CN1146210A - Polyaspartic acid or salt thereof and process for producing the same - Google Patents
Polyaspartic acid or salt thereof and process for producing the same Download PDFInfo
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- CN1146210A CN1146210A CN 95192645 CN95192645A CN1146210A CN 1146210 A CN1146210 A CN 1146210A CN 95192645 CN95192645 CN 95192645 CN 95192645 A CN95192645 A CN 95192645A CN 1146210 A CN1146210 A CN 1146210A
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Abstract
This invention relates to a polyaspartic acid or a salt thereof, having a calcium ion chelating capacity of 4.3 (Ca<++>g/100g polymer) or above; a process for producing the acid or salt by hydrolyzing polysuccinimide obtained by the polycondensation of a monomer selected from the group consisting of reaction products formed between maleic acid and ammonia, aspartic acid, and maleamic acid in the presence of a solvent and an acid catalyst; a polysuccinimide as the precursor therefor; and another process for producing the acid or salt by hydrolyzing polysuccinimide obtained by the polycondensation of a monomer selected from the group consisting of reaction products formed between maleic acid and ammonia, aspartic acid, and maleamic acid in the presence of a mixture of at least two solvents including at least an aprotic polar solvent and an acid catalyst. The obtained polyaspartic acid or salt thereof is useful as a chelating agent, flocculant, scale inhibitor, detergent builder, dispersant, humectant, fertilizer additive, raw material for biodegradable polymer, and so forth.
Description
Technical field
The present invention relates to poly aspartic acid or its salt, and manufacture method.Poly aspartic acid of the present invention or its salt are of great use as sequestrant, scale preventive, detergent use washing assistant, dispersion agent, wetting Agent for Printing Inks, fertilizer with additive, various coating-forming agents etc.
Background technology
Poly aspartic acid just has been used as sequestrant, scale preventive, detergent use washing assistant, dispersion agent, wetting Agent for Printing Inks, fertilizer with additive etc. very early, generally, obtain by the hydrolysis polysuccinimide.Past, manufacture method as polysuccinimide, known have such several method: under the high temperature more than 180 ℃, make aspartic acid or maleinamic acid with the method for solid state reaction (with reference to U.S. Patent No. 5,057, No. 597 specification sheetss, U.S. Patent No. 5,219, No. 986 specification sheetss, U.S. Patent No. 5,315, No. 010 specification sheets, Te Kaiping 6-206937 communique etc.), under the temperature more than 120 ℃, make ammonia and maleic anhydride with the method for solid state reaction (with reference to U.S. Patent No. 4,839, No. 461 specification sheetss, U.S. Patent No. 5,296, No. 578 specification sheetss etc.), at polyoxyethylene glycol, under the existence of N-Methyl pyrrolidone or tetramethylene sulfone equal solvent, under the temperature more than 120 ℃, make the method for aspartic acid or maleinamide acid-respons (open flat 6-145350 communique with reference to the spy, Te Kaiping 6-211982 communique etc.) etc.But, in these methods, be yield in order to improve transformation efficiency, must make raw material reaction for a long time under hot conditions, and the poly aspartic acid that obtains by these methods, the calcium ion sequestering power of any is all very low.
In addition, as the method for short period of time internal reaction, known have make aspartic acid in the presence of phosphoric acid or Tripyrophosphoric acid catalyzer, under 100～250 ℃ with the method for solid state reaction (with reference to special public clear 48-20638 communique, U.S. Patent No. 5,142, No. 062 specification sheetss etc.).But in this method, in order to obtain polysuccinimide, must use a large amount of catalyzer, therefore just produced problem for the necessary loaded down with trivial details operation of catalyzer of in postprocessing working procedures, removing a large amount of uses, and require the problems such as device erosion resistance be used to react, in addition, also produce the problem that is difficult to regulate gained polysuccinimide molecular weight.Have again, in these manufacture method,, because polymerization makes polymer coagulation one-tenth block, therefore also produce the problem that is difficult to the industry manufacturing in the mill owing to carry out solid state reaction.
Invention is described
Problem of the present invention provides a kind of poly aspartic acid or its salt that can be used as sequestrant, scale preventive, washing composition week washing assistant, dispersion agent, wetting Agent for Printing Inks, fertilizer with additive, various coating-forming agents etc., and provides a kind of easy and make the method for this compound with high yield.
The inventor etc. have carried out finding after the deep research in view of above-mentioned problem, make the monomer of the reaction product, aspartic acid and the maleinamic acid that are selected from toxilic acid and ammonia react acquisition in the presence of solvent and acid catalyst, carry out polycondensation, can obtain the high poly aspartic acid of calcium ion sequestering power thus, and, the unavailable high molecular polysuccinimide of the solvent method of can obtaining over, can make various poly aspartic acids easily thus, so far finish the present invention with wide range of molecular weights.
Therefore, the invention provides a kind of calcium ion sequestering power at 4.3 (Ca
++The g/100g polymkeric substance) Yi Shang poly aspartic acid or its salt (hereinafter referred to as " the 1st kind of poly aspartic acid or its salt "), and the manufacture method (hereinafter referred to as " manufacture method of the 1st kind of poly aspartic acid or its salt ") that a kind of above-mentioned poly aspartic acid or its salt are provided, this method comprises makes the reaction product that is selected from toxilic acid and ammonia react acquisition, the monomer of aspartic acid and maleinamic acid, in the presence of solvent and acid catalyst, carry out polycondensation, obtain the polycondensation step of polysuccinimide, and the hydrolyzing process that makes the hydrolysis of polysuccinimide that obtains in the above-mentioned polycondensation step, and provide a kind of precursor for above-mentioned poly aspartic acid or its salt, can make the polysuccinimide of above-mentioned poly aspartic acid or its salt by hydrolysis.
And, the present invention also provides the manufacture method (hereinafter referred to as " manufacture method of the 2nd kind of poly aspartic acid or its salt ") of a kind of poly aspartic acid or its salt, this method comprises the monomer that makes the reaction product, aspartic acid and the maleinamic acid that are selected from toxilic acid and ammonia react acquisition, in the presence of mixed solvent that the solvent more than 2 kinds or 2 kinds that contains non-proton property polar solvent at least constitutes and acid catalyst, carry out polycondensation, obtain the polycondensation step of polysuccinimide, and the hydrolyzing process that makes the hydrolysis of polysuccinimide that obtains in the above-mentioned polycondensation step.
