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Key Questions to Ask When Ordering bulk polysuccinimide

12, May. 2025

Bulk Polysuccinimide Supply | Eco-Friendly Dispersant for Water ...

Product Description

What’s the Polysuccinimide(PSI)

Polysuccinimide (PSI) is a biodegradable, water-soluble polymer made from succinic acid. It is widely used in various industries for its high-performance properties, including chelating and dispersing capabilities. Available in bulk for industrial use, Polysuccinimide is increasingly becoming a preferred choice for manufacturers and formulators who prioritize eco-friendly and cost-effective solutions.

You can find more information on our web, so please take a look.

PSI is an unopened polyaspartic acid, which is a linear polyimide with strong activity and is the hydrolysis precursor of polyaspartic acid salts. Amino ring-opening generates polymers containing side chains. As a sustained-release product, it can be used in various fields of polyaspartic acid application. In recent years, in addition to its good industrial uses, polyaspartic acid also has broad prospects in the field of medicine due to its good biocompatibility.

Why Choose Polysuccinimide for Your Industry Needs?

Polysuccinimide offers multiple benefits across various industries, such as:

1. Water Treatment

Polysuccinimide is widely used in water treatment applications. It functions as a dispersant and scale inhibitor, preventing the formation of scale and deposits in water systems. Its ability to chelate metal ions such as calcium and magnesium helps in reducing hard water effects, improving the efficiency of water treatment processes. Polysuccinimide can be used in both industrial water treatment and municipal water systems, ensuring cleaner water for a wide range of applications.

2. Cosmetics and Personal Care

In the cosmetics industry, PSI is used as a film-forming agent, providing excellent moisturizing and hydrating properties. It helps in improving the smoothness and softness of skin and hair. Polysuccinimide is often found in shampoos, conditioners, and skin care products due to its ability to reduce moisture loss, making it ideal for sensitive skin. Additionally, it offers an environmentally friendly alternative to traditional silicone-based ingredients in cosmetic formulations.

3. Agriculture

PSI plays a significant role in agriculture, particularly as a soil conditioner and fertilizer additive. It can enhance the uptake of essential nutrients in plants by improving soil structure and moisture retention. When added to fertilizers, it increases their efficiency by ensuring a slower and more sustained release of nutrients, which promotes better growth and higher yields. PSI can also be used to prevent soil erosion, making it a valuable tool for sustainable agriculture.

4. Detergents and Cleaning Products

As a dispersant and stabilizer, PSI improves the performance of detergents by enhancing the cleaning power and preventing the deposition of minerals like calcium and magnesium. It can be added to laundry detergents, dishwashing products, and industrial cleaners to ensure more effective cleaning and reduced detergent residue.

FAQs

1. What is Polysuccinimide used for?
It is used in water treatment, cosmetics, agriculture, and detergents. It acts as a dispersant, scale inhibitor, film-forming agent, and soil conditioner.

You will get efficient and thoughtful service from Hebei Think-Do Chemicals Co.ltd.

2. Is Polysuccinimide biodegradable?
Yes, It is a biodegradable polymer, making it an environmentally friendly alternative to traditional chemicals in many industrial applications.

3. How can I order bulk Polysuccinimide?
You can contact us directly to place an order or request a quote for your bulk Polysuccinimide needs.

Process for the preparation of polysuccinimide, polyaspartic acid ...

USA - Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof, and the use of these compounds - Google Patents

Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof, and the use of these compounds Download PDF

Info

Publication number: USA
Authority: US; United States
Prior art keywords: acid; polyaspartic acid; polysuccinimide; preparation; maleamic
Prior art date: -12-24
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

US08/168,847

Inventor

Torsten Groth

Winfried Joentgen

Hans W. Linden

Nikolaus Muller

Heinz-Joachim Rother

Paul Wagner

Martin Kugler

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.)

Bayer AG

Original Assignee

Bayer AG

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.)

-12-24

Filing date

-12-17

Publication date

-08-06

-12-17 Application filed by Bayer AG filed Critical Bayer AG

-12-17 Assigned to BAYER AG reassignment BAYER AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LINDEN, HANS W., ROTHER, HEINZ-JOACHIM, KUGLER, MARTIN, GROTH, TORSTEN, JOENTGEN, WINFRIED, MULLER, NIKOLAUS, WAGNER, PAUL

-08-06 Application granted granted Critical

-08-06 Publication of USA publication Critical patent/USA/en

-12-17 Anticipated expiration legal-status Critical

Status Expired - Fee Related legal-status Critical Current

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
- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
- 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/—Polysuccinimides
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/12—Sulfonates of aromatic or alkylated aromatic compounds
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/—Polyamides or polyimides
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds

Definitions

the invention relates to a process for the preparation of polysuccinimide and polyaspartic acid and salts thereof by reaction of maleic anhydride derivatives, and to the use of these compounds.
PAA polyaspartic acid
derivatives thereof have been described in numerous publications and patents going back some time.
the preparation can be effected by thermal polycondensation of aspartic acid (J. Org. Chem. 26, ()).
Maleic anhydride is converted into the monoammonium salt in aqueous medium with addition of concentrated ammonia solution.
the monoammonium salt is polymerized in the melt to give Polysuccinimide. It is converted to polyaspartic acid or a salt thereof by hydrolysis.
U.S. Pat. No. 4,696,981 uses microwaves in these reactions.
this process uses maleic acid derivatives (monoammonium salt and monoamide, see examples) for the preparation of the intermediate polysuccinimide by thermal polymerization; the polysuccinimide can itself be converted into the desired derivatives by means of amines in suitable solvents.
the PAA can be employed, inter alia, as a scale inhibitor and scale deposit remover (U.S. Pat. No. 4,839,461, EP-A-256 366, U.S. Pat. No. 5,116,513).
Other known applications are, for example, as a detergent additive or fertilizer (U.S. Pat. No. 4,839,461, EP-A-256 366, EP-A 454 126) and for the production of bone replacement materials (EP-A 383 568).
the invention relates to a process for the preparation of polysuccinimide and polyaspartic acid and salts thereof from maleamic acid, characterized in that maleic anhydride and ammonia are reacted, optionally in the presence of a solvent, to give maleamic acid, the maleamic acid is subjected to continuous thermal polymerization at from 100° C. to 350° C. in a reactor at a residence time of from 0.5 to 30 minutes, and the resultant polysuccinimide is, if desired, converted into polyaspartic acid or a salt thereof by hydrolysis.
the polysuccinimide produced according to the present invention contains in a preferred embodiment essentially recurring units of the following formula ##STR1##
polyaspartic acid is taken to mean both free polyaspartic acid and salts thereof.
the polysuccinimide and the polyaspartic acid prepared according to the invention contain further recurring units of the following structure; depending on process conditions and educts:
the recurring units b)and c) are preferably present in an amount of from 1:1 to 1:100, based on the total amount of a).
Analysis of the chemical structure is preferably carried out using 13 C-NMR and, after total hydrolysis, by means of HPLC, GC and GC/MS.
the product obtained directly from polymerization or hydrolysis can contain the abovementioned recurring units a) and simultaneously the imide structures prepared with elimination of H 2 O.
the polymerisation products can be converted into the corresponding salt of the polyaspartic acid by hydrolysis in a base at 20° to 95° C., especially 40° to 70° C., preferred at 50° to 70° C. Furthermore it is possible to obtain the free polyaspartic acid by hydrolysis in water at 80° C. to 100° C. or by treatment of the salt with acids or with acidic ion exchangers.
maleic anhydride and ammonia are reacted in an inert solvent to give maleamic acid.
solvents are halogenated and non-halogenated aromatic hydrocarbons, alkanes and ethers, such as, for example, chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, cumene, tetralin, methylene chloride, chloroform, diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, petroleum ether, hexane and heptane.
Examples of particularly preferred solvents are toluene, xylene, dichlorobenzene and o-dichlorobenzene.
the reaction of the maleic anhydride with ammonia is carried out, in particular, at a pressure of from 0 to 10 bar, preferably at from 0 to 5 bar, in particular at from 0.5 to 3.5 bar, at a temperature of from 15° to 100° C., in particular at from 40° to 80° C., particularly preferably at from 60° to 70° C., and at a molar maleic anhydride:NH 3 ratio of from 1:0.8 to 1:1.5, preferably from 1:0.95 to 1:1.2, particularly 1:1.
first maleic anhydride and ammonia are reacted with one another in an inert solvent (toluene) at from 60° to 70° C. and in the ratio 1:1.
an inert solvent toluene
