WO1993004108A1 - Process for the manufacture of polyamino acids - Google Patents

Process for the manufacture of polyamino acids Download PDF

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Publication number
WO1993004108A1
WO1993004108A1 PCT/US1991/005781 US9105781W WO9304108A1 WO 1993004108 A1 WO1993004108 A1 WO 1993004108A1 US 9105781 W US9105781 W US 9105781W WO 9304108 A1 WO9304108 A1 WO 9304108A1
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Prior art keywords
acid
fluid bed
temperature
amino acid
product
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PCT/US1991/005781
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French (fr)
Inventor
Larry P. Koskan
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Donlar Corporation
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Priority to US07/547,875 priority Critical patent/US5057597A/en
Application filed by Donlar Corporation filed Critical Donlar Corporation
Priority to PCT/US1991/005781 priority patent/WO1993004108A1/en
Priority to ES92904501T priority patent/ES2098498T3/en
Priority to CA002120039A priority patent/CA2120039C/en
Priority to DK92904501.1T priority patent/DK0599842T3/en
Priority to EP92904501A priority patent/EP0599842B1/en
Priority to DE69124628T priority patent/DE69124628T2/en
Priority to AT92904501T priority patent/ATE148721T1/en
Publication of WO1993004108A1 publication Critical patent/WO1993004108A1/en

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    • 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

Definitions

  • a method for the polycondensation of aspartic acid in solid form is disclosed in E. Kokufuta et al., "Temperature Effect on the Molecular Weight and the Optical Purity of Anhydropolyaspartic Acid Prepared by Thermal Polycondensation", Bui. Chem. Soc. Japan. 61(5) :1555-1556 (1978) .
  • the polycondensation reaction described therein requires heating solid L-aspartic acid to 160° to 220°C for five hours.
  • the product, anhydropolyaspartic acid (APAA) is then dialyzed for five to six days. Weight losses during the dialysis step range from 97% to 29%.
  • the highest yield of APAA achieved by the Kokufuta et al. process is 50% by weight of APAA based on the starting weight of the aspartic acid at a reaction temperature of 220°.
  • a typical polycondensation reaction polymerizes an amino acid to form an anhydropolyamino acid by driving water from the amino acid as it polymerizes.
  • aspartic acid when it is subjected to heat and shear, polymerizes to form APAA.
  • APAA the polymerizes to form APAA.
  • every molecule of aspartic acid that is polymerized yields two molecules of water. Therefore, if the aspartic acid is entirely polymerized, the theoretical product yield is 74% by weight APAA and 26% water based on the starting weight of aspartic acid.
  • An amino acid (110 lbs) such as, for example, L- aspartic acid is charged into a fluid bed dryer such as, for example, a model FM-130 Laboratory Mixer obtained from Littleford Bros., Inc.
  • the amount of amino acid depends upon the capacity of the equipment used.
  • the amino acid depends upon the capacity of the equipment used.
  • the amino acid is added in solid, particulate form.
  • the fluid bed dryer is equipped with an agitator which, preferably, has plow-shaped blades to provide maximum fluidization of the particles in the bed.
  • the fluid bed dryer is also equipped with a chopper to break up any lumps or clumps of particles that develop and to provide additional shear forces to the fluid bed. Sufficient mechanical shear should be provided to optimize fluidization of the particles in the bed.
  • At least about .015 horsepower per hour per liter of total dryer capacity is estimated to be required to adequately fluidize the particles in the bed. This is based on utilizing a fluid bed dryer with a 130 liter total capacity. Increasing the shear forces applied was observed to increase the yield obtained from the process.
  • the fluid bed dryer is also equipped with a heating means such as a heat jacket which provides heat for the condensation polymerization of the amino acid.
  • the dryer is preheated to a jacket temperature of about 180° to 260°C (356° to 500°F) .
  • the jacket temperature is maintained at a temperature sufficient to ensure that the particles in the bed are maintained at a temperature of about 180° to 250°C (356° to 482°F) .
  • This temperature is referred to herein as the product temperature.
  • the preferred reaction temperature is approximately 221°C (430°F) .
  • the temperature is maintained at the desired level over the course of the reaction, approximately three to six hours.
  • the dryer is also equipped with a vent and a stack.
  • the stack has a filter therein.
  • Stack gas exits the dryer through a filter, which collects any solid particles entrained therein.
  • the stack gas then flows to a condenser where the moisture therein is collected and measured.