Below explain the present invention.(1) the 1st kind of poly aspartic acid or its salt and manufacture method thereof
The 1st kind of poly aspartic acid of the present invention or its salt, the calcium ion sequestering power of measuring according to the calcium ion electrode method of using calcium chloride is at 4.3 (Ca
++The g/100g polymkeric substance) more than, preferably at 4.6 (Ca
++The g/100g polymkeric substance) more than.The calcium ion sequestering power of this poly aspartic acid or its salt is little to the interdependence of molecular weight.Known calcium ion sequestering power generally is that the raising with molecular weight improves, if but molecular weight is too high, and therefore then dispersed the reduction be disadvantageous.Because the calcium ion sequestering power of the 1st kind of poly aspartic acid of the present invention or its salt is little to the interdependence of molecular weight, even lower molecular weight also can have above-mentioned higher calcium ion sequestering power.
Herein, calcium ion sequestering power among the present invention, be meant that for example the spy opens flat 5-59130 to basis and oiling is learned No. 3 records such as (1986) of the 35th volume, take by weighing sample, after in the aqueous solution that contains calcium chloride and Repone K, dissolving, stir, the measuring ion instrument that use has a calcium ion electrode is measured the calcium ion amount in the solution, the value of being obtained by measurement result.Specifically, in the 50ml beaker, take by weighing sample 10mg, and it is dissolved in calcium chloride is adjusted to 1.0 * 10
-3M, Repone K are adjusted among the aqueous solution 50ml of 0.08M, after 30 ℃ are stirred about 10 minutes down, measure the calcium ion in the solution with calcium ion electrode (the system 93-20 of オ リ カ Application society type) and measuring ion instrument (system Model 720 A of オ リ カ Application society), use the calcium ion gram number of being caught to represent calcium ion sequestering power (unit: Ca by sample polymkeric substance 100g
++The g/100g polymkeric substance).In addition, the calcium ion sequestering power also can adopt other measuring methods such as pigment method, nephelometry to measure.
As the salt of poly aspartic acid, can enumerate alkaline earth salts such as an alkali metal salts such as poly aspartic acid sodium salt, poly aspartic acid sylvite, poly aspartic acid calcium salt, poly aspartic acid magnesium salts etc.
The 1st kind of poly aspartic acid of the present invention or its salt with so high calcium ion sequestering power, can make by a kind of like this method, this method comprises the polycondensation step that makes the monomer that is selected from resultant of reaction, aspartic acid and the maleinamic acid that toxilic acid and ammonia react obtain carry out polycondensation in the presence of solvent and acid catalyst and obtain polysuccinimide, and the hydrolyzing process that makes the hydrolysis of polysuccinimide that obtains in the above-mentioned polycondensation step.
Used monomer is selected from reaction product, aspartic acid and the maleinamic acid of toxilic acid and ammonia react acquisition in the manufacture method of the 1st kind of poly aspartic acid of the present invention or its salt.
Herein, the said reaction product that toxilic acid and ammonia react are obtained is meant and adopts for example German Patent 3,626, No. 672 specification sheetss, U.S. Patent No. 4,839, the method of record in No. 461 specification sheetss, 5,286, No. 810 specification sheetss of U.S. Patent No. etc. and the product that obtains.That is, specifically, can enumerate the method for record in following " optimal mode carries out an invention " hurdle Production Example 1.And the toxilic acid that is used as above-mentioned reaction product raw material also can comprise its acid anhydrides, part ester or whole ester.And, ammonia can be used as common gas or solution uses, under the occasion of using as solution, can adopt to make it be dissolved in that water forms the method for ammonium hydroxide aqueous solution or it is dissolved in the method used in alcohols such as methyl alcohol or ethanol and other suitable organic solvent etc.
Above-mentioned reaction product specifically, mainly is the toxilic acid mono-ammonium, in addition, also can comprise products such as toxilic acid, toxilic acid di-ammonium salts, ammonia, fumaric acid, aspartic acid, l-asparagine, imino-diacetic succsinic acid, maleinamic acid.
Aspartic acid can be D type, L type or its mixture.And maleinamic acid can obtain by for example heating toxilic acid mono-ammonium or di-ammonium salts.
In these monomers, preferred aspartic acid.
And, as monomer, except that reaction product, aspartic acid or maleinamic acid that above-mentioned toxilic acid and ammonia react obtain, can also be in the scope that is no more than monomer total amount 50mol%, but use other monomer of copolymerization.As its example, can enumerate amino acid or its salt such as aspartate, L-glutamic acid, L-Ala, leucine, Methionin; Hydroxycarboxylic acids such as oxyacetic acid, lactic acid, 3-hydroxybutyric acid; With the amino of 2-hydroxyl ethanol, toxilic acid, aniline etc. and/or the compound with an above functional group of carboxyl reaction acquisition etc.
The solvent that uses in the polycondensation step as above-mentioned manufacture method of the present invention then has no particular limits if be generally used for the organic solvent of polycondensation, preferably has the solvent of boiling point more than 100 ℃, most preferably has the solvent of boiling point more than 130 ℃.Preferred solvent is to be selected from varsol, halogenated hydrocarbon solvent, ether solvent, esters solvent and non-proton property polar solvent.
Specifically, as varsol, can enumerate dimethylbenzene, (they can be respectively ortho position, a position or para-isomeride to diethylbenzene individually, also can be mixture of isomers more than 2 kinds.), toluene, penta benzene, isopropyl benzene,, 1,2,3,4-tetralin etc.As halogenated hydrocarbon solvent, can enumerate toluene(mono)chloride, (they can be made of independent ortho position, a position or para-isomeride respectively dichlorobenzene, also can be mixture of isomers more than 2 kinds.), 1,4-dichlorobutane, chlorobenzene etc.As ether solvent, can enumerate dichloroethyl ether, butyl ether, isoamyl ether, methyl-phenoxide etc.As esters solvent, can enumerate n-Amyl acetate, isoamyl acetate, acetic acid methyl isopentyl ester, acetic acid methoxyl group butyl ester, cyclohexyl acetate, Benzyl Acetate, n-butyl propionate, isoamyl propionate, isoamyl butyrate, the positive butyl ester of butyric acid etc.Can enumerate N as non-proton property polar solvent, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, 1, amide solvents such as 3-dimethyl-2-imidazolone, tetramethyl-uric acid; Sulfur-bearing such as dimethyl sulfoxide (DMSO), tetramethylene sulfone kind solvent; Phosphorous kind solvents such as hexamethyl phosphoro group acid amides etc.Wherein, have on the viewpoint of suitable boiling point preferred diethylbenzene,, isopropyl benzene, toluene(mono)chloride, 1,4-dichlorobutane, isoamyl ether, isoamyl butyrate, 1,3-dimethyl-2-imidazolone or tetramethylene sulfone, most preferably, isopropyl benzene, toluene(mono)chloride, 1,3-dimethyl-2-imidazolone or tetramethylene sulfone.Above-mentioned solvent can use separately, also can use mixing more than 2 kinds in them.
