Organic compounds -- part of the class 532-570 series – Organic compounds – Chalcogen in the nitrogen containing substituent
Reexamination Certificate
1999-05-06
2001-05-22
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Chalcogen in the nitrogen containing substituent
C544S096000, C544S097000, C548S229000, C548S237000, C548S238000
Reexamination Certificate
active
06235901
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
None
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
None
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to an aqueous coating composition such as coatings, inks, coverprint varnish and surface treatment applications containing an oxazoline or oxazine acetoacetate polymer.
2. Background Art
In the following description of the prior art and in the Examples, the parenthetical numbers are described in the following Reference section. Acetoacetamide, acetoacetanilide, and acetoacetate functionalized chemicals are readily available, via reaction of amines or hydroxyl substituted molecules with diketene (1-3), alkyl acetoacetates, or the readily used acetoacetalation compound 2,2,6-trimethyl-1,3-dioxin-4-one, which is prepared from reaction of diketene with acetone (2,4). Organic compounds or polymers with the acetoacetamide, acetoacetanilide, or acetoacetate type functionality are known to react with a variety of other functional chemicals (1-5), including such things as amines, aldehydes, and isocyanates, giving various adducts in excellent yields at low reaction temperatures (2). Also, the acetoacetamide, acetoacetanilide, or acetoacetate group, with amine catalysts, will combine readily with the acrylate functionality, via what is commonly called the Michael addition reaction (2,5,6). Further, these acetoacetanilide, acetoacetamide, or acetoacetate groups are known to readily react with various metal compounds, such as CaO, Ca(OH)
2
, BaO, CoCI
2
, NiCI
2
, etc. to form metal complexes (1,3), where the chemistry has been used to prepare polymeric catalysts (2,7,8) and crosslinked coatings (6,9-11). These chemicals with the acetoacetamide, acetoacetanilide, and/or acetoacetate functionality, which have three active centers, have found extensive utility in the formation of metal-complexes, manufacture of dyes and synthesis of heterocycles (1-3).
It is well known that cyclic imino ethers, such as oxazolines and oxazines will undergo cationic, ring-opening polymerizations (12) and zwitterionic copolymerization with such things as acrylic acid, maleimides, anhydrides, lactones, etc. (13-17). It is also well known that molecules with the oxazoline or oxazine residues will undergo ring-opening reactions with compounds such as carboxylic acids, thiols (HS-groups), phenols, alkyl halides, etc., giving 1-to-1 adducts (18-24), allowing for step-growth copolymerizations to be readily achieved with difunctional monomers. Further, it has been shown that alkyl halides will initiate ring-opening polymerization of cyclic imino ethers, as well as give 1:1 adducts (18, 25). Thus oxazolines and oxazines are excellent intermediates for synthesis of variety of polymeric materials, both thermoplastics and thermosets, by chain-growth and step-growth polymerization mechanisms or combinations thereof. In addition, the synthesis and polymerization of oxazoline and oxazine methacrylate aqueous coating compositions are also known (27).
REFERENCES
1. U.S. Pat. No. 3,304,328 (Feb 14, 1967) to FMC Corporation.
2. N.Moszner, U.Salz, V. Rheinberger, MACROAKRON '94, 35th IUPAC Int. Symp. on Macromolecules, Jul. 11-15, 1994 paper.
3. S. M. Hussain, A. M. El-Reedy, S. A. El-Sherabasy, J. Heterocyclic Chem., 25, 9-22 (1988).
4. Wacker Chemicals (USA), Inc. literature, p. 16.
5. R. J. Clemens, J. S. Witzman, F. Del Rector, Communications of Eastman Chemical Products, Inc.
6. K. J. Edgar, K. M. Arnold, W. W. Blount, J. E. Lawniczak, and D. W. Lowman, Macromolecules 1995, 28, 4122-4128.
7. T.Sato, A. Morita, I. Kamiya, T. Ota, Makromol. Chem., Rapid Comm.11 (1990) 553.
8. R.Ran, D.Fu, J. Macromol.Sci.-Chem.A27 (1990) 625.
9. D. L. Trumbo, Polymer Bull.26 (1991) 265,481.
10. J. R. Grawe, B. G. Burkin, J. Coatings Technol. 52 (1980) 73.
11. U.S. Pat. No. 4,247,671 (Jan. 27, 1981) to Rohm and Haas Co.
12. S.Kobayashi and T. Saegusa, Encyclopedia of Polymer Science and Engineering, Wiley & Sons, New York, Vol. 4, pp. 525-537, 1986.
13. G. Odian, M.P. O'Callaghan, C. K. Chien, P. Gunatillake, M. Periyasay and D. L. Schmidt, Macromolecules, 23(4), 918-927 (1990).
