CA2181890C - Production of polyaspartic acid from maleic acid and ammonia - Google Patents

Production of polyaspartic acid from maleic acid and ammonia

Info

Publication number
CA2181890C
CA2181890C CA 2181890 CA2181890A CA2181890C CA 2181890 C CA2181890 C CA 2181890C CA 2181890 CA2181890 CA 2181890 CA 2181890 A CA2181890 A CA 2181890A CA 2181890 C CA2181890 C CA 2181890C
Authority
CA
Grant status
Grant
Patent type
Prior art keywords
temperature
polysuccinimide
ammonia
acid
polyaspartic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA 2181890
Other languages
French (fr)
Other versions
CA2181890A1 (en )
Inventor
Larry P. Koskan
Abdul Rehman Y. Meah
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donlar Corp
Original Assignee
Donlar Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1092Polysuccinimides

Abstract

Polyaspartic acid is produced by thermal condensation of ammonium maleate derived from maleic acid and ammonia. Solid ammonium maleate in particulate form is heated to a temperature of at least about 170 °C to effect thermal condensation to a polysuccinimide which is then base hydrolyzed to a polyaspartic acid salt.

Description

PRODUCTION OF POLYASPARTIC ACID FROM
MALEIC ACID AND AMMONIA

Field of the Invention The invention relates to polymer formation.
More particularly, the invention relates to manufacture of polyaspartic acid.

Background of Invention Polyaspartic acid has been formed by a number of methods. U.S. Patent 5,116,513 to Koskan et al.
teaches the formation of polyaspartic acid by the thermal polymerization of aspartic acid. The polymerization produces a polysuccinimide, which is then base hydrolyzed to polyaspartic acid.
U.S. Patent 4,839,461 to Boehmke teaches the production of polyaspartic acid by reacting maleic acid and ammonia in a molar ratio of 1:1 to 1.5 at the relatively low temperatures of 120-150 C.
Mosig, "Kinetic and Thermal Characterization of the Hydrolysis of Polysuccinimide", Diplomarbeit Thesis, Clemson University, Clemson, SC, April 1992, demonstrated that the rate of base hydrolysis of polysuccinimide to polyaspartate is dependent on hydroxide concentration and temperature, and that the temperature has a pronounced effect on the rate.
Summary of the Invention Polysuccinimide a precursor of polyaspartic acid, can be produced in unexpectedly high yields at elevated temperatures.of at least about 170 C by WO 95/20618 PCT/US95/01008 =

reacting maleic acid with ammonia in an aqueous medium.
Maleic anhydride and ammonia are the usual starting materials to produce ammonium maleate which is then thermally condensed. The resulting polysuccinimide is base hydrolyzed to polyaspartic acid preferably using an alkali metal hydroxide, e.g., sodium hydroxide, and the like. While not a simple reaction, the hydrolysis generally follows an Arrhenius profile where the optimum temperature for the hydrolysis is about 70 C. At a temperature above about 80 C ammonia can be stripped from the polymer.
The presently contemplated method of producing polyaspartic acid combines maleic acid and ammonia in an aqueous medium to produce an aqueous solution of an ammonium maleate, i.e., mono-ammonium maleate or di-ammonium maleate, depending upon the amount of ammonia present. Solid ammonium maleate is recovered from the aqueous solution, usually by evaporating the solution to dryness. The recovered solid ammonium maleate, preferably comminuted to a finely-divided powder form, is then heated to an elevated temperature of at least about 170 C and maintained at that temperature for a time period sufficient to produce the polysuccinimide.
A preferred elevated temperature range for practicing the present invention is about 200 C to about 260 C. A more preferred temperature range is about 220 C to about 240 C.
The yield can be increased by increasing the reaction time. Generally, reaction time of about 6 to about 14 hours is preferred. More preferably, the reaction time is about 7 to about 10 hours.
Maleic acid and ammonia are present in the aforesaid aqueous medium in a mole ratio of at least about 1:1, usually in a respective mole ratio in the WO 95/20618 PCTlU595/01008 range of about 1:1 to about 1:12, preferably in a respective mole ratio of about 1:1 to about 1:5.
To hydrolyze, a suspension of polysuccinimide in water is made with vigorous mixing in order to wet the solids. Tank car caustic is the preferred hydrolysis base and is added to the suspension at a controlled rate. The hydrolysis reaction is monitored so that the pH value of the suspension averages about 9.5 and the temperature does not exceed about 80 C. The amount of base used for the hydrolysis is at least stoichiometric with respect to polysuccinimide present.
Solution strengths from about 5 to about 50 weight percent are obtained with a preferred range of about 40 to about 45 weight percent solids. Analysis of the resulting polyaspartate by C13 NMR spectroscopy shows a copolymer containing at least 50t Q-conformation. A
preferred range for the hydrolyzedpolyaspartic acid product is about 70k to about 80k Q-conformation.