the preparation of maleamic acid has already been disclosed per se in JP-A 49/035 325, U.S. Pat. No. 2,459,964, DE-A 847 287 and DE-A 945 987.
the maleamic acid is converted into a polymerization product in a suitable continuous-operation reactor (paddle dryer, single-screw and twin-screw high-viscosity reactors, for example Discotherm and All-Phasen-Konti units from List, screw machines, preferably self-cleaning multiscrew machines or in a belt reactor) by continuous thermal rapid polymerization with a residence time of from 0.5 to 30 minutes, preferably from 1.5 to 15 minutes, at a temperature of from 100° to 350° C.
a suitable continuous-operation reactor praddle dryer, single-screw and twin-screw high-viscosity reactors, for example Discotherm and All-Phasen-Konti units from List, screw machines, preferably self-cleaning multiscrew machines or in a belt reactor
the polymerization product can be converted into the corresponding polyaspartic acid salt by dissolution in a base at from 20° to 95° C., preferably at from 40° to 70° C., particularly preferably at from 50° to 70° C. It is also possible to obtain the free polyaspartic acid as early as this point by treatment with acids or acidic ion exchangers. The product is obtained as a fine powder by spray drying.
thermal polymerisation can otionally be carried out in the presence of a catalyst for example pyrosulphuric acid, phosphoric acid, sulphonic acid, phosphites, phosphonates or quaternary ammonium salts and the like.
a catalyst for example pyrosulphuric acid, phosphoric acid, sulphonic acid, phosphites, phosphonates or quaternary ammonium salts and the like.
the invention furthermore relates to a process for the preparation of salts of the polyaspartic acid prepared according to the invention, in which the polysuccinimide or the free polyaspartic acid is reacted with bases.
bases which can be used are alkali and alkaline earth metal hydroxides or carbonates, in particular NaOH, KOH or LiOH.
concentration of the base used is not crucial; it is preferably from 5 to 50% by weight in the form of aqueous solutions.
the compounds according to the invention are used, in particular, as dispersants, detergent additives, sequestrants, scale inhibitors, corrosion inhibitors, in particular for brass, and as microbicides and in fertilizers.
the free-flowing product has a bulk density of 0.55 g/ml.
the final part of the experimental apparatus (about 1/5 of the length) is closed, so that the water of reaction formed cannot escape at this point.
the residual water therefore leaves the polymer composition emerging at the end of the screw in gas form, so that the high-viscosity substance expands with an (approximate) doubling in volume.
the rapidly cooling, beige, dry composition is powdered, giving 11,677 g of polymerization product. (Yield of 91.3% of theory, based on the carbon value).
a finely pulverulent, pale-yellow powder is formed with a substance loss (through carbon analysis) of about 10%.
the product can be employed directly as a sequestrant and dispersant and as a corrosion inhibitor.
m 1 weight loss of the metal sample with inhibitor.
the antimicrobial activity of the compounds according to the invention was analysed by determining the minimum inhibition concentration (MIC).
agar prepared from brewers wort and peptone was treated with the compound according to the invention in various concentrations. After the agar had solidified, it was contaminated with pure cultures of the test organisms shown in the table. After storage at 28° C. and relative atmospheric humidity of from 60 to 70% for 2 weeks, the MIC was determined. The MIC is the lowest concentration of active compound at which no colonization by the microbe species used takes place.
a) 0.3 g of PAA Na salt are dispersed in 200 ml of tap water with 10 g of zinc oxide.
the dispersion is introduced into a 250 ml measuring cylinder. After 3 hours, samples are taken from various points of the measuring cylinder and analysed for their zinc oxide content. It was found that the zinc oxide content is always the same as a consequence of the good dispersing action. Furthermore, the sedimentation stability is determined after 3 hours and after 24 hours. In both cases, virtually no sedimentation layer on the base of the measuring cylinder is observed.

