USOO6825313B2 (12) United States Patent (10) Patent No.: US 6,825,313 B2 Sikes (45) Date of Patent: Nov.30, 2004 (54) COPOLYMERS OF AMINO ACIDS AND 5,493,004 A 2/1996 Groth et al. METHODS OF THEIR PRODUCTION 5,548,036 A 8/1996 Kroner et al. 5,594,077 A 1/1997 Groth et al. 5,639,832 A 6/1997 Kroner et al. (75) Inventor: C. Steven Sikes, Eugene, OH (US) 5,714,558 A 2/1998 Groth et al. (73) Assignee: Aquero Company, Eugene, OR (US) 5,981,691 A 11/1999 Sikes 6,054,553 A 4/2000 Groth et al. (*) Notice: Subject to any disclaimer, the term of this 6,063,961 A 5/2000 Kroner patent is extended or adjusted under 35 6,495,658 B2 12/2002 Sikes et al. U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 10/431,124 Copy of International Search Report in Application No. (22) Filed: May 7, 2003 PCT/USO3/14312. (65) Prior Publication Data Primary Examiner Duc Truong US 2004/0006198 A1 Jan. 8, 2004 (74) Attorney, Agent, or Firm-LeeAnn Gorthey; Perkins Coie LLP Related U.S. Application Data (60) Provisional application No. 60/378.915, filed on May 7, (57) ABSTRACT 2002. Disclosed are copolymers based on aspartic acid or its (51) Int. Cl." ................................................ C08G 73/10 precursor molecules and methods of their production. The (52) U.S. Cl. ....................... 528/322; 528/310; 528/328; copolymers are water-Soluble over a wide range of compo 528/489; 525/419; 525/420; 525/422 Sition and molecular weight. Their preparation involves (58) Field of Search ................................. 528/322,310, conversion of a polySuccinimide to copolymers of defined 528/328, 489; 525/419, 420, 422 composition, containing aspartate and Succinimide residues and/or residues of asparagine. In particular, the copolymers (56) References Cited include water-Soluble terpolymers of aspartate, asparagine, and Succinimide. U.S. PATENT DOCUMENTS 5,478,919 A 12/1995 Koskan et al. 29 Claims, 8 Drawing Sheets O O O aqueous, OH O N- mild A co A N NaOH as - 1NN O HN-C-COOH O NH4OH H O O pH 9 to 11 aspartic acid HO polysuccinimide pNa' NH, o NH o=g 9 o=c o o=g 9 adjust pH C-C-C-N C-C-C-NH C-C-C-N H. H. H. H. H. H. remove watc sodium aspartate asparagine ammonium aspartaten solute of the terpolymer of aspartate, asparagine, ammonium aspartate oNa' NH, O=C 9 O-C 9 Oc l80° C. C-C-C-NH-I-C-C-C-NH -rra H. H. H. H. sodium aspartate' asparagine aspartic acid NH' aspartaten Salt of the copolymer of aspartate, asparaginc, aspartic acid, and/or ammonium aspartate O N sodium asparate asparagine succinimidOc. terpolymer of aspartate, asparagine, succinimide U.S. Patent Nov.30, 2004 Sheet 1 of 8 US 6,825,313 B2 O O O aqueous, N- mild A CooH O N NaOH CH 2 ---A N N O -n-Har HN-C-COOH O NH4OH H O O pH 9 to ll aspartic acid H2O polysuccinimide oN a' NH, o NH O=C 9 o=C 9 o=c 9 adjust pH C-C-C-NH C-C-C-NH C-C-C-NH H. H. H H2 b H. H. CInOWe Water sodium aspartate asparagine ammonium aspartaté On solute of the terpolymer of aspartate, asparagine, ammonium aspartate oNa' NH, pH oNH' O=C 9 O-C 9 O=g Q O=c 9 80°C C-C-C-NH C-C-C-NH C-C-C-NH C-C-C-NH -ms