Description of the Preferred Embodiments A series of experiments, described below, were performed to determine the processing parameters for producing polysuccinimide from maleic anhydride or maleic acid and ammonia.
The presently contemplated process entails thermal polymerization by heating a solid, particulate ammonium maleate at an elevated temperature of at least about 170 C for a time period sufficient to produce a polysuccinimide that can be hydrolyzed to polyaspartic acid. Hydrolysis can be effected by adding the produced polysuccinimide to an aqueous sodium hydroxide solution while maintaining the pH of the resulting admixture at a value of at least 9 or higher, preferably at about 9.5, until a substantially clear aqueous polyaspartic acid solution is obtained. In lieu of sodium hydroxide, WO 95/20618 PCT/US95/01008 =

4 _ other alkali metal hydroxides such as potassium hydroxide, can be utilized. Hydrolysis can also be carried out using alkaline earth metal hydroxides or carbonates.
These experiments utilized maleic anhydride as the starting material for reaction with ammonia.
However, maleic anhydride equivalents such as maleic acid and its salts can be used as well, inasmuch as maleic anhydride readily converts to maleic acid in an aqueous medium. For purposes of this invention, the term "polyaspartic acid" asused herein includes also the salts of polyaspartic atid.

98 Grams ofmaleic anhydride (1 mole) were slurried with 50 grams of water and heated to about 55 C
for about 30 minutes in an oil bath. 68 Grams of 30%
ammonium hydroxide in-water-were then added to the slurried maleic anhydride. The resulting mixture was heated for about four hours in an oil bath at a temperature of about 130 C (a reaction mixture temperature of about 115 C). The obtained product was tested, and produced a positive Biuret test for peptide.
The obtained product was hydrolyzed. After hydrolysis, Gel Permeation Chromatography (hereinafter GPC) clearly showed that less than about 10t of any polymer was formed. Titration confirmed this result.

98 Grams (1 mole) of maleic anhydride were slurried with 50 grams of water and heated at about 75 C
for about 30 minutes in order to melt the maleic anhydride. The mixture was placed in water bath, cooled to room temperature, and 68 grams (1 mole) of 30 wtk aqueous solution of ammonium hydroxide were added = WO 95120618 218 1~ 9 0 PCT/US95/01008 dropwise to minimize arnmonia loss during the resulting exotherm.
Upon completion of the ammonia addition, stirring was commenced.. A temperature of 75-85 C was attained and was maintained for 2-3 hours. A glassy, white substance was produced as the product.
This product was transferred to a reaction vessel and heated in an oil bath to a reaction mixture temperature of about 115 C (oil bath temperature --about 135 C). During four hours of heating, water formation indicative of condensation reaction was observed. A brittle solidified product was obtained upon completion of the reaction and was hydrolyzed.
After hydrolysis, GPC clearly showed the presence of a small amount of polymer. Titration showed about 20k polymer.

A portion of the glassy product obtained in Example 2 was ground. 15 Grams of the ground product were placed in a test tube and heated for 4-5 hours at a temperature of about 140 C (oil bath temperature --about 150 C). After heating, the produced substance was hydrolyzed. After hydrolysis, GPC data showed the presence of a polymer shoulder. Titration showed about 30k polymer.

15 Grams of ground product from Example 2 were placed in a test tube, heated to a temperature of about 170 C (oil bath temperature -- about 180 C), and held at that temperature for about 5 hours. The produced substance was hydrolyzed. After hydrolysis, GPC data WO 95/20618 PCT/US95101008 =

clearly showed about 50o polymer. Titration data confirmed this amount.

20 Grams of ground product from Example 2 were placed in a test tube and kept heated in an oil bath for about 5 hours at a temperature of about 220 C. The-obtained product was water insoluble. Upon hydrolysis, GPC analysis of the obtained product evidenced a strong polyaspartic acid peak. Titration showed about 90t polymer.

