Acrylamide derivatives and polymers containing said derivatives

Details Acrylamide derivatives and polymers containing said derivatives Acrylamide derivatives and polymers containing said derivatives

2001-08-30

2002-12-17

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...

C526S303100, C526S314000, C526S305000, C526S307000, C526S307100, C526S307200, C526S307500

Reexamination Certificate

active

06495645

ABSTRACT:

This application is the national phase under 35 U.S.C. §371 of PCT International Application No. PCT/JP00/00314 which has an International filing date of Jan. 24, 2000, which designated the United States of America and was published in English.
TECHNICAL FIELD
The present invention relates to acrylamide derivatives having functional groups on side chains, homopolymers and copolymers of said derivatives, as well as crosslinked products of said polymers. Acrylamide derivatives of the present invention can readily be radical-polymerized to conveniently prepare homopolymers and can also be copolymerized with other monomers. Copolymers synthesized from acrylamide derivatives of the present invention can be temperature-responsive polymers, which are soluble below but insolubilized above a specific temperature in aqueous solutions. Thus, they can be immobilized on the surface of a solid to show hydrophilicity and hydrophobicity below and above the specific temperature, respectively. Copolymers of the present invention can be used not only to switch between hydrophilicity and hydrophobicity in a narrow temperature range but also to switch from an electrically charged state to a non-charged state simply by temperature change. Moreover, their various functional groups can be used to introduce various molecules via covalent or hydrogen bonds.
BACKGROUND ART
N-alkyl-substituted acrylamide polymers are one of temperature-responsive polymers, among which poly(N-isopropyl acrylamide) (hereinafter abbreviated as PIPAAm) is water-soluble below but rapidly insolubilized to form a precipitate above the phase transition temperature of 32° C. Sequences of PIPAAm have been introduced into the surfaces of solids to switch between hydrophilicity and hydrophobicity simply by temperature change for harvesting cells after culture or development into chromatography. Such techniques are described in the following documents, for example:
T. Okano, N. Yamada, H. Sakai, Y. Sakurai, Journal of Biomedical Materials Research, vol. 27, pp. 1243-1251 (1993);
T. Okano, N. Yamada, M. Okuhara, H. Sakai, Y. Sakurai, Biomaterials, vol. 16, pp. 297-303 (1995);
H. Kanazawa, K. Yamamoto, Y. Matsushima, N. Takai, A. Kikuchi, Y. Sakurai, T. Okano, Analytical Chemistry, vol. 68, pp. 100-105 (1996);
H. Kanazawa, Y. Kashiwase, K. Yamamoto, Y. Matsushima, A. Kikuchi, Y. Sakurai, T. Okano, Analytical Chemistry, vol. 69, pp. 823-830 (1997).
These temperature-responsive polymers are commonly copolymerized with comonomers having a functional group such as acrylic acid to introduce the functional group into said polymers. However, straight-chain polymers or hydrogels (i.e. crosslinked products) incorporating an increased rate of acrylic acid inevitably showed a significant rise in phase transition temperature and insensitive transition behaviors. Namely, no method has existed for introducing many functional groups into temperature-responsive polymers or hydrogels while maintaining the sensitive temperature response.
DISCLOSURE OF INVENTION
An object of the present invention is to provide a monomer for preparing a polymer or hydrogel (i.e. crosslinked product) incorporating many functional groups while maintaining the sensitive temperature response, and said polymer or hydrogel (i.e. crosslinked product).
We carefully studied to solve the above problems. As a result, we found that the temperature response of homopolymers can be maintained by copolymerizing them with a monomer having a closely similar structure to that of the homopolymers, and thus attained the present invention.
Accordingly, the present invention provides acrylamide derivatives of the following general formula (I):
wherein R
1
represents a hydrogen atom, a straight-chain or branched alkyl group containing 1 to 6 carbon atoms or a C3-6 cycloalkyl group, R
2
and R
3
each independently represent an alkylene group containing 1 to 6 carbon atoms or R
2
and R
3
may be combined to form a ring, X represents a hydrogen atom, an amino group, a hydroxyl group, a halogen atom, a carboxyl group or a —COOR
4
group wherein R
4
represents a C1-6 straight-chain or branched alkyl, C3-6 cycloalkyl, phenyl, substituted phenyl, benzyl or substituted benzyl group, and Y represents an amino group, a hydroxyl group, a halogen atom, a carboxyl group or a —COOR
4
group wherein R
4
represents a C1-6 straight-chain or branched alkyl, C3-6 cycloalkyl, phenyl, substituted phenyl, benzyl or substituted benzyl group.
The present invention also provides polymers consisting of identical or different repeating units of the following general formula (II):
wherein R
1
represents a hydrogen atom, a straight-chain or branched alkyl group containing 1 to 6 carbon atoms or a C3-6 cycloalkyl group, R
2
and R
3
each independently represent a alkylene group containing 1 to 6 carbon atoms or R
2
and R
3
may be combined to form a ring, X represents a hydrogen atom, an amino group, a hydroxyl group, a halogen atom, a carboxyl group or a —COOR
4
group wherein R
4
represents a C1-6 straight-chain or branched alkyl, C3-6 cycloalkyl, phenyl, substituted phenyl, benzyl or substituted benzyl group, and Y represents an amino group, a hydroxyl group, a halogen atom, a carboxyl group or a —COOR
4
group wherein R
4
represents a C1-6 straight-chain or branched alkyl, C3-6 cycloalkyl, phenyl, substituted phenyl, benzyl or substituted benzyl group.
The present invention also provides copolymers consisting of different or identical repeating units of the above general formula (II) and different or identical repeating units of general formula (III):
wherein R
1
represents a hydrogen atom, a straight-chain or branched alkyl group containing 1 to 6 carbon atoms or a C3-6 cycloalkyl group, R
5
represents a straight-chain or branched alkyl group containing 1 to 6 carbon atoms or a C3-6 cycloalkyl group, and R
6
represents a straight-chain or branched alkyl group containing 1 to 6 carbon atoms or a C3-6 cycloalkyl group, or R
5
and R
6
may be combined to form a 3-, 4-, 5 or 6-membered ring in which the —CH— group to which they are attached is one member.
Additionally, the present invention provides crosslinked products containing said polymers and crosslinked products containing said copolymers.


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Okano et al., J. Biomedical Materials Research, vol. 27 (1993) pp. 1243-1251.
Okano et al., Biomaterials, vol. 16, No. 4 (1995) pp. 297-303.
Kanazawa et al., Analytical Chemistry, vol. 68, No. 1 (1996) pp. 100-105.
Kanazawa et al., Analytical Chemistry, vol. 69, No. 5 (1997) pp. 823-830.
Koyama E. et al., “Syntheses and Radical Polymerizations of Methacrylamides derived from Optically active amino Alcohols”, Macromolecular Chemistry and Physics, vol. 198, No. 11, Nov. 1, 1997, pp. 3699-3707.
Beger J. et al., “Halogenierung Von Olefinen In Gegenwart Organischer Cyanverbindungen”, Journal Fuer Praktische Chemie, vol. 311, Jan. 1, 1969, pp. 15-35.
Meyers, A.I. et al., “The synthesis of chiral. alpha.,. beta.-unsaturated and aryl oxazolines from ketones and arols via their triflates and palladium-catalyzed carbon monoxide and amino alcohol coupling”, Tetrahedron Lett, 1992, p. 1182; figure 5 and p. 1183.

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