WO1994021710A1 - Method of production of copolymers of polyamino acids - Google Patents
Method of production of copolymers of polyamino acids Download PDFInfo
- Publication number
- WO1994021710A1 WO1994021710A1 PCT/US1994/002218 US9402218W WO9421710A1 WO 1994021710 A1 WO1994021710 A1 WO 1994021710A1 US 9402218 W US9402218 W US 9402218W WO 9421710 A1 WO9421710 A1 WO 9421710A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbons
- alcohol
- solution
- ammonia
- agents
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
Definitions
- This invention relates to a method of synthesis of copolymers of polyamino acids and their salts.
- U.S. Pat.3,846,380 discloses the preparation and composition of copolymers of polyamino acids by the reaction of polysuccinimide with primary or secondary aliphatic amines, followed by alkaline r hydrolysis to provide surface active agents.
- the polysuccinimide is formed by high temperature reaction in tetralin and further reacted with amines in the solvent dimethylformamide. Emphasis is placed on long chain alkyiamines having eight to twenty carbon atoms. The products formed are said to have 10 good solubilizing ability, emulsifying and dispersing properties, as well as good foaming properties.
- foaming agents are useful as foaming agents, solubilizing agents, dispersing agents, emulsifying agents, rust- proofing agents, fiber-treating agents, level dyeing agents and retarding agents.
- U.S. Pat. 3,351,520 discloses the preparation wet strength agents from maleic acid esters with amines followed by reaction with epichlorohydrin. E ⁇ xcess alcohol can function as a solvent for the 15 reaction with the amine.
- R" wherein R' is a hydrogen or an alkyl, an alkenyl or an amide group having 1 to 36 carbons and R" is a hydrogen, an alkyl, an alkenyl or an amide group having 1 to 36 carbons, together with at least one of
- CrVCO-NH- CHj-COOZ wherein Z represents a hydrogen atom, an ammonia molecule, an alkali metal or an alkaline earth metal, as a repeating unit, can be prepared by reacting maleic anhydride with an alcohol containing 1 to 36 30 carbons, preferably 1 to 20 carbons, and more preferably 1 to 5 carbons, to form the half ester followed by the addition of an equivalent of ammonia, or ammonia and an amine or a polyamine, containing one to 36 carbons, preferably 8-20 carbons, and heating to 120-350 "C, preferably 140-225 °C and more preferably 150-180 "C, until one equivalent of alcohol is distilled away and hydrolyzing the copolymer of polysuccinimide formed with a hydroxide.
- Suitable alcohols one can mention are methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, lauryl alcohol, nonyl alcohol, oleyl alcohol, stearyl alcohol, allyl alcohol, crotyl alcohol, cyclopentanol, cyclohexanol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, glycerol, trimethyiol propane, pentaerythritol, arabrtol, sorbitol, mannitol and the like.
- the object of this invention is to provide a method for production of polymers and copolymers of amino acids.
- Polysuccinimide is the imide form of polyaspartic acid and is also known as anhydropolyaspartic acid.
- the counterion, "Z" above includes hydrogen, ammonium ion, the alkali and alkaline earth metals examples of which as their cations are, H ⁇ Na + , K ⁇ Mg + , Lf " , and Ca ++ , Zn ++ , Ba ++ , Co ++ , Fe ++ , Fe +++ , and NH, + .
- Polyamino acid derivatives are excellent inhibitors of the formation of hvdroxvlapatite in vitro, which has previously been shown to correlate closely withjn vivo inhibition of tartar deposition.
- the use of these polyamino acid derivatives as inhibitors of scale deposition has been disclosed in U.S. Pat. Appl. Ser. No. 07/968,319 Filed Oct. 29, 1992, Wood, et al., Copolymers of Polyamino Acids as Scale Inhibition Agents, and is incorporated herein by reference.
- Polyamino acid derivatives are excellent inhibitors of the formation of scale deposition, in particular, the types of scale in which deposition is inhibited are those exemplified by hard water, boiler water, cooling water, oil well waters, agricultural sprays and irrigation water. These scales typically consist of the salts of the bivalent metal ions.