  • the progress of the polymerization can be monitored by observing the amount of water recovered from the dryer stack. As the reaction proceeds, the amount of water condensing from the stack gas is observed to decrease. When the rate of condensation decreases significantly, the reaction is nearing complete polymerization. Typically, the reaction will take place over the course of three to six hours.
  • L-aspartic Acid (110.5 lbs.) was placed in the preheated fluid bed dryer. An atmosphere of nitrogen was introduced into the dryer. The jacket had been preheated to 260°C (500°F) . Agitation of the particles was commenced immediately to fluidize the particles in the dryer. The product temperature reached 204°C (400°F) within the first hour. Condensation was observed as the stack gas from the dryer passed through the condenser. The product temperature dropped from 204°C (400°F) to 200°C (393°F) approximately two hours after the aspartic acid was charged into the dryer. The product temperature then increased to 218°C (424°F) although the jacket temperature remained constant.
  • the temperature of the product remained constant until about the third hour of the reaction where a slight increase to 224°C (436°F) was observed.
  • the reaction temperature remained constant at 223°C (434°F) .
  • the amount of coi ensate from the stack gas was observed to decrease at this time.
  • the nitrogen gas flow was stopped and the product was removed from the dryer.
  • the weight of product recovered from the dryer was 83 pounds.
  • the weight of solid product removed from the filter was 10 pounds and the weight of condensate recovered was 12.8 pounds.
  • the average particle size of the product was 50 microns.
  • the product was analyzed and determined to be 74% APAA. Based on 74% polymerization, the yield was 84% of theoretical.
  • the agitator which was equipped with a 10 hp motor and plow-type blades, rotated at a speed of 155 rpm.
  • the agitator utilized was conventionally available for use with the fluid bed dryer used, and required no special modifications. Approximately 2600 watts of power was initially supplied to the agitator, but this was reduced to
  • EXAMPLE 2 L-aspartic acid (110.5 lbs.) was introduced into a fluid bed dryer with the jacket preheated to 260°C (500°F) . An atmosphere of nitrogen was introduced into the dryer, and agitation of the contents using an agitator as described in Example 1, rotating at a shaft speed of 155 rpm, was commenced. For increased agitation, a chopper was utilized. The chopper was equipped with a 10 hp motor and was run at full speed. The chopper utilized was commercially available with the dryer used and required no modification.
  • the product temperature reached 204°C (400°F) in 30 minutes.
  • the product temperature was maintained at 222°C (431°F) for the remaining hour of the three hour and 30 minute reaction time.
  • the jacket temperature remained constant throughout the process, and the reaction temperature was maintained at 222°C (431°F) .
  • the recovered product weighed 80.8 pounds.
  • The" product recovered from the filter weighed 0.5 pounds and the condensate recovered weighed 9.7 pounds.
  • the average particle size of the product was 50 microns.
  • the product was analyzed and determined to be 91% APAA.
  • the actual yield of APAA was 90% of theoretical, based on the starting weight of aspartic acid.
  • the mixing energy provided to the fluid bed dryer was 8.98 hp per hour, based on the reaction time of three and one-half hours. Based on the 130 liter total capacity of fluid bed dryer, the horsepower per hour per liter volume was .069.
  • L-aspartic acid (108 lbs.) was placed in the fluid bed dryer described in Example 1.
  • the jacket was preheated to 260°C (500°F) .
  • the fluid bed dryer was equipped with an agitator as described in Example 1 and a chopper as described in Example 2.
  • the agitator speed was maintained at 122 rpm and the chopper was run at 3/4 power.
  • the product temperature was measured to be 204°C (400°F) , and the reaction temperature was maintained at 223°C (434°F) to 229°C (444°F) throughout the reaction.
  • a nitrogen atmosphere was maintained in the dryer during the reaction.
  • the total reaction time was three and one-half hours after which 85 pounds of product was recovered from the dryer. No product was recovered from the filter. The condensate weight was 17.2 pounds. The average particle size of the product was 50 microns. The product was analyzed and determined to be 69% APAA. The yield was 73% of theoretical, based on the weight of aspartic acid. The agitation energy provided was 5.88 hp per hour, based on a three and one-half hour reaction time. The horsepower per hour per liter of total dryer capacity was .045.
  • the product recovered from the fluid bed dryer weighed 83 pounds and the product recovered from the filter weighed 2 pounds.
  • the weight of the condensate was 18.4 pounds.
  • the average particle size of the product was 50 microns.
  • the product was analyzed and determined to be 91% APAA.