In the manufacture method of the present invention, for monomer 100 weight parts, spendable solvent ratios is generally 100～5000 weight parts, preferred 200～2000 weight parts.
As the acid catalyst that uses in the polycondensation step, can enumerate inorganic acid catalysts such as sulfuric acid, sulphuric anhydride, phosphoric acid, Tripyrophosphoric acid, metaphosphoric acid, condensed phosphoric acid; Organic acid catalysts such as tosic acid, Tricholroacetic Acid, trifluoracetic acid, trifluoromethanesulfonic acid.Wherein, preferred weak acid phosphoric acid.The consumption of acid catalyst for monomer 1mol, is generally 0.0002～2.0mol, preferred 0.01～1.0mol, more preferably 0.01～0.5mol, most preferably 0.03～0.3mol.Like this, in this manufacture method, can carry out polycondensation fully with the acid catalyst that lacks than the method in past.Therefore, can prevent that the polymer coagulation that is produced by polymerization from becoming piece, very favourable to industry thus.
The temperature of reaction of polycondensation in the manufacture method of the present invention is generally 100～280 ℃, and preferred 130～250 ℃, more preferably 150～200 ℃.Condensation temperature is lower than 100 ℃, and then reaction is not easy to carry out, and surpasses 280 ℃, then generates degradation production.Pressure during reaction has no particular limits, normal pressure, decompression or pressurization can, be generally 10Pa～1MPa.Reaction times is 1 minute～100 hours, preferred 10 minutes～50 hours, and most preferably 15 minutes～20 hours.And, react substantial terminal point for the water of by product in the reaction do not take place azeotropic that.
After polycondensation finishes, carry out aftertreatment in order to reclaim the polysuccinimide that obtains by polycondensation.Aftertreatment can suit according to the purposes of polysuccinimide to select.Carry out aftertreatment according to more such ordinary methods, can obtain polysuccinimide, for example, remove the method for desolvating by polycondensation product is filtered or centrifugation etc., or remove desolvate after low boiling point solvent such as water or methyl alcohol, the acetone method of washing etc. again.
The polysuccinimide of Huo Deing can be made above-mentioned poly aspartic acid or its salt for the precursor of the 1st kind of poly aspartic acid of the present invention or its salt by hydrolysis herein.And in addition, this polysuccinimide itself also can be used as purposes such as the lubricant of urethane, various coating-forming agents and uses.
The 1st kind of poly aspartic acid of the present invention or its salt are then to be hydrolyzed by the polysuccinimide that will obtain in the above-mentioned condensation operation to obtain.The hydrolyzing process of polysuccinimide, can carry out according to conventional methods, can enumerate J.Am.Chem.Soc.80 as its typical example, 3361 (1958), J.Org.Chem.26,1084 (1961), 5,221, No. 733 specification sheetss of U.S. Patent No., U.S. Patent No. 5,288, No. 783 specification sheetss, spies open the method for middle records such as clear 60-203636 specification sheets.Specifically, this method is the method that is hydrolyzed with metal hydroxidess such as sodium hydroxide.Can make poly aspartic acid or its salt thus with good calcium ion sequestering power.
The 1st kind of poly aspartic acid of the present invention or its salt of Huo Deing has no particular limits for molecular weight like this, and the weight-average molecular weight that is converted into polyoxyethylene glycol is preferably 500～200, and 000, more specifically be about 4000～100,000.
As mentioned above, the 1st kind of poly aspartic acid of the present invention or its salt, the calcium ion sequestering power is little to the interdependence of molecular weight, even lower molecular weight also can have high calcium ion sequestering power, from the viewpoint of dispersiveness, be the weight-average molecular weight preferred 500～30,000 of base with the polyoxyethylene glycol, more preferably 1000～20,000 poly aspartic acid or its salt are more useful.
The 1st kind of poly aspartic acid of the present invention or its salt can be used for various uses, specifically, are applicable to sequestrant, scale preventive, detergent use washing assistant, dispersion agent, wetting Agent for Printing Inks, fertilizer additive, various coating-forming agents etc.
The manufacture method of (2) the 2nd kinds of poly aspartic acids or its salt
The present invention also provides the manufacture method of a kind of the 2nd kind of poly aspartic acid or its salt, this method comprises, make the monomer that is selected from reaction product, aspartic acid and maleinamic acid that toxilic acid and ammonia react obtain in the presence of mixed solvent that the solvent more than 2 kinds that contains a kind of non-proton property polar solvent at least constitutes and acid catalyst, carry out polycondensation and obtain the polycondensation step of polysuccinimide and the hydrolyzing process that makes the hydrolysis of polysuccinimide that obtains in the above-mentioned polycondensation step.
Past is difficult for making easily the high-molecular weight polysuccinimide, but the method according to this invention, can obtain the high molecular polysuccinimide, for example the weight-average molecular weight of calculating based on polystyrene is 25, polysuccinimide more than about 000, by with its hydrolysis, can obtain to have high molecular weight polyasparagic acid or its salt of good calcium ion sequestering power etc.
The monomer of Shi Yonging is identical with the monomer that is used to make the 1st kind of poly aspartic acid of the present invention or its salt herein, in the manufacture method of the 2nd kind of poly aspartic acid or its salt, use the mixed solvent of the formation of solvent more than 2 kinds that contains a kind of non-proton property polar solvent at least as solvent.More preferably, use is selected from the solvent of varsol, halogenated hydrocarbon solvent, ether solvent and esters solvent and the mixed solvent of non-proton property polar solvent.And, the boiling point of the solvent that uses in the mixed solvent, preferably any is all more than 100 ℃, more preferably more than 130 ℃.The non-proton property polar solvent ratio overall to this mixed solvent is generally 1～99 weight %, preferred 5～99 weight %, more preferably 10～95 weight %, and, as the object lesson of each solvent, can enumerate those solvents of enumerating in the manufacture method of the 1st kind of poly aspartic acid or its salt.