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Organic Chemistry (AREA)
Engineering & Computer Science (AREA)
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Life Sciences & Earth Sciences (AREA)
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Polymers & Plastics (AREA)
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General Health & Medical Sciences (AREA)
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Pest Control & Pesticides (AREA)
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Environmental Sciences (AREA)
Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Preventing Corrosion Or Incrustation Of Metals (AREA)
Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

Polyaspartic acid is prepared by reacting maleic anhydride and ammonia to give maleamic acid, polymerizing the maleamic acid and subsequently hydrolyzing the product to give polyaspartic acid or a salt thereof.

Description

The invention relates to a process for the preparation of polysuccinimide and polyaspartic acid and salts thereof by reaction of maleic anhydride derivatives, and to the use of these compounds. The preparation and use of polyaspartic acid (PAA) and derivatives thereof have been described in numerous publications and patents going back some time. Thus, the preparation can be effected by thermal polycondensation of aspartic acid (J. Org. Chem. 26, ()). U.S. Pat. No. 4,839,461 (=EP-A 0 256 366) describes the preparation of polyaspartic acid from maleic anhydride, water and ammonia. Maleic anhydride is converted into the monoammonium salt in aqueous medium with addition of concentrated ammonia solution. The monoammonium salt is polymerized in the melt to give Polysuccinimide. It is converted to polyaspartic acid or a salt thereof by hydrolysis. U.S. Pat. No. 4,590,260 (=JP-A (59)/) discloses the polycondensation of amino acids together with derivatives of malic, maleic and/or fumaric acid at from 100° to 225° C. U.S. Pat. No. 4,696,981 uses microwaves in these reactions. DE-A 2 253 190 (=U.S. Pat. No. 3,846,380) describes a process for the preparation of polyamino acid derivatives, specifically polyaspartic acid derivatives. In addition to aspartic acid, this process uses maleic acid derivatives (monoammonium salt and monoamide, see examples) for the preparation of the intermediate polysuccinimide by thermal polymerization; the polysuccinimide can itself be converted into the desired derivatives by means of amines in suitable solvents. The PAA can be employed, inter alia, as a scale inhibitor and scale deposit remover (U.S. Pat. No. 4,839,461, EP-A-256 366, U.S. Pat. No. 5,116,513). Other known applications are, for example, as a detergent additive or fertilizer (U.S. Pat. No. 4,839,461, EP-A-256 366, EP-A 454 126) and for the production of bone replacement materials (EP-A 383 568). The invention relates to a process for the preparation of polysuccinimide and polyaspartic acid and salts thereof from maleamic acid, characterized in that maleic anhydride and ammonia are reacted, optionally in the presence of a solvent, to give maleamic acid, the maleamic acid is subjected to continuous thermal polymerization at from 100° C. to 350° C. in a reactor at a residence time of from 0.5 to 30 minutes, and the resultant polysuccinimide is, if desired, converted into polyaspartic acid or a salt thereof by hydrolysis. The polysuccinimide produced according to the present invention contains in a preferred embodiment essentially recurring units of the following formula ##STR1## In the present invention, polyaspartic acid is taken to mean both free polyaspartic acid and salts thereof. In a preferred embodiment, the polysuccinimide and the polyaspartic acid prepared according to the invention contain further recurring units of the following structure; depending on process conditions and educts: a) aspartic acid units of the formula ##STR2## Generally at least 50%, especially at least 70% of the polyaspartic acid units are present in the β-form. b) malic units of the formula ##STR3## c) maleic and fumaric units of the formula ##STR4## The recurring units b)and c) are preferably present in an amount of from 1:1 to 1:100, based on the total amount of a). Analysis of the chemical structure is preferably carried out using 13 C-NMR and, after total hydrolysis, by means of HPLC, GC and GC/MS. The product obtained directly from polymerization or hydrolysis can contain the abovementioned recurring units a) and simultaneously the imide structures prepared with elimination of H2 O. The polymerisation products can be converted into the corresponding salt of the polyaspartic acid by hydrolysis in a base at 20° to 95° C., especially 40° to 70° C., preferred at 50° to 70° C. Furthermore it is possible to obtain the free polyaspartic acid by hydrolysis in water at 80° C. to 100° C. or by treatment of the salt with acids or with acidic ion exchangers. It is assumed that the following structures are intermediates in the reaction according to the invention:

Maleic anhydride+NH.sub.3 →maleamic acid ##STR5##

hydrolysis→polyaspartic acid (salt)