  • the actual yield of APAA was 95% of theoretical, based on the starting weight of aspartic acid.
  • the agitation energy provided was 12.38 hp per hour.
  • the horsepower per hour per liter of dryer capacity was .095.

Abstract

A process for the manufacture of polyamino acids, particularly polyaspartic acid. A solid, particulate, amino acid is fluidized by agitation in a nitrogen atmosphere and heated to a temperature of at least 180 °C and maintained at that temperature for a sufficient amount of time to polymerize the amino acid and to drive off water from the heated bed. A degree of agitation sufficient to substantially fluidize the particles is provided and a particle size of no more than 150 microns is maintained throughout the process. The resultant anhydropolyamino acid is then hydrolyzed to a polyamino acid.

Description

PROCESS FOR THE MANUFACTURE OF POLYAMINO ACIDS Technical Field
The present invention relates to a process for the manufacture of polyamino acids, preferably polyaspartic acid. Background of the Invention
Polyamino acids such as polyaspartic acid (PAA) are useful in fertilizers, as scale inhibitors, and scale deposit removers. Polyamino acids have been synthesized by thermal polycondensation reactions. Unfortunately, the known methods for the synthesis of polyamino acids are complex, expensive and provide low product yields.
A method for the polycondensation of aspartic acid in solid form is disclosed in E. Kokufuta et al., "Temperature Effect on the Molecular Weight and the Optical Purity of Anhydropolyaspartic Acid Prepared by Thermal Polycondensation", Bui. Chem. Soc. Japan. 61(5) :1555-1556 (1978) . The polycondensation reaction described therein requires heating solid L-aspartic acid to 160° to 220°C for five hours. The product, anhydropolyaspartic acid (APAA) , is then dialyzed for five to six days. Weight losses during the dialysis step range from 97% to 29%. The highest yield of APAA achieved by the Kokufuta et al. process is 50% by weight of APAA based on the starting weight of the aspartic acid at a reaction temperature of 220°.
Another method for the synthesis of polyaspartic acid is disclosed in Boehmke, U.S. Patent No. 4,839,461. This process combines aleic acid or maleic anhydride and an ammonia solution in a molar ratio of 1:1 - 1.5. The mixture is then heated to 120° - 150°C and the resulting solution of ammonium salt and maleic acid is evaporated, leaving a crystal mash. The crystal mash is then melted, during which time the water of condensation and crystallization distill off. A porous mass of polyaspartic acid results. The entire process requires six to eight hours to complete. The prior art methods for the synthesis of polyamino acids are time consuming and complex. It is an object of this invention to provide a relatively simple process for the manufacture of polyamino acids that results in a high percentage conversion of amino acid to polymer. Summary of the Invention
A process for the manufacture of a polyamino acid, preferably polyaspartic acid, in relatively high yields is disclosed wherein a freely flowing, solid, particulate, amino acid is agitated sufficiently to form a fluid bed of the amino acid. The fluid bed is heated to a temperature of at least about 180°C (356°F) and maintained at a temperature in the range of about 180°C (356°F) to about 250°C (482°F) for a time period sufficient to polymerize the amino acid and to drive off water from the heated bed while maintaining a mean particle size of no more than 150 microns. The degree of agitation provided is at least sufficient to maintain the particles in a substantially free-flowing state throughout the requisite time period. An anhydropolya ino acid results.
The resultant solid product contains a high percentage of polymerized amino acid, heretofore not achieved by prior art processes that utilize thermal polycondensation reactions. The process provides yields of anhydropolyamino acid in excess of 95% of theoretical, based on the starting weight of polyamino acid.
The anhydropolyamino acid is then hydrolyzed, preferably using alkaline hydrolysis. Description of the Preferred Embodiment
The process disclosed herein utilizes a thermal polycondensation reaction to manufacture polyamino acids, preferably polyaspartic acid. While the present invention is susceptible of embodiment in various forms, there is hereinafter described presently preferred embodiments, with the understanding that the present disclosure is to be considered as an exemplification of the invention and is not intended to limit the invention to the specific embodiment illustrated. The process utilizes a thermal polycondensation reaction to produce an anhydropolyamino acid from an amino acid. The process utilizes heat and shear forces in the form of mechanical agitation to drive water from the amino acid particles, causing them to condense and polymerize. A typical polycondensation reaction polymerizes an amino acid to form an anhydropolyamino acid by driving water from the amino acid as it polymerizes. For example, aspartic acid, when it is subjected to heat and shear, polymerizes to form APAA. Theoretically, every molecule of aspartic acid that is polymerized yields two molecules of water. Therefore, if the aspartic acid is entirely polymerized, the theoretical product yield is 74% by weight APAA and 26% water based on the starting weight of aspartic acid.