14. C. I. Simionescu, et.al., Polymer.Bull. (Berlin), 14(1), 79-83 (1985).
15. T. Saegusa, Makromol. Chem., Suppl., 4, 73-84 (1981).
16. B. L. Rivas and G. D. Pizarro, Eur. Polym. J., 25(10), 1001-1005 (1989).
17. G. S. Canessa, A. S. Pooley, M.Parra and B. L. Rivas, Polym. Bull.(Berlin), 11(5), 465-70 (1984).
18. J. A. Frump, Chem.Rev., 71(5), 483-505 (1971).
19. U.S. Pat. No. 3,758,629 (Sept. 11, 1973), to Dow Chemical.
20. U.S. Pat. No. 4,600,766 (Jul. 15, 1986) to Takeda Chemical Co.
21. T. Nishikubo, T. Iizawa and A. Tokairin, Mackromol. Chem., 185, 1307-1316 (1984).
22. T. Kagiya, S. Narisawa, T. Maeda and K. Fukui, Polymer Letters, 4, 257-260 (1966).
23. U.S. Pat. No. 4,430,491 (Feb. 7, 1984) to Ashland Chemical Co.
24. B. M. Culbertson, M. L. Deviney, 0. Tiba and D. D. Carlos, 33rd SAMPE Symp., March 7-10, pp. 1530-1545 (1988), Ibid. 34h SAMPE Symp. May 8-11, 1989. PP.2483-2497.
25. S. Kobayashi, H. Uyama, Y. Narita and J. Ishiyama, Macromolecules, 25(12), 3232-3236 (1992).
26. H. Witte and W. Seelinger, Liebigs Ann. Chem., 996-1009 (1974).
27. H. A. A. Rasoul, D. B. Obuchowski, D. L. Trumbo, B. M. Culbertson, and Y. Xue, Oxazoline Hydrolysis, Synthesis and Polymerization of a New Oxazoline Methacrylate, PP. 871-872 (1997).
The prior art fails to disclose chemical compositions, monomeric or polymeric having both the cyclic imino ether and the acetoacetamide, acetoacetenilide or acetoacetate residues on the same molecule.
SUMMARY OF THE INVENTION
The novel compound of this invention has the following formula:
wherein R is an alkyl group containing 1-5 carbon atoms or an aryl, substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl, alkylether-aryl or O; R
1
and R
2
are hydrogen or a methyl group; X is O, NH, NR′ wherein R′ is an alkyl group containing 1-5 carbon atoms, or O—R″ or NR″ wherein O—R″ is O-alkyl-O or O-alkyl, NR″ is O-alkyl-OHN, ) or
wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.
The compounds of this invention are monomers which may be polymerized or opolymerized, via cationic, ring-opening polymerization of the cyclic imino ether residues, producing polymers with pendant acetoacetamide, acetoacetanilide and/or acetoacetate groups. Polymers of the aforesaid type may be readily crosslinked, via a variety of reactions as explained in the background art, to produce crosslinked materials useful in coatings, adhesives, and other applications. Further, these monomers and polymers are shown to readily form metal complexes with a variety of metal salts, giving in many cases, highly colored monomer-metal or macromolecular-metal complexes.
Referring to the previous formula, in the instance where R is aryl, X is NH, R
1
and R
2
are H and n is 0, this compound can be readily prepared by reacting an aminophenyl oxazoline with diketene. In the instance where R is aryl, X is NH, R
1
and R
2
are H and n is 1,2-(4-aminophenyl) oxazine was reacted with diketene. The compound where R is aryl, X is NR′, R
1
and R
2
are H and n is 0, this compound is prepared by reacting aminobenzonitrile with an alkyl iodide to obtain an alkylaminobenzonitrile which is treated with ethanolamine to obtain alkylaminophenyl oxazoline. The resulting oxazoline compound is subsequently treated with 2,2,6-trimethyl-1,3-dioxin-4-one (TDO). The compound where R is aryl, X is NH, R, R
1
and R
2
are CH
3
and n is 0 is prepared by reacting ethylaminobenzoate with methylaminopropanol to yield a dimethyl derivative of aminophenyl oxazoline with the resulting oxazaline treated with TDO. The compound where R is alkyl, X is alkyl, R
1
and R
2
are hydrogen and n is 0 is prepared by reacting an alkylamino alkylnitrile with ethanolamine to obtain alkylamino alkyloxazoline which is subsequently treated with TDO. As to the compound where R, R
1
, R
2
and n are as immediately and previously described but X is O-alkyl, it i
Culbertson Bill M.
Trumbo David L.
Bovee Warren R.
Hamilton Neil E.
Raymond Richard L.
Rymarz Renee J.
S. C. Johnson Commercial Markets, Inc.
LandOfFree
Oxazoline or oxazine acetoacetate aqueous coating compositions does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Oxazoline or oxazine acetoacetate aqueous coating compositions, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Oxazoline or oxazine acetoacetate aqueous coating compositions will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2565431