WO2001048056A1 - Procede de production d'acide (sel) polyaspartique reticule - Google Patents

Procede de production d'acide (sel) polyaspartique reticule Download PDF

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Publication number
WO2001048056A1
WO2001048056A1 PCT/JP2000/009292 JP0009292W WO0148056A1 WO 2001048056 A1 WO2001048056 A1 WO 2001048056A1 JP 0009292 W JP0009292 W JP 0009292W WO 0148056 A1 WO0148056 A1 WO 0148056A1
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Prior art keywords
salt
polyaspartic acid
acid
crosslinked
weight
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PCT/JP2000/009292
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English (en)
Japanese (ja)
Inventor
Makoto Sukegawa
Yoshihiro Irizato
Chojiro Higuchi
Takeshi Ishitoku
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Mitsui Chemicals, Incorporated
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Priority claimed from JP37431299A external-priority patent/JP3933359B2/ja
Priority claimed from JP37431499A external-priority patent/JP2001181392A/ja
Application filed by Mitsui Chemicals, Incorporated filed Critical Mitsui Chemicals, Incorporated
Publication of WO2001048056A1 publication Critical patent/WO2001048056A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1092—Polysuccinimides

Definitions

  • the present invention relates to a method for producing a crosslinked polyaspartic acid (salt) useful as a water-absorbent resin having biodegradability.
  • the water-absorbent resin is a resin that can absorb tens to thousands of times its own weight of dry weight.
  • Disposable hygiene products are designed to efficiently absorb bodily fluids such as urine, blood, menstrual blood, sweat, etc., and include disposable paper, sanitary napkins, incontinence pads, breast milk pads, medical underpads, It is used for surgical underpads and pet seats.
  • These sanitary articles are mainly composed of a top sheet made of a nonwoven fabric, a porous polyethylene film or a polypropylene film material, a back sheet made of polyethylene, and an absorbent core in which a water-absorbing resin is dispersed in pulp. Therefore, except for pulp, these sanitary products do not have biodegradability, and disposal after use is a problem. The current status of the disposal of these sanitary materials is based on incineration and landfill methods.
  • the resin obtained by crosslinking the polyamino acid is a material that is friendly to the global environment because it absorbs water and swells and has biodegradability.
  • the production method of these cross-linked polyamino acids is described in Japanese Patent Application Laid-Open Nos. Hei 6-50464 and Hei 8-504192, and polyaspartic acid, aspartic acid and a crosslinking agent are heated by heat. A method of reacting is disclosed.
  • Japanese Patent Application Laid-Open No. Hei 8-58920 discloses a method in which an acidic polyamino acid and a basic polyamino acid are mixed, and the mixture is heated to be crosslinked.
  • the present inventors reacted a polyamino acid with a cross-linking agent such as a polyepoxy compound, a polyol, a polythiol, a polyisocyanate, a polyaziridine, a polyvalent metal, etc. in Japanese Patent Application Laid-Open No. 11-060729.
  • a method for producing a crosslinked polyamino acid was disclosed. These methods have a feature that a uniform cross-linking can be performed without the need for a non-protonic polar solvent for dissolving the polysuccinic acid imide.
  • the weight is 2 to 40. /.
  • a method for producing a polyamino acid-based water-absorbing resin which is cross-linked with a polydaricidyl compound in a water-soluble aqueous solution of a polyamino acid having a concentration of 1% or less is disclosed.
  • the time required for the reaction is long, and polyaspartic acid is hydrolyzed to break the main chain, and the resulting water-absorbent resin has insufficient physical properties such as water absorbing ability.
  • It has many problems such as generation of a large amount of water-soluble components (uncrosslinked polymer and salt) and low yield. In particular, its low water absorption makes it difficult to use for sanitary articles such as disposable diapers.
  • a method for producing a crosslinked polyamino acid in which an aqueous solution of a polyamino acid is brought into contact with a diglycidylaldehyde compound or a diaziridine compound, water is removed by freeze-drying or the like, and heat treatment is performed.
  • this production method has a problem that it is industrially uneconomical in terms of energy and equipment required for freeze-drying. Disclosure of the invention
  • An object of the present invention is to solve the above-mentioned conventional problems, and to provide a crosslinked polyaspartic acid (salt) having excellent water absorption ability, high productivity, low cost and biodegradability, and its production. It's about complicating the way.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, they can be obtained by performing a crosslinking reaction using a polyvalent epoxy compound in an aqueous solution containing polyaspartic acid (salt) at a high concentration in a specific range. They found that various excellent results were obtained, such as high water absorption of cross-linked polyaspartic acid (salt). Reached.