In a preferred embodiment of the invention, maleic anhydride and ammonia are reacted in an inert solvent to give maleamic acid. Particularly preferred solvents are halogenated and non-halogenated aromatic hydrocarbons, alkanes and ethers, such as, for example, chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, cumene, tetralin, methylene chloride, chloroform, diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, petroleum ether, hexane and heptane. Examples of particularly preferred solvents are toluene, xylene, dichlorobenzene and o-dichlorobenzene. The reaction of the maleic anhydride with ammonia is carried out, in particular, at a pressure of from 0 to 10 bar, preferably at from 0 to 5 bar, in particular at from 0.5 to 3.5 bar, at a temperature of from 15° to 100° C., in particular at from 40° to 80° C., particularly preferably at from 60° to 70° C., and at a molar maleic anhydride:NH3 ratio of from 1:0.8 to 1:1.5, preferably from 1:0.95 to 1:1.2, particularly 1:1. In a particularly preferred embodiment of the invention, first maleic anhydride and ammonia are reacted with one another in an inert solvent (toluene) at from 60° to 70° C. and in the ratio 1:1. This forms a suspension of maleamic acid in the solvent in question. Removal of the solvent gives, without further purification, a maleamic acid in high purity and virtually quantitative yield. The preparation of maleamic acid has already been disclosed per se in JP-A 49/035 325, U.S. Pat. No. 2,459,964, DE-A 847 287 and DE-A 945 987. The maleamic acid is converted into a polymerization product in a suitable continuous-operation reactor (paddle dryer, single-screw and twin-screw high-viscosity reactors, for example Discotherm and All-Phasen-Konti units from List, screw machines, preferably self-cleaning multiscrew machines or in a belt reactor) by continuous thermal rapid polymerization with a residence time of from 0.5 to 30 minutes, preferably from 1.5 to 15 minutes, at a temperature of from 100° to 350° C. (preferably from 155° to 230° C.), if desired in vacuo; the polymerization product can be converted into the corresponding polyaspartic acid salt by dissolution in a base at from 20° to 95° C., preferably at from 40° to 70° C., particularly preferably at from 50° to 70° C. It is also possible to obtain the free polyaspartic acid as early as this point by treatment with acids or acidic ion exchangers. The product is obtained as a fine powder by spray drying. The above mentioned thermal polymerisation can otionally be carried out in the presence of a catalyst for example pyrosulphuric acid, phosphoric acid, sulphonic acid, phosphites, phosphonates or quaternary ammonium salts and the like. The polymer prepared exhibits different chain lengths and molecular weights according to analysis by gel-permeation chromatography of Mw =500 to 10,000, preferably from to , particularly preferably to , depending on the reaction conditions, for example residence time and temperature of the thermal polymerization in the Konti reactor. The invention furthermore relates to a process for the preparation of salts of the polyaspartic acid prepared according to the invention, in which the polysuccinimide or the free polyaspartic acid is reacted with bases. Examples of bases which can be used are alkali and alkaline earth metal hydroxides or carbonates, in particular NaOH, KOH or LiOH. The concentration of the base used is not crucial; it is preferably from 5 to 50% by weight in the form of aqueous solutions. The compounds according to the invention are used, in particular, as dispersants, detergent additives, sequestrants, scale inhibitors, corrosion inhibitors, in particular for brass, and as microbicides and in fertilizers. SPECIFIC EXAMPLES 1. Preparation of Maleamic Acid g of toluene dried by distillation and g=16.7 mol of maleic anhydride are introduced into a 10 l autoclave (V4A). The mixture is heated to 60° C. with stirring. After the mixture has been held at this temperature for 0.5 hour, 283 g=16.7 mol of dry NH3 gas are introduced to a maximum pressure of 3 bar over the course of about 6 hours while the temperature is kept constant. When the calculated amount of NH3 gas has been consumed, a residual pressure of 0.5 bar remains. The mixture is stirred at 60° c. for a further 2 hours and cooled to room temperature. The fine, milky white product suspension is filtered, giving g of filtrate and g of toluene-moist maleamic acid. Drying gives g of maleamic acid=97.5% of theory, melting point 168° C. The free-flowing product has a bulk density of 0.55 g/ml. 2. Preparation of Maleamic Acid (Concentrated Version in Order to Increase the Spacetime Yield and Efficiency) g of toluene dried by distillation and g=23.0 mol of maleic anhydride are introduced into a 10 l V4A autoclave. The mixture is heated to 60° C. with stirring. After 0.5 hour, 391 g=23.0 mol of dry NH3 gas are introduced at from 60° to 70° C. and at a maximum pressure of 2.6 bar over the course of 4.5 hours. When the introduction is complete, the mixture is stirred for a further 2 hours. A residual pressure of about 0.5 bar remains. The reaction mixture is cooled to room temperature and filtered, giving g of toluene filtrate (the evaporation losses in the laboratory can be avoided in industry) and g of toluene-moist maleamic acid. Drying gives g of maleamic acid=93.2% of theory (yield based on carbon). Melting point 165.2° C. 3. Preparation of Polysuccinimide (Polyimide Form) 14 kg of maleamic acid=121.7 mol (melting point: 166°-168° C., bulk density: 64.3 g/100 ml) were conveyed continuously from a feed hopper to the water-cooled part of a reactor screw by a conveying screw. At a mean residence time of from 1.5 to 5 minutes, the initially finely crystalline, white maleamic acid is conveyed into a prewarming zone at about 130° C. and then into the reaction zone at from about 155° to 185° C. A melt in which the polyaddition or polycondensation step takes place is formed in the reaction zone. The water of reaction formed (and any decomposition products ) escape via a gas-emission tower. The final part of the experimental apparatus (about 1/5 of the length) is closed, so that the water of reaction formed cannot escape at this point. The residual water therefore leaves the polymer composition emerging at the end of the screw in gas form, so that the high-viscosity substance expands with an (approximate) doubling in volume. The rapidly cooling, beige, dry composition is powdered, giving 11,677 g of polymerization product. (Yield of 91.3% of theory, based on the carbon value). 4. Preparation of the Na Salt of Polyaspartic Acid, Spray-dried 11,246 g of the product obtained from 3)=107 mol (from carbon) are metered simultaneously with g of 48.8% strength NaOH=101.3 mol into g of H2 O at from 50° to 60° C. A pH of 9 is not exceeded. During dissolution of the crude product, complete hydrolysis of the imide units without hydrolysis of the amide bonds of the polymer chain must take place. The approximately 50% strength solution prepared (density at 20° C.=1.342, pH=8.4) is spray-dried at evaporator temperatures of 80°/180° C. and a volume throughput of from 2 to 3 l/h). A finely pulverulent, pale-yellow powder is formed with a substance loss (through carbon analysis) of about 10%. The product can be employed directly as a sequestrant and dispersant and as a corrosion inhibitor. 14,605 g of PAA Na salt, spray-dried, are obtained. Content: 31.7% by weight of carbon 5.7% by weight of water Yield:90% of theory, from carbon It is also possible to use the aqueous aspartic acid Na salt solution directly without spray-drying. FURTHER ANALYSES 1. Molecular Weight Determination by GPC