H. H. H. H. L H H, HH, 3h. sodium aspartate asparagine aspartic acid c NH' aspartate C salt of the copolymer of aspartate, asparaginc, aspartic acid, and/or ammonium aspartate oNa' NH, p O=c Q O=C 9 N C-C-C-NH C-C-C-NH C H H. H. H. A. b O c sodium asparate asparagine succinimid terpolymer of aspartate, asparagine, succinimide Fig. 1 U.S. Patent Nov.30, 2004 Sheet 2 of 8 US 6,825,313 B2 o P O O N- aqueous 9 COOH A N-l- mild A CH, ? O O H.N-COOH ) O NH4OH O pH 9 to ll aspartic acid HO polysuccinimide NH, pNH' O=g 9 O=g 9 adjust pH C-C-C-NH C-C-C-NH -b- H H2 H H2 renOVC Water asparagine aspartic acid solute of the copolymcr of asparagine and ammonium aspartate NH, pH ?o NH O=g 9 O-C 9. 180° C C-C-C-NH C-C-C-NH-H -- H H2 H. H. 3 h. asparagine c salt of the copolymer of asparagine with ammonium aspartate or aspartic acid NH, p o=cOH / ONHO H4 O=C O C c-C-C-NH N C-NH H H2 C 2 c2 by O Jel asparagine succinimide terpolymer of asparagine and succinimide with ammonium aspartate or aspartic acid Fig. 2 U.S. Patent Nov.30, 2004 Sheet 3 of 8 US 6,825,313 B2 100 a 7 8 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm) Fig. 3 U.S. Patent Nov.30, 2004 Sheet 4 of 8 US 6,825,313 B2 1316 94.5 395 94.0 1520 93.5 1582 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm) Fig. 4 U.S. Patent Nov.30, 2004 Sheet 5 of 8 US 6,825,313 B2 100 98 96 94 92 90 88 86 84 82 80 | 78 76 74 72 70 68 66 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm) Fig. 5 U.S. Patent Nov.30, 2004 Sheet 6 of 8 US 6,825,313 B2 100 98 97 96 95 93 92 91 90 89 88 87 86 85 83 82 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm) Fig. 6 U.S. Patent Nov.30, 2004 Sheet 7 of 8 US 6,825,313 B2 100 98 88824.6 8 O 4000 3500 3000 2500 2000 1500 1000 50 Wavenumbers (cm) Fig. 7 U.S. Patent Nov.30, 2004 Sheet 8 of 8 US 6,825,313 B2 102 100 98 96 94. 92 90 88 86 2.944 1407 84 3078 82 80 313 78 76 1185 74 72 70 1720 68 1526 66 1645 64 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm) Fig. 8 US 6,825,313 B2 1 2 COPOLYMERS OF AMINO ACIDS AND Groth, T., W. Joentgen, P. Wagner, H-J. Traenckner, and METHODS OF THEIR PRODUCTION D. Jovcic. 1997. Process for preparing polymers which contain aspartic acid. U.S. Pat. No. 5,594,077. This application claims priority to U.S. Provisional Groth, T., W. Joentgen, P., and N. Miller. 1998. Process Application Ser. No. 60/378,915, filed May 7, 2002, which for preparing polyaspartic acid. U.S. Pat. No. 5,714,558. is hereby incorporated by reference in its entirety. Groth, T., W. Joentgen, F. Dobert, K-P. Heise, T. Menzel, FIELD OF THE INVENTION U. Pentling, H-G. Pirkl, P. Wagner, and J. Weinschenck. The present invention relates to aspartate copolymers of 2000. Process for the preparation of polymers having recur defined composition and methods of their production from ring agents. U.S. Pat. No. 6,054,553. poly Succinimide. More particularly, the invention relates to Guth, J. J., S. A. Vona, J. S. Thomaides, and A. C. Savoca. water-Soluble aspartate/Succinimide and aspartate/ 2000. 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