In the manufacture method of the 2nd kind of poly aspartic acid of the present invention or its salt,, in polycondensation step, can make the polysuccinimide of higher molecular weight by using this mixed solvent.And, owing to do not need to use a large amount of acid catalysts, can prevent to become piece, so this method is the manufacture method useful to industry by the polymer coagulation that polymerization causes, and, identical in the manufacture method of the consumption of acid catalyst and above-mentioned the 1st kind of poly aspartic acid or its salt, for monomer 1mol, be generally 0.0002～2.0mol, preferred 0.01～1.0mol, more preferably 0.01～0.5mol, most preferably 0.03～0.3mol.
In the manufacture method of the 2nd kind of poly aspartic acid of the present invention or its salt, about conditions such as polycondensation temperature, pressure, reaction times, postprocessing working procedures, identical with in the manufacture method of above-mentioned the 1st kind of poly aspartic acid or its salt.
In the polycondensation step of the 2nd kind of poly aspartic acid or its salt, polycondensation can be carried out in the presence of primary amine or secondary amine and above-mentioned solvent and acid catalyst.By interpolation amine, the molecular weight of may command polysuccinimide, acquisition conforms with the polysuccinimide of the hope molecular weight of various uses, and, can make poly aspartic acid or its salt of wishing molecular weight thus.
Have no particular limits as the primary amine or the secondary amine that use herein, preferably the acid dissociation constant in the aqueous solution (pKa) is below 7, more preferably at the amine below 6.And, be used for the value that herein pKa refers to the conjugate acid of amine, this value can be from the dissociation constant or " the Critical Stability Constants Vol.1; 2; 3; 5 of the organic compound in aqueous solution of " chemical brief guide-basis compile " (Japanization association volume) " find in (A.E.Martell, R.M.Smith, Plenum Press).Specifically have morpholine, hexylamine, neighbour-,-, to aminopyridine, butylamine, aniline, Triethylenetetramine (TETA), naphthalidine, 2-naphthylamines etc., be the Ortho-Aminophenol enumerated, 4-aminobutyric acid of two functional groups etc.Wherein, the amine as pKa≤6 has aniline, Triethylenetetramine (TETA), naphthalidine, 2-naphthylamines etc., the Ortho-Aminophenol enumerated of two functional groups, 4-aminobutyric acid etc.These amine may be used alone, can also be two or more kinds in combination.
The method of adding primary amine or secondary amine in polycondensation step has no particular limits, and can all add when polycondensation begins, and also can add along with the time in polycondensation.And its addition can change according to the weight of employed amine and the change of molecular weight of the polysuccinimide that will obtain, if seek out the polysuccinimide of lower molecular weight, preferably uses the amine of more amount.Specifically,, be generally below the 100mol%, below the preferred 80mol%, more preferably below the 60mol% for monomer.And, also to consider of the effect of these amine as the polymer ends encapsulant.In other words, consider by carboxyl reaction and hinder reaction with the polymer of monomers reactive terminal with polymer ends, thus the control molecular weight.
The polysuccinimide that obtains in this polycondensation step is the precursor of the 2nd kind of poly aspartic acid of the present invention or its salt, can make above-mentioned poly aspartic acid or its salt by hydrolysis.And in addition, polysuccinimide itself also can be used as purposes such as the lubricant, Biodegradable polymer raw material of urethane and uses.
The 2nd kind of poly aspartic acid of the present invention or its salt then obtain the polysuccinimide that obtains in the above-mentioned polycondensation step by using same procedure with the occasion of above-mentioned the 1st kind of poly aspartic acid or its salt to be hydrolyzed.
The 2nd kind of poly aspartic acid of the present invention or its salt, in various uses, specifically, at aspects such as flocculation agent, Biodegradable polymer raw materials of great use.
The optimal morphology that carries out an invention
Below, further describe the present invention by embodiment, but the present invention is not subjected to the restriction of these embodiment.
In addition, the transformation efficiency (%) that is transformed into polysuccinimide by aspartic acid is to make 10g reaction mixture or product at 200g N, stirring and dissolving is 4 hours in the dinethylformamide (DMF), filtering is not dissolved in the aspartic acid (the insoluble composition of DMF) of this solvent and obtains its weight, is calculated by following formula.
The molecular weight of the polysuccinimide of manufacturing is that what to adopt that GPC chromatographic instrument (differential refractometer) obtains is the value that benchmark calculates with the polystyrene, Shi Yong East ソ-Co., Ltd.'s system " TSKgel " " GMHHR-M " pillar and " TSKgel " " G2000HHR " pillar in this GPC chromatographic instrument are as the dimethyl formamide solution of eluant use 10mM lithiumbromide; The molecular weight of poly aspartic acid or its salt is that what to adopt that GPC chromatographic instrument (differential refractometer) obtains is the value that benchmark calculates with the polyoxyethylene glycol, be higher than under 30000 the occasion Shi Yong East ソ-Co., Ltd.'s system " TSKgel " " G6000PWXL " pillar Yi in the weight-average molecular weight of polysuccinimide Ji East ソ-Co., Ltd.'s system " TSKgel " " G3000PWXL " pillar, be lower than in the weight-average molecular weight of polysuccinimide under 30000 the occasion, use Liang Gen East ソ-Co., Ltd.'s system " TSKgel " " G3000PWXL " pillar, use the 0.4M sodium nitrate aqueous solution as eluant.
In addition, as the calcium ion sequestering power is to open flat 5-59130 and oiling according to spy for example to learn the record of the 35th volume No. 3 (1986) in waiting, and the use calcium ion electrode also uses the measuring ion instrument to measure the capture ability of every 100g polymkeric substance to the calcium ion that comes from calcium chloride.Specifically, in the 50ml beaker, take by weighing sample 10mg, and it is dissolved in calcium chloride is adjusted to 1.0 * 10
-3M, Repone K are adjusted among the aqueous solution 50ml of 0.08M, after 30 ℃ are stirred about 10 minutes down, with calcium ion electrode (オ リ カ Application society system 93-20 type) and use measuring ion instrument (system Model 720 A of オ リ カ Application society) to measure the calcium ion in the solution, use the gram number of the calcium ion of being caught to represent the sequestering power of calcium ion by sample 100g.