______________________________________                                    
M.sub.n    /     M.sub.w      /   M.sub.z                                 
______________________________________                                    
       /              /                                       
______________________________________

USE EXAMPLE 1. Test as Corrosion Inhibitor Bare, degreased brass samples (MS 63) were used for the corrosion test. The test solution used was artificial seawater according to ASTM D 665-IP 135, to which the substance under test had been added. During the experimental period of 7 hours, the metal samples were fully immersed in the test solution at 55° C., into which about 100 ml/min of air were introduced. After the test, the metal samples were cleaned for 15 seconds in semiconcentrated hydrochloric acid and washed with water and acetone. The dry metal samples were weighed before and after the test. The weight loss was used to calculate the percentage protective action S, based on a control sample: ##EQU1## where m=weight loss of the metal sample without inhibitor (control sample), m1 =weight loss of the metal sample with inhibitor. The results of the percentage protective action are shown in the table below:

______________________________________                                    
Concentration Protective action S                                         
in mg/l       in %                                                        
______________________________________                                    
10            9                                                           
25            70                                                          
50            81                                                          
0             0                                                           
______________________________________

2. Test for Antimicrobial Activity The antimicrobial activity of the compounds according to the invention was analysed by determining the minimum inhibition concentration (MIC). To this end, agar prepared from brewers wort and peptone was treated with the compound according to the invention in various concentrations. After the agar had solidified, it was contaminated with pure cultures of the test organisms shown in the table. After storage at 28° C. and relative atmospheric humidity of from 60 to 70% for 2 weeks, the MIC was determined. The MIC is the lowest concentration of active compound at which no colonization by the microbe species used takes place. The table below shows the MIC values for the compound according to the invention.

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Test organism    MIC values in mg/l                                       
______________________________________                                    
Bacillus subtilis                                                         
                                                                      
Pseudomonas aeruginosa                                                    
                                                                      
Penicillium brevicaule                                                    
                                                                      
Chaetomium globosum                                                       
                                                                      
Aspergillus niger                                                         
                                                                      
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3. Sequestration of a Surfactant Assessment of the turbidity intensity of an alkylbenzenesulphonic acid Na salt solution in tap water. 1 ml of 10% strength Marlon A 375 solution is made up to 100 ml with tap water (total hardness 14.1 (German hardness)) with addition of 0.1 g of spray-dried PAA Na salt. The resultant solution has a stability of more than 7 days. Without addition of PAA Na salt, the solution becomes turbid in a few minutes. 4. Dispersion of Zinc Oxide a) 0.3 g of PAA Na salt are dispersed in 200 ml of tap water with 10 g of zinc oxide. The dispersion is introduced into a 250 ml measuring cylinder. After 3 hours, samples are taken from various points of the measuring cylinder and analysed for their zinc oxide content. It was found that the zinc oxide content is always the same as a consequence of the good dispersing action. Furthermore, the sedimentation stability is determined after 3 hours and after 24 hours. In both cases, virtually no sedimentation layer on the base of the measuring cylinder is observed.

Claims (18)