  • the present invention relates to a method for producing a crosslinked polyaspartic acid (salt) in which polyaspartic acid (salt) is reacted with a polyvalent epoxy compound, wherein the concentration of polyaspartic acid (salt) is 41 to 70% by weight.
  • This is a method for producing cross-linked polyaspartic acid (salt), which is characterized in that a crosslinking reaction is carried out in an aqueous solution of / as polyaspartic acid (salt).
  • the present invention relates to a method for producing a crosslinked polyaspartic acid obtained by reacting a polyaspartic acid (salt) with a polyvalent epoxy compound, wherein the water absorption after one hour with respect to a physiological saline measured by a tea bag method is obtained.
  • Acid (salt) Crosslinked polyaspartic acid (salt) that is 28 to 100 times its weight.
  • the present invention relates to a method for producing a crosslinked polyaspartic acid obtained by reacting a polyaspartic acid (salt) with a polyepoxy compound, which is obtained by reacting polyaspartic acid (salt) with a polyvalent epoxy compound after one hour with respect to distilled water as measured by the tea bag method.
  • Salt Crosslinked polyaspartic acid (salt) that is 200 to 1500 times its weight.
  • the raw material polymer [polyaspartic acid (salt)] before cross-linking has a molecular weight distribution and non-uniformity in the cross-linking reaction.
  • the average degree of crosslinking is high, the water absorption of the crosslinked polymer [crosslinked polyaspartic acid (salt)] is low, and when the average degree of crosslinking is low, the water absorption of the crosslinked polymer is high.
  • the conventional production method when trying to obtain a crosslinked polyaspartic acid (salt) with a low degree of crosslinking, the water absorption of the water-insoluble portion increases, but the water-soluble portion increases, resulting in the water absorption. The water absorption of the resin as a whole decreases.
  • the average degree of crosslinking may be increased, but in this case, as described above, the water absorption of the crosslinked polymer which is the water-insoluble portion decreases.
  • a hydrolysis reaction of the main chain of the raw material polymer occurs, and the molecular weight distribution of the polymer and the heterogeneity of the crosslinking reaction increase.
  • the concentration of the raw material polymer [Polyaspartic acid (salt)] in the aqueous solution used for the cross-linking reaction is set to a high concentration within a specific range, whereby the hydrolysis reaction of the main chain of the raw material polymer is performed.
  • the concentration of the raw material polymer [Polyaspartic acid (salt)] in the aqueous solution used for the cross-linking reaction is set to a high concentration within a specific range, whereby the hydrolysis reaction of the main chain of the raw material polymer is performed.
  • To reduce the molecular weight distribution and the non-uniformity of the cross-linking reaction to produce a cross-linked polymer with a relatively low degree of cross-linking, and to generate water-soluble components. Suppress.
  • high water absorption A crosslinked polymer [crosslinked polyaspartic acid (salt)] can be obtained.
  • crosslinked polyaspartic acid is produced by crosslinking polyaspartic acid (salt).
  • the method for producing polyaspartic acid (salt) to be used is not particularly limited.
  • polyaspartic acid (salt) can be obtained by hydrolyzing polysuccinic acid imid obtained by polymerization of aspartic acid.
  • J. Amer. Chem. Soc., Vol. 80, pp. 3361- (1958) discloses a method in which aspartic acid is used as a raw material and heated and condensed at 200 C for 2 to 3 hours.
  • Japanese Patent Publication No. 48-20638 discloses a method of obtaining a high molecular weight polysuccinic acid imide by performing a reaction in a thin film state using a rotary evaporator using 85% phosphoric acid as a catalyst.
  • U.S. Pat. No. 5,057,597 discloses a method for industrially obtaining polysuccinimide by heating polyaspartic acid using a fluidized bed.
  • the method of P. Neri et al. Journal of Medicinal Chemistry, 16, 8, 1973
  • U.S. Pat. No. 5,142,062 JP-A-7-216084, JP-A-8-231710
  • U.S. Pat. No. 4,363,797, JP-B-52-8873, JP-A-7-1966796, JP-A-8-176297, JP-A-9-114365, and the like can be used.
  • the ⁇ Can be treated with a condensing agent such as dicyclohexylcarposimid.