The process utilizes conventional equipment that is commercially available to provide the mechanical shear forces and heat required to manufacture polyamino acids. A fluid bed dryer that provides both mechanical shear and heat has proven suitable for use in this process. It would be apparent to one skilled in the art, however, that any type of processing equipment capable of providing the process conditions herein described would be suitable for use in the disclosed process.
An amino acid (110 lbs) such as, for example, L- aspartic acid is charged into a fluid bed dryer such as, for example, a model FM-130 Laboratory Mixer obtained from Littleford Bros., Inc. The amount of amino acid depends upon the capacity of the equipment used. The amino acid depends upon the capacity of the equipment used. The amino acid is added in solid, particulate form. The fluid bed dryer is equipped with an agitator which, preferably, has plow-shaped blades to provide maximum fluidization of the particles in the bed. The fluid bed dryer is also equipped with a chopper to break up any lumps or clumps of particles that develop and to provide additional shear forces to the fluid bed. Sufficient mechanical shear should be provided to optimize fluidization of the particles in the bed. At least about .015 horsepower per hour per liter of total dryer capacity is estimated to be required to adequately fluidize the particles in the bed. This is based on utilizing a fluid bed dryer with a 130 liter total capacity. Increasing the shear forces applied was observed to increase the yield obtained from the process.
The fluid bed dryer is also equipped with a heating means such as a heat jacket which provides heat for the condensation polymerization of the amino acid. The dryer is preheated to a jacket temperature of about 180° to 260°C (356° to 500°F) . The jacket temperature is maintained at a temperature sufficient to ensure that the particles in the bed are maintained at a temperature of about 180° to 250°C (356° to 482°F) . This temperature is referred to herein as the product temperature. The preferred reaction temperature is approximately 221°C (430°F) . The temperature is maintained at the desired level over the course of the reaction, approximately three to six hours.
The dryer is also equipped with a vent and a stack. The stack has a filter therein. Stack gas exits the dryer through a filter, which collects any solid particles entrained therein. The stack gas then flows to a condenser where the moisture therein is collected and measured. The progress of the polymerization can be monitored by observing the amount of water recovered from the dryer stack. As the reaction proceeds, the amount of water condensing from the stack gas is observed to decrease. When the rate of condensation decreases significantly, the reaction is nearing complete polymerization. Typically, the reaction will take place over the course of three to six hours.
The reaction optionally takes place in a nitrogen atmosphere. Nitrogen gas is provided to the fluid bed dryer at atmospheric pressure from a conventional nitrogen source such as a nitrogen gas cylinder.
The resultant anhydropolyamino acid is then hydrolyzed by alkaline hydrolysis to produce a polyamino acid. The alkaline hydrolysis is conventional. A suitable method is disclosed in Kovacs, J. et al. , J. Orσ. Chem.. 26:1084 (1961).
The following examples are embodiments of the general process discussed hereinabove and are intended by way of illustration only. These examples are not intended to limit the invention in any way, other than in the spirit and scope of the appended claims. In all of the examples below, the Littleford fluid bed dryer described hereinabove was used.
EXAMPLE 1
L-aspartic Acid (110.5 lbs.) was placed in the preheated fluid bed dryer. An atmosphere of nitrogen was introduced into the dryer. The jacket had been preheated to 260°C (500°F) . Agitation of the particles was commenced immediately to fluidize the particles in the dryer. The product temperature reached 204°C (400°F) within the first hour. Condensation was observed as the stack gas from the dryer passed through the condenser. The product temperature dropped from 204°C (400°F) to 200°C (393°F) approximately two hours after the aspartic acid was charged into the dryer. The product temperature then increased to 218°C (424°F) although the jacket temperature remained constant. The temperature of the product remained constant until about the third hour of the reaction where a slight increase to 224°C (436°F) was observed. The reaction temperature remained constant at 223°C (434°F) . The amount of coi ensate from the stack gas was observed to decrease at this time.
After three hours, the nitrogen gas flow was stopped and the product was removed from the dryer. The weight of product recovered from the dryer was 83 pounds. The weight of solid product removed from the filter was 10 pounds and the weight of condensate recovered was 12.8 pounds. The average particle size of the product was 50 microns. The product was analyzed and determined to be 74% APAA. Based on 74% polymerization, the yield was 84% of theoretical.