We claim: 1. Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof from maleamic acid, wherein maleic anhydride and ammonia are reacted, optionally in the presence of a solvent, to give maleamic acid, the maleamic acid is subjected to continuous thermal polymerization at from 100° C. to 350° C. in a reactor at a residence time of from 0.5 to 30 minutes, and the resultant polysuccinimide is, if desired, converted into polyaspartic acid or a salt thereof by hydrolysis. 2. Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof from maleamic acid, characterized in that maleic anhydride and ammonia are reacted, optionally in the presence of a solvent, to give maleamic acid, the maleamic acid is subjected to continuous thermal polymerization at from 155° C. to 230° C. in a reactor at a residence time of from 1.5 to 15 minutes, and the resultant polysuccinimide is, if desired, converted into polyaspartic acid or a salt thereof by hydrolysis. 3. Process according to claim 1, wherein the molecular weight of the polyaspartic acid, determined by gel permeation chromatography with absolute calibration, is from 500 to 10,000. 4. Process according to claim 1, wherein the polyaspartic acid contains recurring units which, in the form of the free acid, conform to the following structure: ##STR6## 5. Process for the preparation of polyaspartic acid salts according to claim 1, wherein the polysuccinimide obtained according to claim 1 is hydrolyzed by means of a base. 6. Process according to claim 2, wherein the molecular weight of the polyaspartic acid, determined by gel permeation chromatography with absolute calibration, is from 500 to 10,000. 7. Process according to claim 2, wherein the polyaspartic acid contains recurring units which, in the form of the free acid, conform to the following structure: ##STR7## 8. Process according to claim 3, wherein the polyaspartic acid contains recurring units which, in the form of the free acid, conform to the following structure: ##STR8## 9. Process for the preparation of polyaspartic acid salts according to claim 2, wherein the polysuccinimide obtained according to claim 1 is hydrolyzed by means of a base. 10. Process for the preparation of polyaspartic acid salts according to claim 3, wherein the polysuccinimide obtained according to claim 1 is hydrolyzed by means of a base. 11. Process for the preparation of polyaspartic acid salts according to claim 4, wherein the polysuccinimide obtained according to claim 1 is hydrolyzed by means of a base. 12. Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof from maleamic acid, wherein maleic anhydride and ammonia are reacted, in the presence of a solvent, to give maleamic acid, the maleamic acid is subjected to continuous thermal polymerization at from 100° C. to 350° C. in a reactor at a residence time of from 0.5 to 30 minutes, and the resultant polysuccinimide is, if desired, converted into polyaspartic acid or a salt thereof by hydrolysis. 13. Process according to claim 12, wherein the solvent is selected from the group consisting of halogenated aromatic hydrocarbons, non-halogenated aromatic hydrocarbons, halogenated alkanes, non-halogenated alkanes, halogenated ethers and non-halogenated ethers. 14. Process according to claim 12, wherein the solvent is selected from the group consisting of chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, cumene, tetralin, methylene chloride, chloroform, diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, petroleum ether, hexane and heptane. 15. Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof from maleamic acid, wherein maleic anhydride and ammonia are reacted, in the presence of a solvent, to give maleamic acid, the maleamic acid is subjected to continuous thermal polymerization at from 155° C. to 230° C. in a reactor at a residence time of from 1.5 to 15 minutes, and the resultant polysuccinimide is, if desired, converted into polyaspartic acid or a salt thereof by hydrolysis. 16. Process according to claim 14, wherein the solvent is selected from the group consisting of halogenated aromatic hydrocarbons, non-halogenated aromatic hydrocarbons, halogenated alkanes, non-halogenated alkanes, halogenated ethers and non-halogenated ethers. 17. Process according to claim 14, wherein the solvent is selected from the group consisting of chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, cumene, tetralin, methylene chloride, chloroform, diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, petroleum ether, hexane and heptane. 18. Process according to claim 12, wherein the hydrolysis is effected by using a base selected from the group consisting of alkali earth metal hydroxides, alkali earth metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates. US08/168,847 -12-24 -12-17 Process for the preparation of polysuccinimide, polyaspartic acid and salts thereof, and the use of these compounds Expired - Fee Related USA (en)

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* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title USA (en) * -03-01 -08-18 Agfa-Gevaert Photographic silver halide material AUB2 (en) * -09-12 -04-29 Rohm And Haas Company Method of inhibiting corrosion in aqueous systems USA (en) * -04-23 -11-09 University Of South Alabama Imide-free and mixed amide/imide thermal synthesis of polyaspartate USA (en) * -04-03 -07-25 Bayer Aktiengellschaft Process for the preparation of polymers with repeating succinyl units using catalysts USA (en) * -03-05 -08-01 Bayer Aktiengesellschaft Simultaneous washing and bleaching of native fibres and textile products therefrom USB1 (en) * -03-06 -01-30 Bayer Ag Polyasparaginic acid homopolymers an copolymers, biotechnical production and use thereof EPA1 (en) * -04-07 -01-23 National Starch & Chemical Company Use of polyamino acid salts in water-borne adhesive applications USB1 (en) -06-21 -04-02 Mississippi Chemical Corporation Process for production of polyasparagine and the high nitrogen content polymer formed thereby USB1 (en) -10-05 -05-28 Bayer Aktiengesellschaft Process for preparing biodegradable polymers having repeating succinyl units USA1 (en) * -08-30 -06-20 Thomas Klein Polyaspartic acid concentration determination by fluorometry USA1 (en) * -10-26 -09-19 Wood Thomas K. Preventing corrosion with beneficial biofilms USA1 (en) * -03-04 -09-07 Berger Patricia S Automatic dishwashing composition with corrosion inhibitors CNC (en) * -01-15 -05-30 同济大学 Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid EPA4 (en) * -03-30 -11-17 Mitsui Chemicals, Inc. AGENTS AGAINST DEPOSITION AND DETERGENT COMPOSITION CNA (en) * -05-31 -07-29 郑伟雄 Preparation method of polyaspartic acid potassium and application of polyaspartic acid potassium in plant growth promoter