  • polysuccinic acid imide In addition to aspartic acid, asparagin, aspartic acid ester, aspartic acid diester, maleamide, maleimide, maleic acid and ammonia, maleic acid ammonium salt, fumaric acid salt, as well as aspartic acid, are used as raw materials for the production of polysuccinic acid imide. Fumaric acid and ammonia, ammonium fumarate, and the like can be used. These raw materials can be used alone or as a mixture of two or more.
  • the polysuccinic acid imid used in the present invention includes a polymer having a main chain of a difunctional or higher functional monomer such as an amino acid.
  • amino acids include, for example, the following 20 types of amino acids 1 to 4.
  • Amino acids with non-polar or hydrophobic R groups alanine, palin, oral isin, isoleucine, methionine, tryptophan, phenylalanine, and oral phosphorus
  • Polar but uncharged amino acids glycine, serine, threonine, cystine, tyrosine, asparagine, glutamine
  • amino acids having a negatively charged R group aspartic acid, glutamic acid
  • amino acids include L-orditin, a series of amino acids, ⁇ -alanine, ⁇ -aminobutyric acid, and ⁇ of acidic amino acids.
  • Esters, ⁇ -substituted basic amino acids, and aspartic acid amino acids and amino acid derivatives such as L-phenylalanine dimer (aspartame); and aminosulfonic acids such as L-cysteine acid.
  • the amino acid may be an optically active form (L-form, D-form) or a racemic form.
  • the polyamino acid may be a copolymer containing another monomer component.
  • Examples of other copolymerizable difunctional or higher-functional monomers include aminocarboxylic acid, aminosulfonic acid, aminophosphonic acid, hydroxycarboxylic acid, mercaptocarbonic acid, mercaptosulfonic acid, mercaptophosphonic acid, and the like. .
  • polyamines examples include polyvalent aziridine compounds, polyvalent carbamate compounds, polyvalent rubamic acid compounds, polyvalent oxazoline compounds, polyvalent reactive unsaturated bond compounds, and polyvalent metals.
  • copolymer When it is a copolymer, it may be a block copolymer or a random copolymer. Further, it may be a graft copolymer.
  • the weight-average molecular weight of the polysuccinic acid imid used in the present invention is not particularly limited as long as a product having desired characteristics is substantially obtained, but is generally from 2000 to 100. 0000 is preferable, 50,000 to 50,000 is more preferable, and 7000 to 2,500 is particularly preferable in practical use.
  • the method for producing polyaspartic acid (salt) used in the present invention is not particularly limited.
  • hydrolyzed polysuccinic acid imide described in (1) manufactured by fermentation or enzymatic method, N-carboxy- ⁇ -amino acid anhydride (NCA) of aspartic acid monoester 141 And those obtained by polymerizing to remove the ester group.
  • NCA N-carboxy- ⁇ -amino acid anhydride
  • those obtained by hydrolyzing polysuccinic acid imide are industrially preferable.
  • part or all of the main chain is usually an imido ring.
  • Boriaspartic acid (salt) can be obtained by reacting this imid ring with an alkali or a nucleophile to open the ring.
  • Alkali or amine is used as a reagent that acts on the imido ring to open the ring.
  • alkali metal hydroxide such as sodium hydroxide, lithium hydroxide
  • alkali metal carbonate such as sodium carbonate, potassium carbonate, lithium carbonate
  • sodium hydrogen carbonate Alkali metal bicarbonates such as potassium bicarbonate, alkali metal acetates such as sodium acetate and acetic acid sodium salt, organic carboxylic acid alkali metal salts such as sodium oxalate, triethylamine, triethanolamine, etc. in this aqueous solution may be used c such grade Amin, inexpensive hydroxide Natoriumu, Shi preferred hydroxide force Riumu les.
  • Lysine Such as amino acids, optionally branched alkylamines having 1 to 18 carbon atoms, cycloalkylamines having 3 to 8 carbon atoms, aralkylamines, optionally substituted phenylamines, optionally substituted naphthylamines , Ammonia and the like.
  • alkalis and nucleophiles can be used in any of an aqueous solution, a solution of a water-miscible organic solvent, or a solid.
  • the reaction temperature of the alkali ring-opening reaction of imid of polysuccinic acid is preferably 5 to 100 ° C, more preferably 20 to 80 ° C, and particularly preferably 40 to 60 ° C. I like it.
  • the alkali ring-opening reaction of the imido ring is preferably carried out at a pH of 7 to 13, more preferably 9 to 12.
