Vinyl-phenyl pyridine monomers and polymers prepared thereform

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

2003-02-14

2003-12-09

Pezzuto, Helen L. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S241000, C526S259000

Reexamination Certificate

active

06660821

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
Monomer
Cl
e
Polymerization
Anionic Polymerization
0.02
−1.8
⊚
X

0.96
−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 serene.
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, Clem
., 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,
Clem. 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 polyesters 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:
patent: 3-34382 (1991-02-01), None
patent: 11-80326 (1999-03-01), None
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