98 Grams of maleic anhydride were slurried with 50 grams of water and heated at about 75 C for about 30 minutes in order to melt the maleic anhydride.
The mixture was placed in a water bath, cooled to room temperature, and 68 grams of 30 wtt aqueous ammonium hydroxide was added dropwise to minimize ammonia loss during the resulting exotherm.
Upon completion of the ammonia addition, stirring was commenced. A temperature of about 75-85 C
was attained and was maintained for 2-3 hours. A
glassy, white substance was produced as the product.
This product was transferred to a reaction vessel and heated to a reaction mixture temperature of about 110 C (oil bath temperature -- about 125 C). The temperature was maintained for about four hours. During the four hours of heating, water formation indicative of condensation reaction was observed. A brittle solidified product was observed upon completion of the reaction and was hydrolyzed. Titration data showed less than about 5k polysuccinimide formation. No polymer in the hydrolyzed product was detected by GPC.

196 Grams (2 moles) of maleic anhydride were slurried with 100 grams of water and heated at about 75 C for about 45 minutes in order to melt the maleic anhydride. The mixture was placed in a water bath, cooled to room temperature, and 204 grams (3 moles) of 30 wtt ammonium hydroxide in water was added dropwise to minimize ammonia loss during the exotherm.
Upon completion of the ammonia addition, stirring was commenced. A temperature of 75-85 C was attained and was maintained for about 6 hours. A
glassy, white substance was obtained as the product.
This product was transferred to a reaction vessel and heated in an oil bath to a reaction mixture temperature of about 120 C (oil bath temperature --about 135 C). The heating was continued for fourteen hours. Water formation indicative of a condensation reaction was observed during heating. Upon completion of the reaction, a yellowish, hard material was obtained. Titration showed 0k polymer. GPC results were consistent with the titration.

196 Grams (2 moles) of maleic anhydride were slurried with 100 grams of water and heated to about 55 C with stirring for about 45 minutes. The mixture was placed in a water bath, cooled to room temperature, and 405 grams (6 moles of 30 wt k aqueous ammonium hydroxide was slowly added with cooling to minimize ammonia loss. Upon completion of the addition, stirring = was commenced and the mixture was heated to 75-85 C for about 6 hours. A white, glassy substance was obtained as the product. This obtained product was heated in an oil bath to a reaction mixture temperature of about 240 C (oil bath temperature -- about 250 C) and held at - -S -that temperature for about 7 hours. A dark, yellow brittle product was obtained. Titration showed 100t polymer. This was confirmed by GPC of the hydrolyzed product.
In the Examples presented above, there was no strong experimental suggestion that polysuccinimide had been produced in significant amounts at temperatures less than 150 C. However, at temperatures of about 150 C or lower a maleic anhydride/ammonia adduct, ammonium maleate, was formed. At elevated temperatures the produced ammonium maleate participated in a polymerization reaction. Once the 200 C threshold was reached or surpassed, GPC and titration studies gave clear evidence of polysuccinimide formation. The observed yield was high, over about 70t. At temperatures above about 220 C the yield attained the maximum of 100k of theoretical, and generally exceeded about 90t of theoretical. At temperatures above about 150 C, a yield of at least about 60% theoretical was obtained. At temperatures exceeding about 170 C, at least about 70% of the theoretical yield was obtained.
At temperatures exceeding about 200 C at least about 80%
of theoretical yield was obtained.

Polysuccinimide (about 30 grams) was slurried in water (about 40 grams) and the slurry stirred.
Caustic (about 25 grams of 50t wt/wt solution) was added to the stirred slurry at a rate so that the slurry temperature did not exceed about 80 C, and the pH value of the slurry did not exceed about 9.5. After the caustic addition was complete, sufficient water was added to provide a solids concentration of about 42 i ;~181$9~

weight percent, constituted substantially by hydrolyzed ~ polysuccinimide.