  • the upper limit of each of the above ranges of pH is significant in that the amide bond in the main chain is not broken and the water absorbing ability of the water-absorbing resin is not reduced. Further, the lower limit of each range is significant in that the reaction is appropriately accelerated and the practicality is improved.
  • the post-treatment of polyaspartic acid (salt) obtained by subjecting the imido ring of polysuccinic acid imid to alkaline hydrolysis is not particularly limited. If necessary, the salt can be exchanged for another type of salt.
  • the carboxyl group of polyaspartic acid usually forms an alkali metal salt or an ammonium salt, and the reaction solution is alkaline. If necessary, the pH can be adjusted by adding a mineral acid such as hydrochloric acid or sulfuric acid, a carboxylic acid such as acetic acid, or a sulfonic acid such as methanesulfonic acid.
  • a mineral acid such as hydrochloric acid or sulfuric acid
  • a carboxylic acid such as acetic acid
  • a sulfonic acid such as methanesulfonic acid.
  • polyaspartic acid salt
  • polyaspartic acid salt
  • ion exchange resin since polyaspartic acid (salt) is hydrolyzed on the acidic side, it is preferable to isolate it on the acidic side when isolating it.
  • the use of a stable polyaspartate in water prevents cleavage of the main chain and a decrease in the molecular weight, so that the crosslinking reaction can be advantageously performed.
  • Its isolation method is not particularly limited. For example, it can be isolated by discharging into a poor solvent such as methanol or distilling off a reaction solvent such as water.
  • the concentration can be adjusted by concentration or the like. However, when the concentration is performed, the energy efficiency is low, and the polymer main chain may be cut. It is preferable to adjust the concentration to a high level during hydrolysis of polysuccinic acid imid. In order to adjust to a high concentration during hydrolysis, it is difficult to disperse the polysuccinate imide in water at once, so it is difficult to stir the polysuccinate imide.
  • the method of adding while adding is preferable. By hydrolyzing little by little, the reaction can be carried out with sufficient stirring.
  • One of the features of the present invention is that when polyaspartic acid (salt) is subjected to a cross-linking reaction using a polyepoxy compound, the concentration of polyaspartic acid (salt) is 41 to 70% by weight. / 0 aqueous solution of polyaspartic acid (salt). If this concentration exceeds 70% by weight, the polyaspartic acid (salt) does not dissolve, it is difficult to stir, and even cross-linking reaction cannot be performed, the water-soluble component increases, and the yield, Both water absorption capacity decreases. This concentration is 41 weight. When the ratio is less than / 0 , the reaction time is extremely long, the amount of water-soluble components increases, and both the yield and the water absorption capacity decrease.
  • the lower limit of this concentration is just 45 weight. /. Or more, more preferably 50% by weight or more.
  • the upper limit is preferably 60% by weight or less.
  • the concentration of polyaspartic acid (salt) is defined as 100% by weight of the total weight of all the reagents (including water) used in the crosslinking reaction, and defined as the weight% of polyaspartic acid (salt) based on the total weight. .
  • the solubility of polyaspartic acid (salt) is related to its molecular weight, counter ion and neutralization degree.
  • high molecular weight polymers have low solubility and low molecular weight polymers have high solubility.
  • counter ions relatively small ions such as sodium, potassium and ammonium have high solubility.
  • degree of neutralization the solubility is higher when a salt is formed than when a free carboxylic acid is formed.
  • the reaction is performed at a concentration lower than the solubility.
  • reaction conditions such as reaction temperature, pH, amount and valency of the crosslinking agent are important. Preferred reaction conditions differ depending on these combinations.
  • the reaction between polyaspartic acid and the crosslinking agent is fast at high temperatures and low pH, while the hydrolysis of the main chain of polyaspartic acid is also quick at high temperatures and low pH.
  • the hydrolysis reaction of the epoxy group of the cross-linking agent is accelerated at high temperature and low pH.
  • crosslinking reaction and side reaction hydrolysis reaction of polymer main chain, The hydrolysis reaction of the epoxy group of the crosslinking agent
  • the pH of the aqueous solution one of the reaction conditions, determines the amount of carboxyl groups involved in the crosslinking reaction.
  • the pH of the aqueous solution used for the crosslinking reaction is preferably 3 to 7, more preferably 4 to 6, and particularly preferably 4.5 to 5.5.