The agitator, which was equipped with a 10 hp motor and plow-type blades, rotated at a speed of 155 rpm.
The agitator utilized was conventionally available for use with the fluid bed dryer used, and required no special modifications. Approximately 2600 watts of power was initially supplied to the agitator, but this was reduced to
1650 watts after the first hour of reaction time and held steady throughout the remainder of the reaction. The horsepower per hour, based on three hours of reaction time, was 2.35. Based on the total fluid capacity of the fluid bed dryer being 130 liters, the horsepower per hour per liter volume was 0.018.
EXAMPLE 2 L-aspartic acid (110.5 lbs.) was introduced into a fluid bed dryer with the jacket preheated to 260°C (500°F) . An atmosphere of nitrogen was introduced into the dryer, and agitation of the contents using an agitator as described in Example 1, rotating at a shaft speed of 155 rpm, was commenced. For increased agitation, a chopper was utilized. The chopper was equipped with a 10 hp motor and was run at full speed. The chopper utilized was commercially available with the dryer used and required no modification.
The product temperature reached 204°C (400°F) in 30 minutes. The product temperature was maintained at 222°C (431°F) for the remaining hour of the three hour and 30 minute reaction time. The jacket temperature remained constant throughout the process, and the reaction temperature was maintained at 222°C (431°F) .
The recovered product weighed 80.8 pounds. The" product recovered from the filter weighed 0.5 pounds and the condensate recovered weighed 9.7 pounds. The average particle size of the product was 50 microns. The product was analyzed and determined to be 91% APAA. The actual yield of APAA was 90% of theoretical, based on the starting weight of aspartic acid. The mixing energy provided to the fluid bed dryer was 8.98 hp per hour, based on the reaction time of three and one-half hours. Based on the 130 liter total capacity of fluid bed dryer, the horsepower per hour per liter volume was .069.
EXAMPLE 3
L-aspartic acid (108 lbs.) was placed in the fluid bed dryer described in Example 1. The jacket was preheated to 260°C (500°F) . The fluid bed dryer was equipped with an agitator as described in Example 1 and a chopper as described in Example 2. The agitator speed was maintained at 122 rpm and the chopper was run at 3/4 power. The product temperature was measured to be 204°C (400°F) , and the reaction temperature was maintained at 223°C (434°F) to 229°C (444°F) throughout the reaction. A nitrogen atmosphere was maintained in the dryer during the reaction.
The total reaction time was three and one-half hours after which 85 pounds of product was recovered from the dryer. No product was recovered from the filter. The condensate weight was 17.2 pounds. The average particle size of the product was 50 microns. The product was analyzed and determined to be 69% APAA. The yield was 73% of theoretical, based on the weight of aspartic acid. The agitation energy provided was 5.88 hp per hour, based on a three and one-half hour reaction time. The horsepower per hour per liter of total dryer capacity was .045.
EXAMPLE 4
L-aspartic acid (110.5 lbs.) in solid, particulate form was introduced into a fluid bed dryer equipped with an agitator as described in Example 1 and a chopper as described in Example 2. The agitator speed was maintained at 122 rpm and the chopper was run at full power. The jacket was preheated to 246°C (475°F) and a nitrogen atmosphere was provided. The reaction temperature was maintained at 222° to 223°C (431° to 434°F) throughout the reaction, while the product temperature was maintained at 204°C (400°F) . The total reaction time was six hours and two minutes.
The product recovered from the fluid bed dryer weighed 83 pounds and the product recovered from the filter weighed 2 pounds. The weight of the condensate was 18.4 pounds. The average particle size of the product was 50 microns. The product was analyzed and determined to be 91% APAA. The actual yield of APAA was 95% of theoretical, based on the starting weight of aspartic acid. Based on the reaction time, the agitation energy provided was 12.38 hp per hour. The horsepower per hour per liter of dryer capacity was .095.
The following Tables I and II summarize the results obtained from the above examples.
Figure imgf000010_0001
Actual Weight of 93 81.3 85 85
Solid Product Recovered from Process, lbs.
Actual Yield of APAA, lbs. 68.8 74.0 58.7 77.3
Yield of APAA, 84 90 73 95
% Theoretical Yield
Figure imgf000011_0001
. EXAMPLE 5
The APAA obtained from any of the previous examples is hydrolyzed using alkaline hydrolysis to produce PAA. To hydrolyze 1000 pounds of APAA, water (300 gal.) and a solution that is 50% by weight sodium hydroxide (NaOH) (60 gal.) were mixed together for about five minutes. APAA (1000 lbs.) was then added to the solution. The APAA was mixed with the solution for about 30 minutes. Water (100 gal.) was then added to the mixture. The pH of the mixture was then adjusted to 9.0 to 9.5, using a solution of 50% NaOH (approximately 11 gal.). The solution was mixed until a clear solution was obtained. The resulting PAA solution was then cooled to 50°C (122°F) .