- R" wherein R' is a hydrogen or an alkyl, an alkenyl or an amide group having 1 to 36 carbons and R" is a hydrogen, an alkyl, an alkenyl or an amide group having 1 to 36 carbons, together with at least one of the groups
- the polyamino acid derivatives are prepared by reacting maleic anhydride with an alcohol containing 1 to 36 carbons, preferably 1 to 20 carbons, and more preferably 1 to 5 carbons, to form the half ester followed by the addition of an equivalent of ammonia, or ammonia and an amine or a polyamine, containing one to 36 carbons, preferably 8-20 carbons, and heating to 120-300 °C, preferably 140-225 ⁇ C and more preferably 150-180 °C, until one equivalent of alcohol is distilled away.
- the resulting polymer or copolymer of polysuccinimide may be hydrolyzed with an alkaline earth or alkali metal hydroxide or ammonium hydroxide, forming the polyamino acid derivatives.
- Alkaline earth and alkali metal hydroxides include magnesium, calcium, strontium, barium, lithium sodium, and potassium hydroxides. They may be used in their solid form or as their aqueous or organic solutions.
- R' and R" are hydrogen, methyl, oleyl, stearyl, and lauryl.
- the residual oil was raised to 150 ° C and then slowly raised to 230 ° C over a four hour period.
- the resultant 49.5 g of brown gummy solid was heated to 240-245 °C for an additional 20 minutes yielding 48.1 g of brown solids.
- the material to be tested as an inhibitor of scale formation was added in appropriate quantities to a solution of 10 ml of calcium chloride solutions (21.6 g/L of CaCl, dihydrate and 41.4 g/L of NaCI) and 10 ml of sulfate solution (20.9 g/L of Na ⁇ SQ, and 41.4 g NaCI). The mixture was then placed in an oven at 16G°F for 12 hours. Finally the mixture was filtered through Whatman #2 paper and dried at 160° F for 8 hours, after which the weight of precipitate was determined.
- the blank gave 82 mg of precipitate, while at 2.5 ppm of the above copolymer, 67 mg was obtained and at 5.0 ppm, 36 mg was obtained.
- Example 3 These solids were treated as in Example 3 to give a light orange solution containing 39% solids consisting of a copolymer of oleyl- ⁇ , ⁇ -polyaspartic acid as an aqueous solution of its sodium salt. When shaken, the solution gave a stable foam.
- the CaSQ, precipitation assay given in Example 3, the blank gave 82 mg of precipitate, while at 2.5 ppm of the above copolymer, 78 mg was obtained and at 5.0 ppm, 50 mg was obtained.
- Example 3 In an identical fashion to that of Example 3, 125 g of cyclohexanol was added 39.2 g (0.4 moles) of maleic anhydride and treated as in Example 3 resulting in 63 g red-brown solid. The solid was washed with two 25 ml portions of isopropanol to remove 1.8 g of brown gum.
- Example 3 These solids were then hydrolyzed as in Example 3 to give a dark red-brown aqueous solution and 15 g of a colorless phase consisting of cyclohexanol. When shaken, the aqueous solution gave a stable foam.
- the blank gave 82 mg of precipitate, while at 2.5 ppm of the above copolymer, 85 mg was obtained and at 5.0 ppm, 54 mg was obtained.
- Diethylene triamine (4,0 g, 0.039 moles) was added to tall oil fatty acids (over 95% oleic acid) (2.25 g) and heated for 10 min with stirring at 190-200° C and the mixture was dissolved in 40 g of methanol.
- Maleic anhydride (39.2 g, 0.4 moles) was added to this mixture and the reaction exothermed to 60° C.
- the reaction mix was cooled to 25 ° C and ammonia (6.8 g) was added over a period of 20 min.
- the solution was heated with stirring at 175-195° C for 20 min resulting in an orange syrup.
- the reaction was then heated for 8 min at 195-225° C and the resulting foam was broken up.
- the mixture was then headed for 10 min at 225-245° C, broken up and heated for 10 min at 235-245° C resulting in 41.3 go of a tan powder.
- the powder was mixed with 60 g of water and NaOH (15 g in 24 g water) was slowly added. Addition of 120 ml of water gave a fluid solution which was very sudsy, in the CaSQ, precipitation assay of E ⁇ xample 3, the blank gave 81 mg of precipitate, while at 2.5 ppm of the above copolymer, 51 mg was obtained and at 5.0 ppm, 3 mg was obtained.
- the sodium polyaspartate was tested for inhibition of calcium carbonate precipitation by the calcium drift assay.