  • the cross-linking reaction largely depends on the concentration of the carboxyl group and the cross-linking agent in polyaspartic acid. When the concentration of polyaspartic acid (salt) is low, the preferred pH of pH 3 to 7 is low, the number of carboxyl groups involved in the reaction is small, the cross-linking reaction time is long, and the hydrolysis reaction proceeds, so the bridge It is disadvantageous for the reaction.
  • the crosslinking reaction time is shortened at a preferable pH of 3 to 7 because the concentration is high even if the number of carboxyl groups involved in the reaction is small, even if the number is small.
  • the hydrolysis reaction does not proceed, it is advantageous for the crosslinking reaction.
  • polyaspartic acid it is preferable to carry out a crosslinking reaction in an aqueous solution in which an inorganic salt such as an alkali metal halide and / or other than polyaspartic acid (salt) is present.
  • an inorganic salt such as an alkali metal halide and / or other than polyaspartic acid (salt) is present.
  • an inorganic salt and / or an organic salt alleviates the interaction between the functional groups in the molecule and between the functional groups in the molecule, and expands the polymer molecular chain.
  • Those having no and having are preferably those having an effect of expanding the chain of polyaspartic acid in water without impairing the solubility of polyaspartic acid (salt).
  • the liquid property of the aqueous solution is not largely changed or that the aqueous solution is mild enough to adjust the liquid property.
  • whether salts can be easily removed, or some of them are preferred to have excellent safety even if they remain in the polymer.
  • the inorganic salt and the organic salt to be used are not particularly limited as long as the above action can be exerted, and general salts such as neutral salt, basic salt and acidic salt can be widely used.
  • a polyvalent metal salt is used, the polyvalent metal salt is formed by hydrolysis of the imido ring.
  • the carboxyl groups are ionically cross-linked and the degree of cross-linking increases, so it is better to add them in consideration of the change in the degree of cross-linking after addition.
  • the inorganic salt and the organic salt may be added to the reaction solution in a solid state, a solution obtained by dissolving the salt in water may be added, or the salt may be formed by neutralization in water. Good.
  • a method of generating a salt by neutralization is preferable.
  • salts used include, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, sulfurous acid, disulfite, amide sulfate, thiosulfate, nitric acid, nitrous acid, phosphoric acid, Phosphorous acid, orthophosphoric acid, metaphosphoric acid, hypophosphoric acid, pyrophosphoric acid, phosphinic acid, phosphonic acid, carbonic acid, percarbonic acid, boric acid, orthoboric acid, metaboric acid, hydrochloric acid, perchloric acid, hypochlorous acid , Bromate, perbromate, hypobromite, iodic acid, periodate, hypoiodite, keic acid, orthokeic acid, metasilicic acid, aluminate, telluric acid, isocyanic acid, thiocyanate, manganese Inorganic mineral acids such as acids, permanganic acid, periodic acid, chromic acid, dichromic acid, sulfur
  • hydrochloric acid hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphinic acid, phosphonic acid, carbonic acid, boric acid Metal salts or basic salts of orthoboric acid, metaboric acid, citric acid, orthokeic acid, metasilicic acid, oxalic acid, organic phosphonic acid, organic sulfonic acid, and organic carboxylic acid are preferred.
  • metal salts or organic salts of each acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, organic phosphonic acid, organic sulfonic acid and organic carboxylic acid are particularly preferable.
  • Metals constituting the metal salts include lithium, sodium, potassium, beryllium, magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, dumbbell, gallium, gallium, , Rubidium, strontium, yttrium, zirconium, diobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, Examples include tin, tellurium, cesium, barium, cerium, gold, mercury, thallium, and lead. Of these, lithium, sodium, and potassium, which are excellent in safety, low in cost, and have high solubility in water, are preferable.
  • examples include ammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, and ethyltrimethyl.
  • Ammonium trimethylpropynoleammonium, butyltrimethizoleammonium, pentyltrimethylammonium, hexyltrimethylammonium, cycle mouth hexyltrimethylammonium, benzyltrimethylammonium, triethylpropylammonium Ammonia, triethylbutylammonium, triethylpentylammonium, triethylhexylammonium, cyclohexyltriethylammonium, ammonium salts such as benzyltriethylammonium, and trimethyme Lamine, Triethylamine, Tripropylamine, Tributylamine, Tripentylamine, Trihexylamine, Triethanolamine, Tripropanolamine, Tributanolamine, Tripentanolamine, Trihexanolamine, Dimethylamine, Diethylamine, Dipropylamine , Dibutyl
  • ammonium salts such as luammonium and benzyltriethylammonium
  • amine salts such as trimethylamine, triethylamine, tripropylamine, tributylamine and triethanolamine.