Production Example 1
(manufacturing of the reaction product that obtains from toxilic acid and ammonia)
In the 300mL four-hole boiling flask that reflux exchanger, thermometer, agitator and dropping funnel are housed, add maleic anhydride 98g and water 50g, heating is 30 minutes in 75 ℃ of oil baths.Then shift out outside the oil bath,, then, in 85 ℃ of oil baths, stirred 3 hours while use ice-cooled flask to splash into 25% ammoniacal liquor 68.1g.After the reaction, under 80～85 ℃ of temperature, decompression, (with the reaction mixture dephlegmate, obtain white solid 130g under 200～10hPa).
Embodiment 1
In the 200mL four-hole boiling flask that condenser, thermometer, agitator and water separator are housed, add reaction product 25g, as 85% phosphoric acid 2.5g of acid catalyst, as the 80g of solvent as toxilic acid that obtains in the Production Example 1 of raw material and ammonia.Then under normal pressure, under the solvent refluxing (162 ℃) kept 4.5 hours, carry out polycondensation.The water that generates in the reaction is outside solvent distills out system.
After reaction finishes, filter, divide washed product 4 times, again with methyl alcohol 100g washing with pure water 100g.Then, under reduced pressure 80 ℃ were descended dry 24 hours, obtained the polysuccinimide powder 13.6g of brown.
The transformation efficiency of this polysuccinimide is 99%, and what measured by GPC is the molecular weight that benchmark calculates with the polystyrene, and weight-average molecular weight is 4500, and number-average molecular weight is 3500.
Then, in the 100cc beaker that stirrer is housed, add the polysuccinimide 3g and the water 10g of above-mentioned acquisition, adding sodium hydroxide 1.4g is dissolved in the aqueous solution among the water 20g under ice-cooled, stirs thereafter 1 hour, carries out the hydrolysis of polysuccinimide thus.Reaction is poured into reaction solution among the methyl alcohol 300ml after finishing, and separates out crystallization thus, obtains the poly (sodium aspartate) 3.3g of yellow-white.
What measured by GPC is the molecular weight that benchmark calculates with the polyoxyethylene glycol, and weight-average molecular weight is 4200, and number-average molecular weight is 3600, and the calcium ion sequestering power is 5.0 (Ca
++The g/100g polymkeric substance).
Embodiment 2
In the 200mL four-hole boiling flask that reflux exchanger, thermometer, agitator, nitrogen ingress pipe and water separator are housed, add reaction product 25g, as 85% phosphoric acid 2.5g of acid catalyst, as the tetramethylene sulfone 80g of solvent as toxilic acid that obtains in the Production Example 1 of raw material and ammonia.Then under normal pressure, temperature of reaction kept 4.5 hours down for 180 ℃, carried out polycondensation.The water that generates in the reaction is outside nitrogen gas stream distills out system.
Reaction makes product separate out crystallization with pure water 300g after finishing, and after the filtration, divides 4 washings with pure water 100g, again with methyl alcohol 100g washing.Then, under reduced pressure 80 ℃ were descended dry 24 hours, obtained the polysuccinimide powder 10.1g of yellow-white.The transformation efficiency of this polysuccinimide is more than 99%, and what measured by GPC is the molecular weight that benchmark calculates with the polystyrene, and weight-average molecular weight is 6000, and number-average molecular weight is 4800.
And, carry out the hydrolysis of polysuccinimide in the same manner with embodiment 1, obtain the poly (sodium aspartate) 3.1g of yellow-white.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 5800, and number-average molecular weight is 4600, and the calcium ion sequestering power is 5.1 (Ca
++The g/100g polymkeric substance).
Embodiment 3
Use is reacted with embodiment 1 in the same manner as the maleinamic acid 25g of raw material, as 85% phosphoric acid 2.5g of acid catalyst, as the 56g and the tetramethylene sulfone 24g of solvent, obtains polysuccinimide powder 12.9g.
The transformation efficiency of this polysuccinimide is 99%, and by the molecular weight that is scaled polystyrene that GPC measures, weight-average molecular weight is 7100, and number-average molecular weight is 4800.
Then, carry out the hydrolysis of polysuccinimide in the same manner, obtain the poly (sodium aspartate) 3.4g of yellow-white with embodiment 1.
What measured by GPC is the molecular weight that benchmark calculates with the polyoxyethylene glycol, and weight-average molecular weight is 6900, and number-average molecular weight is 4600, and the calcium ion sequestering power is 5.4 (Ca
++The g/100g polymkeric substance).
Embodiment 4
In the solvent among the embodiment 3, except 56g being changed into the positive butyl ester 56g of butyric acid,, obtain polysuccinimide powder 13.7g by reacting in the same manner with embodiment 3.The transformation efficiency of this polysuccinimide is more than 99%, and what measured by GPC is the molecular weight that benchmark calculates with the polystyrene, and weight-average molecular weight is 7200, and number-average molecular weight is 4800.
And, by carrying out the hydrolysis of polysuccinimide, obtain the poly (sodium aspartate) 3.2g of yellow-white with embodiment 5 identical operations.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 6800, and number-average molecular weight is 4600, and the calcium ion sequestering power is 4.8 (Ca
++The g/100g polymkeric substance).
Embodiment 5
Use is reacted in temperature of reaction 164 ℃ times and embodiment 1 in the same manner as the aspartic acid 25g of raw material, as 85% phosphoric acid 2.5g of acid catalyst, as the parachlorotoluene 80g of solvent, obtains the powder 17.4g of the polysuccinimide of yellow-white.The transformation efficiency of this polysuccinimide is more than 99%, and by the molecular weight that is scaled polystyrene that GPC measures, weight-average molecular weight is 19000, and number-average molecular weight is 11000.
And, by carrying out the hydrolysis of polysuccinimide, obtain the poly (sodium aspartate) 3.8g of yellow-white with embodiment 1 identical operations.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 19000, and number-average molecular weight is 12000, and the calcium ion sequestering power is 4.63 (Ca
++The g/100g polymkeric substance).
Embodiment 6
Use is reacted in temperature of reaction 180 ℃ times and embodiment 1 in the same manner as the aspartic acid 25g of raw material, as 85% phosphoric acid 2.5g of acid catalyst, as the tetramethylene sulfone 80g of solvent.Reaction makes product separate out crystallization with pure water 300g after finishing, and after the filtration, divides 4 washings with pure water 100g, again with methyl alcohol 100g washing.Then, obtain the polysuccinimide powder 17.1g of yellow-white decompression, 80 ℃ dry 24 hours down.The transformation efficiency of this polysuccinimide is more than 99%, and what measured by GPC is the molecular weight that benchmark calculates with the polystyrene, and weight-average molecular weight is 14000, and number-average molecular weight is 9000.