- a supersaturated solution of calcium carbonate is formed by adding
- the 2500 mol wt sodium polyacryiate had a change of 0.34 at both times.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU64428/94A AU689470B2 (en) | 1993-03-16 | 1994-03-01 | Method of production of copolymers of polyamino acids |
EP94912170A EP0690885A1 (en) | 1993-03-16 | 1994-03-01 | Method of production of copolymers of polyamino acids |
JP6521056A JPH08507822A (en) | 1993-03-16 | 1994-03-01 | Method for producing polyamino acid copolymer |
KR1019950703904A KR960701126A (en) | 1993-03-16 | 1994-03-01 | METHOD OF PRODUCTION OF COPOLYMERS OF POLYAMINO ACIDS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/031,856 US5292858A (en) | 1993-03-16 | 1993-03-16 | Method of production of copolymers of polyamino acids |
US08/031,856 | 1993-03-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994021710A1 true WO1994021710A1 (en) | 1994-09-29 |
Family
ID=21861767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/002218 WO1994021710A1 (en) | 1993-03-16 | 1994-03-01 | Method of production of copolymers of polyamino acids |
Country Status (7)
Country | Link |
---|---|
US (1) | US5292858A (en) |
EP (1) | EP0690885A1 (en) |
JP (1) | JPH08507822A (en) |
KR (1) | KR960701126A (en) |
AU (1) | AU689470B2 (en) |
CA (1) | CA2158072A1 (en) |
WO (1) | WO1994021710A1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5466760A (en) * | 1992-08-07 | 1995-11-14 | Srchem, Inc. | Copolymers of polyaspartic acid |
US5410017A (en) * | 1993-05-21 | 1995-04-25 | Rohm And Haas Company | Continuous thermal polycondensation process for preparing polypeptide polymers |
US5457176A (en) * | 1993-09-21 | 1995-10-10 | Rohm And Haas Company | Acid catalyzed process for preparing amino acid polymers |
EP0650995B1 (en) * | 1993-11-02 | 2000-01-05 | Bayer Ag | Process for preparing aspartic acid polymers |
US5491213A (en) * | 1994-01-28 | 1996-02-13 | Donlar Corporation | Production of polysuccinimide |
US5552516A (en) * | 1994-06-22 | 1996-09-03 | Donlar Corporation | Soluble, crosslinked polyaspartates |
US5681920A (en) * | 1994-06-28 | 1997-10-28 | Donlar Corporation | Process for production of a polysuccinimide and derivatives thereof |
DE4425952A1 (en) * | 1994-07-21 | 1996-01-25 | Bayer Ag | Process for the preparation of polysuccinimide or maleic acid |
US5478919A (en) * | 1994-07-29 | 1995-12-26 | Donlar Corporation | Aspartic acid copolymers and their preparation |
DE19545678A1 (en) | 1995-12-07 | 1997-06-12 | Goldschmidt Ag Th | Copolymers of polyamino acid esters |
US5869027A (en) * | 1996-04-22 | 1999-02-09 | Wood; Louis L. | Method for odor reduction |
US5872285A (en) * | 1996-06-10 | 1999-02-16 | Donlar Corporation | Production of D,L-aspartic acid |
US5981691A (en) * | 1997-04-23 | 1999-11-09 | University Of South Alabama | Imide-free and mixed amide/imide thermal synthesis of polyaspartate |
DE19822599C2 (en) * | 1998-05-20 | 2003-02-06 | Goldschmidt Ag Th | Copolymers hydrophobically modified polyaspartic esters and their use |
US6365706B1 (en) | 2000-06-21 | 2002-04-02 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
DE10342926A1 (en) * | 2003-09-17 | 2005-04-14 | Bayer Chemicals Ag | Polyether-modified polymers as leather auxiliaries |
US7888297B2 (en) * | 2005-01-06 | 2011-02-15 | Halliburton Energy Services, Inc. | Compositions for reducing the viscosity of treatment fluids |
KR100764933B1 (en) * | 2006-09-25 | 2007-10-09 | 애경유화 주식회사 | Manufacturing method of polyaspartic acid using maleic anhydride |
KR102273808B1 (en) * | 2015-06-11 | 2021-07-06 | 주식회사 케이씨씨 | Polyamide curing agent with ring-opening product of acid anhydride by alcohol |
CN107328929B (en) * | 2017-06-24 | 2019-06-04 | 安徽师范大学 | A kind of quantitative detecting method of PSI-OAm-NAPI amphiphilic polymer/nanometer material |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2306918A (en) * | 1940-02-15 | 1942-12-29 | Research Corp | Amine reaction product |
US3052655A (en) * | 1958-08-01 | 1962-09-04 | Sidney W Fox | Thermal polymerization of amino acid mixtures containing aspartic acid or a thermal precursor of aspartic acid |