It would be apparent to one skilled in the art that the foregoing illustrations are subject to numerous modifications which do not depart from the spirit and scope of this invention. The invention herein disclosed is therefore not to be construed as limited except as recited in the claims hereinbelow.

Claims

I Claim:
1. A method for producing a polyamino acid in relatively high yields comprising the steps of: a.) providing an agitated, fluid bed constituted by freely flowing, solid, particulate, amino acid; b.) heating the fluid bed to a temperature of at least about 180°C (356°F) and maintaining the heated bed at a temperature in the range of about 180°C (356°F) to about 250°C (482°F) for a time period sufficient to polymerize the amino acid and to drive off water from the heated bed while maintaining the mean bed particle size and a value of no more than about 150 microns and while providing a degree of agitation sufficient to maintain the particles in a substantially free-flowing state throughout the time period; and c.) recovering anhydropolyamino acid from the fluid bed.
2. The method of claim 1 wherein the amino acid is L-aspartic acid.
3. The method of claim 1 further comprising hydrolyzing the recovered anhydropolyamino acid to produce a polyamino acid.
4. The method of claim 3 wherein the recovered anhydropolyamino acid is hydrolyzed by alkaline hydrolysis.
5. The method of claim 1 wherein the fluid bed is vented to allow the water to escape therefrom.
6. The method of claim 5 further comprising recovering the water.
7. The method of claim 1 further comprising providing a nitrogen atmosphere to the fluid bed.
8. The method of claim 1 where in the degree of agitation is at least about 0.015 horsepower per hour per liter, of fluid bed volume.
PCT/US1991/005781 1990-07-03 1991-08-15 Process for the manufacture of polyamino acids WO1993004108A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US07/547,875 US5057597A (en) 1990-07-03 1990-07-03 Process for the manufacture of anhydro polyamino acids and polyamino acids
PCT/US1991/005781 WO1993004108A1 (en) 1991-08-15 1991-08-15 Process for the manufacture of polyamino acids
ES92904501T ES2098498T3 (en) 1991-08-15 1991-08-15 PROCEDURE FOR THE PREPARATION OF POLYAMINOACIDS.
CA002120039A CA2120039C (en) 1991-08-15 1991-08-15 Process for the manufacture of polyamino acids
DK92904501.1T DK0599842T3 (en) 1991-08-15 1991-08-15 Process for producing polyamino acids
EP92904501A EP0599842B1 (en) 1991-08-15 1991-08-15 Process for the manufacture of polyamino acids
DE69124628T DE69124628T2 (en) 1991-08-15 1991-08-15 METHOD FOR PRODUCING POLYAMINO ACIDS
AT92904501T ATE148721T1 (en) 1991-08-15 1991-08-15 METHOD FOR PRODUCING POLYAMINO ACIDS

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US5152902A (en) * 1991-03-19 1992-10-06 Donlar Corporation Polyaspartic acid as a calcium carbonate and a calcium phosphate inhibitor
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US5288783A (en) * 1992-05-14 1994-02-22 Srchem Incorporated Preparation of salt of polyaspartic acid by high temperature reaction
US5610267A (en) * 1992-05-14 1997-03-11 Bayer Ag Process for preparing polysuccinimide by high temperature reaction
US5380817A (en) * 1992-07-10 1995-01-10 Rohm And Haas Company Process for preparing polysuccinimides from aspartic acid
US5371177A (en) * 1992-07-10 1994-12-06 Rohm And Haas Company Process for preparing polysuccinimides from maleamic acid
US5371179A (en) * 1992-07-10 1994-12-06 Rohm And Haas Company Polysuccinimide polymers and process for preparing polysuccinimide polymers
US5319145A (en) * 1992-07-10 1994-06-07 Rohm And Haas Company Method for preparing polysuccinimides with a rotary tray dryer
US5266237A (en) * 1992-07-31 1993-11-30 Rohm And Haas Company Enhancing detergent performance with polysuccinimide