And, by carrying out the hydrolysis of above-mentioned polysuccinimide, obtain the poly (sodium aspartate) 3.6g of yellow-white with embodiment 1 identical operations.The molecular weight that is scaled polyoxyethylene glycol that this material is measured by GPC, weight-average molecular weight is 15000, and number-average molecular weight is 9800, and the calcium ion sequestering power is 5.0 (Ca
++The g/100g polymkeric substance).
Embodiment 7
Use is as the aspartic acid 25g of raw material, as 85% phosphoric acid 2.5g of acid catalyst, as the 56g and the tetramethylene sulfone 24g of solvent, react in the same manner with embodiment 1, obtaining the polysuccinimide powder 17.9g of yellow-white, is 98% to the yield of theoretical amount.It is the molecular weight that benchmark calculates with the polystyrene that the gained polysuccinimide is measured what obtain by GPC, and weight-average molecular weight is 66000, and number-average molecular weight is 25000.
And, by carrying out the hydrolysis of above-mentioned polysuccinimide, obtain the poly (sodium aspartate) 4.0g of yellow-white with embodiment 1 identical operations.The molecular weight that is scaled polyoxyethylene glycol that this material is measured by GPC, weight-average molecular weight is 72000, and number-average molecular weight is 28000, and the calcium ion sequestering power is 5.0 (Ca
++The g/100g polymkeric substance).
Embodiment 8
Use is as the aspartic acid 25g of raw material, as 85% phosphoric acid 2.5g of acid catalyst, as the parachlorotoluene 40g and the tetramethylene sulfone 40g of solvent, react in the same manner with embodiment 1, obtaining the polysuccinimide powder 16.9g of yellow-white, is 93% to the yield of theoretical amount.It is the molecular weight that benchmark calculates with the polystyrene that the gained polysuccinimide is measured what obtain by GPC, and weight-average molecular weight is 59000, and number-average molecular weight is 27000.
And, by carrying out the hydrolysis of above-mentioned polysuccinimide, obtain the poly (sodium aspartate) 4.0g of yellow-white with embodiment 1 identical operations.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 64000, and number-average molecular weight is 25000, and the calcium ion sequestering power is 5.1 (Ca
++The g/100g polymkeric substance).
Embodiment 9
As solvent, 24g changes 1 into tetramethylene sulfone, and in addition 3-dimethyl-2-imidazolone 24g, reacts in the same manner with embodiment 7, obtains the polysuccinimide powder 17.3g of yellow-white, is 95% to the yield of theoretical amount.It is the molecular weight that benchmark calculates with the polystyrene that the gained polysuccinimide is measured what obtain by GPC, and weight-average molecular weight is 42000, and number-average molecular weight is 23000.
And, by carrying out the hydrolysis of above-mentioned polysuccinimide, obtain the poly (sodium aspartate) 3.7g of yellow-white with embodiment 1 identical operations.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 46000, and number-average molecular weight is 18000, and the calcium ion sequestering power is 5.0 (Ca
++The g/100g polymkeric substance).
Embodiment 10
As acid catalyst, change 85% phosphoric acid 2.5g into tosic acid 3.6g, in addition, react in the same manner with embodiment 8, obtain the powder 17.3g of the polysuccinimide of yellow-white, be 95% to the yield of theoretical amount.It is the molecular weight that benchmark calculates with the polystyrene that the gained polysuccinimide is measured what obtain by GPC, and weight-average molecular weight is 41000, and number-average molecular weight is 23000.
And, by carrying out the hydrolysis of above-mentioned polysuccinimide, obtain the poly (sodium aspartate) 3.7g of yellow-white with embodiment 1 identical operations.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 42000, and number-average molecular weight is 17000, and the calcium ion sequestering power is 4.9 (Ca
++The g/100g polymkeric substance).
Embodiment 11
As solvent, change 56g into isoamyl ether 56g, in addition, react in the same manner with embodiment 7, obtain the polysuccinimide powder 17.8g of yellow-white, be 98% to the yield of theoretical amount.It is the molecular weight that benchmark calculates with the polystyrene that the gained polysuccinimide is measured what obtain by GPC, and weight-average molecular weight is 35000, and number-average molecular weight is 20000.
And, by carrying out the hydrolysis of above-mentioned polysuccinimide, obtain the poly (sodium aspartate) 3.6g of yellow-white with embodiment 1 identical operations.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 36000, and number-average molecular weight is 15000, and the calcium ion sequestering power is 4.9 (Ca
++The g/100g polymkeric substance).
Embodiment 12
Aniline 0.18g with addings such as other raw materials, in addition, is reacted with embodiment 7 in the same manner.Its result, the polysuccinimide powder 17.8g of acquisition yellow-white.Yield to theoretical amount is 98%.The weight-average molecular weight of gained polysuccinimide is 61000, and number-average molecular weight is 23000.By this polysuccinimide being hydrolyzed, obtain poly (sodium aspartate) with embodiment 1 identical operations.
Embodiment 13
Aniline 0.87g with addings such as other raw materials, in addition, is reacted with embodiment 7 in the same manner.Its result, the polysuccinimide powder 18.0g of acquisition yellow-white.Yield to theoretical amount is 99%.The weight-average molecular weight of gained polysuccinimide is 29000, and number-average molecular weight is 10000.And, this polysuccinimide is measured
1H-NMR, its result, the absorption peak that affirmation is caused by aniline, thus confirm that aniline enters in the polysuccinimide molecule.By this polysuccinimide being hydrolyzed, obtain poly (sodium aspartate) with embodiment 1 identical operations.
Embodiment 14
Morpholine 0.17g with addings such as other raw materials, in addition, is reacted with embodiment 7 in the same manner.Its result, the polysuccinimide powder 17.7g of acquisition yellow-white.Yield to theoretical amount is 97%.The weight-average molecular weight of gained polysuccinimide is 63000, and number-average molecular weight is 24000.By this polysuccinimide being hydrolyzed, obtain poly (sodium aspartate) with embodiment 1 identical operations.