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* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title ATET1 (en) * -02-22 -11-15 Bayer Ag METHOD FOR PRODUCING POLYSUCCINIMIDE AND POLYASPARAGIC ACID DEA1 (en) * -07-21 -01-25 Bayer Ag Process for the preparation of polysuccinimide or maleic acid DEA1 (en) * -11-03 -05-09 Bayer Ag Mixture for corrosion inhibition of metals KRA (en) * -12-21 -07-18 미우라 아끼라 Method for preparing polyaspartic acid and salts thereof DEA1 (en) * -05-04 -11-07 Bayer Ag Process for the preparation of polymers with recurring succinyl units DEA1 (en) * -01-29 -07-31 Bayer Ag Process for the preparation of polymers with repeating succinyl units DEA1 (en) * -02-21 -08-27 Bayer Ag Process for carrying out polycondensation reactions USB2 (en) -03-03 -07-29 Nippon Skokubai Co., Ltd. Water-absorbent agents containing polycarboxylic amine chelating agents JPB2 (en) * -04-15 -05-30 株式会社日本触媒 Water-absorbing agent, absorber, absorbent article, and method for measuring absorption characteristics ATB (en) -06-24 -09-25 Aware Chemicals Llc METHOD FOR PRE-TREATING A METAL WORKPIECE FOR A PAINTING USB2 (en) * -11-29 -04-01 Toda Kogyo Corporation Purifying agent for purifying soil or ground water, process for producing the same, and method for purifying soil or ground water using the same EPB1 (en) -02-18 -01-18 Mitsui Chemicals, Inc. Processes for production of polyaspartic acid precursor polymer and polyaspartic acid salts CNB (en) * -05-05 -11-28 西安交通大学 Method for synthesizing polyaspartic ester in presence of supported alkali metal fluoride serving as catalyst USB2 (en) -02-08 -09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin USB2 (en) -02-08 -09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin CNA (en) * -11-28 -06-03 天津工业大学 Microbial compound fertilizer and production method thereof ATA2 (en) -05-13 -11-15 Univ Wien Tech Process for the preparation of crystalline polyimides

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Cited By (21)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title AUB2 (en) * -09-12 -04-29 Rohm And Haas Company Method of inhibiting corrosion in aqueous systems USA (en) * -03-01 -08-18 Agfa-Gevaert Photographic silver halide material USB1 (en) * -03-06 -01-30 Bayer Ag Polyasparaginic acid homopolymers an copolymers, biotechnical production and use thereof USA (en) * -04-23 -11-09 University Of South Alabama Imide-free and mixed amide/imide thermal synthesis of polyaspartate USA (en) * -03-05 -08-01 Bayer Aktiengesellschaft Simultaneous washing and bleaching of native fibres and textile products therefrom USA (en) * -04-03 -07-25 Bayer Aktiengellschaft Process for the preparation of polymers with repeating succinyl units using catalysts USB1 (en) -10-05 -05-28 Bayer Aktiengesellschaft Process for preparing biodegradable polymers having repeating succinyl units EPA1 (en) * -04-07 -01-23 National Starch & Chemical Company Use of polyamino acid salts in water-borne adhesive applications EPA4 (en) * -04-07 -10-16 Nat Starch & Chemical Company USE OF POLYAMINE ACID SALTS IN AQUEOUS ADHESIVE APPLICATIONS USB1 (en) -06-21 -04-02 Mississippi Chemical Corporation Process for production of polyasparagine and the high nitrogen content polymer formed thereby USB2 (en) -06-21 -05-13 Mississippi Chemical Corporation Process for production of polyasparagine and the high nitrogen content polymer formed thereby USA1 (en) * -08-30 -06-20 Thomas Klein Polyaspartic acid concentration determination by fluorometry USB2 (en) -08-30 -01-24 Thomas Klein Polyaspartic acid concentration determination by fluorometry USA1 (en) * -10-26 -09-19 Wood Thomas K. Preventing corrosion with beneficial biofilms CNC (en) * -01-15 -05-30 同济大学 Process for preparation of biodegradable corrosion-scale inhibitor poly-aspartic acid USA1 (en) * -03-04 -09-07 Berger Patricia S Automatic dishwashing composition with corrosion inhibitors USB2 (en) -03-04 -07-17 The Procter & Gamble Company Automatic dishwashing composition with corrosion inhibitors EPA4 (en) * -03-30 -11-17 Mitsui Chemicals, Inc. AGENTS AGAINST DEPOSITION AND DETERGENT COMPOSITION USB2 (en) -03-30 -03-05 Mitsui Chemicals, Inc. Antiredeposition agent and detergent composition CNA (en) * -05-31 -07-29 郑伟雄 Preparation method of polyaspartic acid potassium and application of polyaspartic acid potassium in plant growth promoter CNB (en) * -05-31 -12-08 杨凌德尔生物科技有限公司 Preparation method of potassium polyaspartate and application of potassium polyaspartate in plant growth promoter

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