US5286810A (en) * 1992-08-07 1994-02-15 Srchem Incorporated Salt of polymer from maleic acid, polyamind and ammonia
US5292864A (en) * 1992-08-07 1994-03-08 Srchem Incorporated Decolorizing polyaspartic acid polymers
US5296578A (en) * 1992-09-18 1994-03-22 Donlar Corporation Production of polysuccinimide and polyaspartic acid from maleic anhydride and ammonia
US5219952A (en) * 1992-09-18 1993-06-15 Donlar Corporation Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia
US5393868A (en) * 1992-10-13 1995-02-28 Rohm And Haas Company Production of polysuccinimide by thermal polymerization of maleamic acid
US6001956A (en) * 1992-12-22 1999-12-14 Bayer Ag Copolymers of polyaspartic acid and polycarboxylic acids and polyamines
US5408028A (en) * 1992-12-22 1995-04-18 Bayer Ag Copolymers of polyaspartic acid and polycarboxylic acids and polyamines
DK0745102T3 (en) * 1992-12-22 2000-09-25 Bayer Ag Copolymers of polyaspartic acid and polycarboxylic acids and polyamines
DE4244031A1 (en) * 1992-12-24 1994-06-30 Bayer Ag Process for the preparation and use of polyaspartic acid and its salts
DE4300020A1 (en) * 1993-01-02 1994-07-07 Basf Ag Process for the preparation of polymers of aspartic acid and their use
US5292858A (en) * 1993-03-16 1994-03-08 Srchem Incorporated Method of production of copolymers of polyamino acids
EP0621300B1 (en) * 1993-04-23 1998-09-30 Rhodia Chimie Polyanhydroaspartic acid and its biodegradable hydrolysats
US5410017A (en) * 1993-05-21 1995-04-25 Rohm And Haas Company Continuous thermal polycondensation process for preparing polypeptide polymers
US5424391A (en) * 1993-07-20 1995-06-13 Rohm And Haas Company Production of polysuccinimide by thermal polymerization of fumaramic acid
US5484945A (en) * 1993-08-24 1996-01-16 Mitsui Toatsu Chemicals, Inc. Preparation process of polysuccinimide
US5389303A (en) * 1993-09-10 1995-02-14 Srchem Incorporated Mixtures of polyamino acids and citrate
CA2132112A1 (en) * 1993-09-21 1995-03-22 David Elliott Adler Acid catalyzed process for preparing amino acid polymers
US5457176A (en) * 1993-09-21 1995-10-10 Rohm And Haas Company Acid catalyzed process for preparing amino acid polymers
US5408029A (en) * 1993-10-06 1995-04-18 Srchem, Inc. Amino acid copolymers of maleic acid
DE59409048D1 (en) * 1993-11-02 2000-02-10 Bayer Ag Process for the preparation of aspartic acid-containing polymers
US5461085A (en) * 1993-12-17 1995-10-24 Mitsui Toatsu Chemicals, Incorporated Superabsorbent polymer and process for producing same
DE4408478A1 (en) * 1994-03-14 1995-09-21 Bayer Ag Water treatment agents
US5552516A (en) * 1994-06-22 1996-09-03 Donlar Corporation Soluble, crosslinked polyaspartates
DE4427287A1 (en) * 1994-08-02 1996-02-08 Basf Ag Process for the preparation of polycondensates of aspartic acid with improved biodegradability and their use
DE4428596A1 (en) * 1994-08-12 1996-02-15 Basf Ag Process for the preparation of condensates of aspartic acid
AU701456B2 (en) * 1994-09-12 1999-01-28 Rohm And Haas Company Method of inhibiting sulfate scale in aqueous systems
US5612384A (en) * 1994-09-13 1997-03-18 Donlar Corporation Superabsorbing polymeric networks
US5998492A (en) * 1994-09-13 1999-12-07 Donlar Corporation Super-absorbing polymeric networks
US5508434A (en) * 1994-09-28 1996-04-16 Donlar Corporation Production of a polysuccinimide and derivatives thereof in the presence of a sulfur-containing dehydrating agent
US5496922A (en) * 1994-12-27 1996-03-05 Monsanto Company Decolorization of polysuccinimide
US5449748A (en) * 1994-12-27 1995-09-12 Monsanto Company Preparation of anhydropolyamino acids at temperatures of 350° C. or above
US5521257A (en) * 1995-01-03 1996-05-28 Donlar Corporation Hydrolysis of polysuccinimide to produce low-color polyaspartic acid and salts thereof
US5470942A (en) * 1995-02-16 1995-11-28 Monsanto Company Preparation of anhydropolyamino acids