Softened water (about 287 pounds) was pumped into a 150-gallon stainless steel tank. The tank contents were stirred as polysuccinimide (about 381 pounds) was slowly introduced therein. Stirring of the tank contents was continued until a substantially uniform suspension was produced.
Thereafter, aqueous sodium hydroxide solution (about 317 pounds; 50t wt/wt) was pumped into the tank at a rate of about 1-2 gallons per minute. The suspension began to clear as the sodium hydroxide solution was introduced into the tank. The rate of addition of the sodium hydroxide solution was slowed down as the hydrolysis reaction came to completion as evidenced by a substantially clear solution being formed in the tank.
During addition of the sodium hydroxide solution, the tank contents were maintained at a temperature below about 80 C by adding more water. Upon completion of the sodium hydroxide addition, the resulting solution had a pH value of about 9.5. The produced aqueous sodium polyaspartate solution had a solids content of about 42 weight percent.
The foregoing Examples and accompanying discussion are intended as illustrative, and are not intended to be limiting. Still other variations within the spirit and scope of this invention are possible and will readily present themselves to those skilled in the art.
.

Claims (2)

1. A method of producing polyaspartic acid which comprises heating particulate solid ammonium maleate to an elevated temperature of 220 to 240°C
and maintaining the solid ammonium maleate at the elevated temperature for a time period sufficient to produce a polysuccinimide; and base hydrolyzing the produced polysuccinimide to polyaspartic acid by the addition of aqueous sodium hydroxide at a weight ratio of polysuccinimide;
sodium hydroxide of 2.4:1, and at a rate sufficient to maintain an elevated hydrolysis temperature that does not exceed 80°C and a pH value that does not exceed 9.5.
2. A method as claimed in claim 1 wherein the produced polyaspartic solution has 42% weight solids.
CA 2181890 1992-09-18 1995-01-26 Production of polyaspartic acid from maleic acid and ammonia Expired - Fee Related CA2181890C (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US08188539 US5373088A (en) 1992-09-18 1994-01-28 Production of polyaspartic acid from maleic acid and ammonia
US188,539 1994-01-28
PCT/US1995/001008 WO1995020618A1 (en) 1994-01-28 1995-01-26 Production of polyaspartic acid from maleic acid and ammonia

Publications (2)

Publication Number Publication Date
CA2181890A1 true CA2181890A1 (en) 1995-08-03
CA2181890C true CA2181890C (en) 2007-05-22

Family

ID=38152575

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2181890 Expired - Fee Related CA2181890C (en) 1992-09-18 1995-01-26 Production of polyaspartic acid from maleic acid and ammonia

Country Status (1)

Country Link
CA (1) CA2181890C (en)

Also Published As

Publication number Publication date Type
CA2181890A1 (en) 1995-08-03 application

Similar Documents

Publication Publication Date Title
US5387359A (en) Alkaline earth metal potassium acetate, a process for its preparation and its use
US5393868A (en) Production of polysuccinimide by thermal polymerization of maleamic acid
US5116513A (en) Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor
US3846380A (en) Polyamino acid derivatives and compositions containing same
US4307211A (en) Preparation of an ethylene-ethyl acrylate-acrylic acid terpolymer
US4623699A (en) Preparation of linear, basic polymer powders
Schwamborn Chemical synthesis of polyaspartates: a biodegradable alternative to currently used polycar☐ ylate homo-and copolymers
US5747635A (en) Modified polyaspartic acids, preparation thereof and use thereof
US5908885A (en) Polysuccinimide and polyaspartate as additives to cementitious materials
US5876623A (en) Biodegradable aspartic acid polymers for preventing scale formation in boilers
US5478919A (en) Aspartic acid copolymers and their preparation
US5536813A (en) Detersive polyanhydroaspartic acids and biodegradable hydrolysates thereof
US6063961A (en) Process for preparing cocondensates of aspartic acid amines
US5981691A (en) Imide-free and mixed amide/imide thermal synthesis of polyaspartate
US5292858A (en) Method of production of copolymers of polyamino acids
US5315010A (en) Polyaspartic acid manufacture
Kao et al. Investigation of alkaline hydrolysis of polyethylene terephthalate by differential scanning calorimetry and thermogravimetric analysis
US4839461A (en) Polyaspartic acid from maleic acid and ammonia
GB2246786A (en) Preparation of polysuccinimide
US2387735A (en) Method of forming carboxylic amino acids
US5373086A (en) Polyaspartic acid having more than 50% β form and less that 50% α form
US5508434A (en) Production of a polysuccinimide and derivatives thereof in the presence of a sulfur-containing dehydrating agent
US5552516A (en) Soluble, crosslinked polyaspartates
US5998492A (en) Super-absorbing polymeric networks
US5057597A (en) Process for the manufacture of anhydro polyamino acids and polyamino acids

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed

Effective date: 20150126