Embodiment 15
Morpholine 0.82g with addings such as other raw materials, in addition, is reacted with embodiment 7 in the same manner.Its result, the polysuccinimide powder 17.6g of acquisition yellow-white.Yield to theoretical amount is 97%.The weight-average molecular weight of gained polysuccinimide is 32000, and number-average molecular weight is 13000.By this polysuccinimide being hydrolyzed, obtain poly (sodium aspartate) with embodiment 1 identical operations.
Embodiment 16
Hexahydroaniline 0.92g with addings such as other raw materials, in addition, is reacted with embodiment 7 in the same manner.Its result, the polysuccinimide powder 17.3g of acquisition yellow-white.Yield to theoretical amount is 95%.The weight-average molecular weight of gained polysuccinimide is 40000, and number-average molecular weight is 17000.By this polysuccinimide being hydrolyzed, obtain poly (sodium aspartate) with embodiment 1 identical operations.
Comparative example 1
In the 300mL four-hole boiling flask that reflux exchanger, thermometer, agitator and dropping funnel are housed, add maleic anhydride 98g and water 50g, heating is 30 minutes in 75 ℃ of oil baths.Then shift out outside the oil bath,,, then, in 85 ℃ of oil baths, stirred 3 hours Yi Bian splash into 25% ammoniacal liquor 68.1g Yi Bian use ice-cooled flask.Reaction mixture is transferred in the 500ml eggplant type flask, with rotatory evaporator (200～10hPa) dephlegmates under 80～85 ℃ of temperature, decompression.Then, under the normal pressure nitrogen gas stream, under 120 ℃ of temperature, carry out polycondensation 1 hour, (under 20～10hPa), carried out polycondensation 4 hours under 135 ℃ of the temperature, obtain white solid 106g in decompression again.
The transformation efficiency of this polysuccinimide is 87%, and what measured by GPC is the molecular weight that benchmark calculates with the polystyrene, and weight-average molecular weight is 2900, and number-average molecular weight is 2400.
And, in the same manner the gained polysuccinimide is hydrolyzed with embodiment 1, obtain the poly (sodium aspartate) 1.3g of yellow-white.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 2500, and number-average molecular weight is 2400, and the calcium ion sequestering power is 2.4 (Ca
++The g/100g polymkeric substance).
Comparative example 2
Add the toxilic acid of acquisition in the Production Example 1 and the reaction mixture 10g of ammonia in the 200mL eggplant type flask, under nitrogen gas stream, heating is 4 hours in 220 ℃ of oil baths, carries out polycondensation, obtains the polysuccinimide powder 6.9g of brown with rotatory evaporator.The transformation efficiency of this polysuccinimide is more than 99%, and what measured by GPC is the molecular weight that benchmark calculates with the polystyrene, and weight-average molecular weight is 6500, and number-average molecular weight is 4400.
And, in the same manner this polysuccinimide is hydrolyzed with embodiment 1, obtain the poly (sodium aspartate) 3.5g of yellow-white.The molecular weight that is scaled polyoxyethylene glycol that this material is measured by GPC, weight-average molecular weight is 6500, and number-average molecular weight is 3500, and the calcium ion sequestering power is 3.4 (Ca
++The g/100g polymkeric substance).
Comparative example 3
In the 500mL four-hole boiling flask that reflux exchanger, thermometer, agitator and water separator are housed, add aspartic acid 200g.Then, under nitrogen gas stream,, carried out polycondensation 6 hours on one side on one side with the oil bath heating that maintains 260 ℃.Reaction obtains umbrinaceous polysuccinimide powder 140.0g after finishing.Yield to theoretical amount is 97%.It is the molecular weight that benchmark calculates with the polystyrene that the gained polysuccinimide is measured what obtain by GPC, and weight-average molecular weight is 15000, and number-average molecular weight is 8800.And, in the same manner this polysuccinimide is hydrolyzed with embodiment 1, obtain the poly (sodium aspartate) 3.6g of yellow-white.This material is the molecular weight that benchmark calculates with the polyoxyethylene glycol by GPC mensuration, and weight-average molecular weight is 16000, and number-average molecular weight is 8900, and the calcium ion sequestering power is 4.2 (Ca
++The g/100g polymkeric substance).
Comparative example 4
Use as the 80g of solvent, is not used acid catalyst as the aspartic acid 25g of other raw materials, reacts in the same manner with embodiment 1, does not generate water in the reaction, and transformation efficiency is almost 0%.
Comparative example 5
In the eggplant type flask of 1L, add aspartic acid 50g and 85% phosphoric acid 3.0g.Then, above-mentioned flask is installed on the rotatory evaporator, heated 4 hours, make it carry out polycondensation with the oil bath that maintains 180 ℃.With its cooling, the glass agglomerate that generates is dissolved in N after reaction finishes, in the dinethylformamide, adds water and form precipitation, it is filtered and the collecting precipitation thing.The throw out that obtains is washed with water to neutral to remove phosphoric acid.To clean thing and descend dry 24 hours, obtain the polysuccinimide powder 17.1g of yellow-white at 85 ℃.Yield to theoretical amount is 47%.The weight-average molecular weight of gained polysuccinimide is 22000, and number-average molecular weight is 9000.
Utilize possibility on the industry
The 1st kind of poly-aspartate of the present invention or its salt have good calcium ion sequestering power, do Be chelating agent, scale powder, detergent use builder, dispersant, NMF, fertilizer interpolation Agent, various coating agents etc. are extremely useful. System according to above-mentioned poly-aspartate of the present invention or its salt Making method can be made this poly-aspartate or its salt easily, and the receipts of ratio past method Rate is much higher.
In addition, according to the manufacture method of the 2nd kind of poly-aspartate of the present invention or its salt, can make The polysuccinimide of HMW can obtain to have the height of good calcium ion sequestering power thus The molecular weight polyisoprene aspartic acid more can be controlled molecular weight according to purposes in wide region.
Claims (18)
1. a poly aspartic acid or its salt, the calcium ion sequestering power of measuring according to the calcium ion electrode method of using calcium chloride is at 4.3 (Ca
++The g/100g polymkeric substance) more than.
2. the poly aspartic acid described in the claim 1 or its salt, the calcium ion sequestering power of measuring according to the calcium ion electrode method of using calcium chloride is at 4.6 (Ca
++The g/100g polymkeric substance) more than.
