20, No. 12, pp 2968-2972 (1977).
J. Lee, et al., Polymerization of Monomers Containing Functional Silyl Groups. 7. Porous Membranes with Controlled Microstructures, Macromolecules, vol. 22, No. 6, pp. 2602-2606 (1989).
S. Nakahama et al., Protection and Polymerization of Functional Monomers: Anionic Living Polymerization of Protected Monomers, Program of Polymer Science, vol. 15, pp. 299-335, (1990).
R. Kwong et al., Organic Light-Emitting Devices Based on Phosphorescent Hosts & Dyes, Advanced Materials, vol. 12, No. 1

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