US3351520A (en) * | 1964-11-13 | 1967-11-07 | Union Carbide Corp | Poly-beta-asparaginepolyalkylenepoly-amine halohydrin resins and application thereof in production of wet strength paper and flocculation of solids |
US3846380A (en) * | 1972-10-31 | 1974-11-05 | M Teranishi | Polyamino acid derivatives and compositions containing same |
US4169924A (en) * | 1977-06-09 | 1979-10-02 | Gaf Corporation | Preparation of linear cyclic polyimides from latices |
US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
US5057597A (en) * | 1990-07-03 | 1991-10-15 | Koskan Larry P | Process for the manufacture of anhydro polyamino acids and polyamino acids |
-
1993
- 1993-03-16 US US08/031,856 patent/US5292858A/en not_active Expired - Fee Related
-
1994
- 1994-03-01 CA CA002158072A patent/CA2158072A1/en not_active Abandoned
- 1994-03-01 EP EP94912170A patent/EP0690885A1/en not_active Withdrawn
- 1994-03-01 WO PCT/US1994/002218 patent/WO1994021710A1/en not_active Application Discontinuation
- 1994-03-01 AU AU64428/94A patent/AU689470B2/en not_active Ceased
- 1994-03-01 KR KR1019950703904A patent/KR960701126A/en not_active Application Discontinuation
- 1994-03-01 JP JP6521056A patent/JPH08507822A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2306918A (en) * | 1940-02-15 | 1942-12-29 | Research Corp | Amine reaction product |
US3052655A (en) * | 1958-08-01 | 1962-09-04 | Sidney W Fox | Thermal polymerization of amino acid mixtures containing aspartic acid or a thermal precursor of aspartic acid |
US3351520A (en) * | 1964-11-13 | 1967-11-07 | Union Carbide Corp | Poly-beta-asparaginepolyalkylenepoly-amine halohydrin resins and application thereof in production of wet strength paper and flocculation of solids |
US3846380A (en) * | 1972-10-31 | 1974-11-05 | M Teranishi | Polyamino acid derivatives and compositions containing same |
US4169924A (en) * | 1977-06-09 | 1979-10-02 | Gaf Corporation | Preparation of linear cyclic polyimides from latices |
US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
US5057597A (en) * | 1990-07-03 | 1991-10-15 | Koskan Larry P | Process for the manufacture of anhydro polyamino acids and polyamino acids |
Non-Patent Citations (1)
Title |
---|
See also references of EP0690885A4 * |
Also Published As
Publication number | Publication date |
---|---|
AU6442894A (en) | 1994-10-11 |
KR960701126A (en) | 1996-02-24 |
US5292858A (en) | 1994-03-08 |
AU689470B2 (en) | 1998-04-02 |
EP0690885A1 (en) | 1996-01-10 |
CA2158072A1 (en) | 1994-09-17 |
EP0690885A4 (en) | 1995-11-15 |
JPH08507822A (en) | 1996-08-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5292858A (en) | Method of production of copolymers of polyamino acids | |
US5708126A (en) | Process for the preparation of copolymers of polysuccinimides | |
US5357004A (en) | Copolymers of polyaspartic acid | |
EP1085033B1 (en) | Salts of polyaspartic acid by high temperature reaction | |
US5442038A (en) | Polymers of maleic acid with amines | |
CA2173485A1 (en) | Amino acid copolymers of maleic acid | |
JP3528000B2 (en) | Polyaspartic acid and copolymers of polycarboxylic acids and polyamines | |
US6001956A (en) | Copolymers of polyaspartic acid and polycarboxylic acids and polyamines | |
US5610267A (en) | Process for preparing polysuccinimide by high temperature reaction | |
KR100293134B1 (en) | Copolymers of Polyaspartic Acid, Polycarboxylic Acid and Polyamine | |
AU740017B2 (en) | Copolymers of polyaspartic acid and polycarboxylic acids and polyamines | |
CA2495360A1 (en) | Copolymers of polyaspartic acid and polycarboxylic acids and polyamines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA HU JP KR NO |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1994912170 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2158072 Country of ref document: CA |
|
WWP | Wipo information: published in national office |
Ref document number: 1994912170 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1994912170 Country of ref document: EP |