US5552517A (en) * 1995-03-03 1996-09-03 Monsanto Company Production of polysuccinimide in an organic medium
JPH09165447A (en) 1995-12-15 1997-06-24 Mitsubishi Chem Corp Copolyaspartic acid and its production
US5856427A (en) * 1996-01-16 1999-01-05 Solutia Inc. Process for the production of polysuccinimide
US5646133A (en) * 1996-03-14 1997-07-08 Donlar Corporation Polyaspartic acid and its analogues in combination with insecticides
US5869027A (en) * 1996-04-22 1999-02-09 Wood; Louis L. Method for odor reduction
US6005069A (en) * 1996-12-18 1999-12-21 Donlar Corporation Production of polysuccinimide and derivatives thereof in a sulfur-containing solvent
US5889072A (en) * 1997-02-24 1999-03-30 Solutia Inc. Process for preparing superabsorbing crosslinked polyaspartate salt
US5834568A (en) * 1997-03-17 1998-11-10 Solutia, Inc. Forming crosslinked polysuccinimide
US5859179A (en) * 1997-03-17 1999-01-12 Solutia Inc. Forming superabsorbent polymer
US5981691A (en) * 1997-04-23 1999-11-09 University Of South Alabama Imide-free and mixed amide/imide thermal synthesis of polyaspartate
US5997791A (en) 1997-11-14 1999-12-07 Solutia Inc. Superabsorbing fibers and films and processes for preparing same
US5998491A (en) * 1998-01-27 1999-12-07 Donlar Corporation Super-absorbing polymeric networks
CA2383814C (en) * 1999-09-03 2010-08-17 Sigma-Tau Healthscience S.P.A. Ultrafine l-carnitine, methods of preparing the same, compositions containing the same, and methods of using the same
US6870026B1 (en) 1999-09-17 2005-03-22 Lidochem, Inc. Chelation compositions
US6365706B1 (en) 2000-06-21 2002-04-02 Mississippi Chemical Corporation Process for production of polyasparagine and the high nitrogen content polymer formed thereby
US7166688B1 (en) 2000-07-08 2007-01-23 Lidochem, Inc. Chelation compositions
DE10200075A1 (en) * 2002-01-03 2003-07-17 Goldschmidt Ag Th Process for the preparation of copolymeric hydrophobically modified polyglutamic acid derivatives and their use
ES2364405T3 (en) * 2004-02-20 2011-09-01 Chemetall Gmbh SURFACE CONDITIONER AND SURFACE CONDITIONING METHOD.
EP2537876B1 (en) 2010-02-18 2017-01-18 Mitsui Chemicals, Inc. Processes for production of polyaspartic acid precursor polymer and polyaspartic acid salts
MX2021009268A (en) * 2019-02-21 2021-08-24 Invista Textiles Uk Ltd Process for the preparation of polyamides.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA641493A (en) * 1962-05-22 Notarbartolo Luigi Process for making synthetic linear polyamides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0646615A2 (en) * 1993-10-05 1995-04-05 Monsanto Company Preparation of polysuccinimide
EP0646615A3 (en) * 1993-10-05 1995-05-03 Monsanto Co
EP0707026A1 (en) * 1994-10-12 1996-04-17 Rhone-Poulenc Chimie Preparation of polycondensates of aminoacids and of their biodegradable polypeptidic hydrolysates, their use in detergent compositions
FR2725723A1 (en) * 1994-10-12 1996-04-19 Rhone Poulenc Chimie PROCESS FOR PREPARING POLYCONDENSATES OF AMINOACIDS AND THEIR BIODEGRADABLE POLYPEPTIDIC HYDROLYSATES AND THEIR USE IN DETERGENT COMPOSITIONS
US5688903A (en) * 1994-10-12 1997-11-18 Rhone-Poulenc Chimie Process for the preparation of polycondensates of amino acids and the biodegradable polypeptide hydrolysates thereof, and their use in detergent compositions
US5824765A (en) * 1994-10-12 1998-10-20 Rhone-Poulenc Chimie Preparation of polycondensates of amino acids and the biodegradable polypeptide hydrolysates thereof
CN1068351C (en) * 1994-10-12 2001-07-11 罗纳·布朗克化学公司 Prepn. method and application of amino acid condensation polymers and their hydrolytic products

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EP0599842B1 (en) 1997-02-05
ES2098498T3 (en) 1997-05-01
CA2120039C (en) 2001-11-20
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ATE148721T1 (en) 1997-02-15

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