3. the manufacture method of the poly aspartic acid described in the claim 1 or its salt, this method comprises: the monomer that makes the reaction product, aspartic acid and the maleinamic acid that are selected from toxilic acid and ammonia react acquisition, in the presence of solvent and acid catalyst, carry out polycondensation, obtain the polycondensation step of polysuccinimide, and the hydrolyzing process that makes the hydrolysis of polysuccinimide that obtains in the above-mentioned polycondensation step.
4. the manufacture method described in the claim 3, wherein, above-mentioned monomer is an aspartic acid.
5. the manufacture method described in the claim 3, wherein, above-mentioned solvent is selected from varsol, halogenated hydrocarbon solvent, ether solvent, esters solvent and non-proton property polar solvent.
6. the manufacture method described in the claim 3, wherein, the boiling point of above-mentioned solvent is more than 100 ℃.
7. the manufacture method described in the claim 3, wherein, the boiling point of above-mentioned solvent is more than 130 ℃.
8. the manufacture method described in the claim 3, wherein, the consumption of above-mentioned acid catalyst for monomer 1mol, is 0.0002～2mol.
9. polysuccinimide, it is the precursor of the poly aspartic acid described in the claim 1 or its salt, can make above-mentioned poly aspartic acid or its salt by hydrolysis.
10. the polysuccinimide described in the claim 9 is the monomer that makes in resultant of reaction, aspartic acid and the maleinamic acid that is selected from toxilic acid and ammonia react acquisition, carries out polycondensation and obtain in the presence of solvent and acid catalyst.
11. the manufacture method of a poly aspartic acid or its salt, this method comprises: the monomer that makes the reaction product, aspartic acid and the maleinamic acid that are selected from toxilic acid and ammonia react acquisition, in the presence of mixed solvent that the solvent more than 2 kinds that contains at least a non-proton property polar solvent constitutes and acid catalyst, carry out polycondensation, obtain the polycondensation step of polysuccinimide, and the hydrolyzing process that makes the hydrolysis of polysuccinimide that obtains in the above-mentioned polycondensation step.
12. the manufacture method described in the claim 11, wherein, above-mentioned monomer is an aspartic acid.
13. the manufacture method described in the claim 11, wherein, above-mentioned more than 2 kinds any boiling point of solvent all more than 100 ℃.
14. the manufacture method described in the claim 11, wherein, above-mentioned more than 2 kinds any boiling point of solvent all more than 130 ℃.
15. the manufacture method described in the claim 11, wherein, above-mentioned mixed solvent is to be selected from the solvent of varsol, halogenated hydrocarbon solvent, ether solvent, esters solvent and the mixed solvent of non-proton property polar solvent.
16. the manufacture method described in the claim 11, wherein, the consumption of above-mentioned acid catalyst for monomer 1mol, is 0.0002～2mol.
17. the manufacture method described in the claim 11 wherein, in the above-mentioned polycondensation step, makes monomer carry out polycondensation in the presence of solvent, acid catalyst and primary amine or secondary amine.
18. the manufacture method of the poly aspartic acid described in the claim 17 or its salt, wherein, above-mentioned primary amine or the secondary amine acid dissociation constant (pKa) in the aqueous solution is below 7.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP318638/94 | 1994-12-21 | ||
| JP31863894A JPH08176297A (en) | 1994-12-21 | 1994-12-21 | Preparation of polysuccinimide |
| JP5155895A JPH08245785A (en) | 1995-03-10 | 1995-03-10 | Production of polysuccinimide |
| JP51558/95 | 1995-03-10 | ||
| JP98492/95 | 1995-04-24 | ||
| JP98493/95 | 1995-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1146210A true CN1146210A (en) | 1997-03-26 |
Family
ID=26392107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95192645 Pending CN1146210A (en) | 1994-12-21 | 1995-12-21 | Polyaspartic acid or salt thereof and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1146210A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504253A (en) * | 2011-10-25 | 2012-06-20 | 石家庄开发区德赛化工有限公司 | Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement |
| US8729218B2 (en) | 2006-09-25 | 2014-05-20 | Aekyung Petrochemical Co., Ltd. | Manufacturing method of polyaspartic acid using maleic anhydride |
| CN104327267A (en) * | 2014-11-04 | 2015-02-04 | 中国林业科学研究院林产化学工业研究所 | Preparation method of polyaspartic acid in liquid medium |
| CN105555836A (en) * | 2013-09-16 | 2016-05-04 | 巴斯夫欧洲公司 | Methods for producing polyaspartic acids |
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| CN111286026A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院大连化学物理研究所 | Method for synthesizing polyaspartic acid through catalytic system |
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-
1995
- 1995-12-21 CN CN 95192645 patent/CN1146210A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8729218B2 (en) | 2006-09-25 | 2014-05-20 | Aekyung Petrochemical Co., Ltd. | Manufacturing method of polyaspartic acid using maleic anhydride |
| CN102504253A (en) * | 2011-10-25 | 2012-06-20 | 石家庄开发区德赛化工有限公司 | Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement |
| CN102504253B (en) * | 2011-10-25 | 2013-05-15 | 石家庄开发区德赛化工有限公司 | Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement |
| CN105555836A (en) * | 2013-09-16 | 2016-05-04 | 巴斯夫欧洲公司 | Methods for producing polyaspartic acids |
| CN105555836B (en) * | 2013-09-16 | 2018-10-02 | 巴斯夫欧洲公司 | The method for producing poly-aspartate |
| CN104327267A (en) * | 2014-11-04 | 2015-02-04 | 中国林业科学研究院林产化学工业研究所 | Preparation method of polyaspartic acid in liquid medium |
| CN111171316A (en) * | 2018-11-13 | 2020-05-19 | 中国科学院大连化学物理研究所 | Method for synthesizing polysuccinimide by adopting catalytic system |
| CN111286026A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院大连化学物理研究所 | Method for synthesizing polyaspartic acid through catalytic system |
| CN109852316A (en) * | 2018-12-28 | 2019-06-07 | 怀远县赛尔商贸有限公司 | A kind of high-intensitive, water-resistant type cloud stone glue |
| CN109852316B (en) * | 2018-12-28 | 2021-10-29 | 蚌埠赛尔时代工贸有限公司 | High-strength water-resistant marble adhesive |
| CN113896601A (en) * | 2021-10-14 | 2022-01-07 | 河北协同化学有限公司 | Polyaspartic acid chelated calcium magnesium fertilizer for preventing and treating physiological diseases of potatoes in storage period and preparation method thereof |
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