  • examples of specific salts include sodium chloride, potassium chloride, and lithium chloride.
  • P-toluenesulfonic acid tetrabutylammonium 'P-toluenesulfonate, triethanolamine pp-toluenesulfonate, sodium benzoate, potassium benzoate, ammonium benzoate, sodium oxalate, potassium oxalate, ammonium oxalate, sodium acetate Um, acetic force Riumu acetate Anmoniumu, Natoriumu propionate, Kariumu propionate are preferred.
  • each of the salts listed above may be used alone or in combination of two or more.
  • inorganic salts and organic salts can be used in combination.
  • the concentration of the salt in the reaction solution is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 5% by weight, as long as polyaspartic acid (salt) does not precipitate. If the concentration is appropriately increased, the effect of the salt is exhibited, and if the concentration is appropriately reduced, the salt can be prevented from being mixed into the resin.
  • inorganic and / or Z or polyaspartic acid (salt) other than polyaspartic acid (salt) in aqueous solution of polyaspartic acid (salt) (when the carboxyl group is 100 moles) 5 is preferably 0 mole 0/0 corresponding acid and generates a result of the added pressure.
  • the weight average molecular weight (Mw) of the polyaspartic acid (salt) used in the present invention is not particularly limited as long as a product having desired properties can be substantially obtained. : L 0000 000 is preferable, 2,000 000 to 500 000 force S is more preferable, and 300 000 to 2,500 000 is particularly preferable. Further, as the polyaspartic acid (salt), it is preferable to use a polyaspartic acid metal salt or a polyaspartic acid ammonium salt partially having a carboxylic acid group.
  • the temperature at which the crosslinking reaction is carried out is preferably from 10 to 100 ° C, more preferably from 30 to 70 ° C. If the reaction temperature is too high, the main chain is broken, a large amount of a crosslinking agent is required, and the performance of the resulting water-absorbent resin tends to be low. Is too low The reaction between the paraginic acid and the cross-linking agent becomes slow, which tends to be industrially uneconomical.
  • a polyvalent epoxy compound is used as a crosslinking agent.
  • polyvalent epoxy compound examples include ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and diglycerol.
  • Polyglycidyl ethers of (C 2 -C 6) alkanepolyols and poly (alkylene glycols) such as polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether; Sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, erythritol polyglycidyl ether, trimethicone luethamboli glycidyl ether, trimet Roll propane polyglycidyl ether, 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8 — (C4-C8) diepoxyalkanes and diepoxyalkanes such as epoxyoctane, 1,4- and 1,3-
  • the amount of the cross-linking agent to be used is preferably 0.1 to 30 mol when the functional group of polyaspartic acid (salt) is 100 mol. /. , More preferably 1 to 5 mol 0/0, the properly especially preferred is a 3-1 0 mol 0/0.
  • the upper limit of each of the above ranges is significant in terms of economic efficiency and preventing the degree of cross-linking from becoming too high, thereby reducing the amount of water absorption, and preventing the unreacted cross-linking agent from remaining.
  • the lower limit is that the crosslinking cannot be performed sufficiently, the crosslinking reaction time becomes longer, the water absorption decreases, the water-soluble component increases, the yield decreases, etc. It is significant in preventing it.
  • the cross-linking reaction time varies depending on the reaction temperature, the reaction concentration, and the amount of the cross-linking agent used, and can be adjusted by the reaction temperature, the pH, and the amount of the cross-linking agent used, and is generally 1 minute to 20 hours. Suitable crosslinking reaction time depends on the reaction apparatus, but is preferably 5 minutes to 10 hours, more preferably 5 minutes to 5 hours, and particularly preferably 5 minutes to 1 hour. (4) Water absorption capacity of cross-linked polyaspartic acid (salt)
  • the water-absorbing ability of the crosslinked polyaspartic acid obtained by the production method of the present invention is not particularly limited, but when used for sanitary articles such as disposable diapers, high performance is required.
  • the water absorption of physiological saline in one hour measured by the tea bag method is preferably 28 to 200 times, more preferably 30 to 150 times that of the polymer, and substantially Preferably, it is 40 to 100 times, more preferably 50 to 100 times.
  • the amount of water absorption after 1 hour with respect to distilled water measured by the tea bag method is preferably 200 to 150 times the weight of the dry crosslinked polyaspartic acid (salt), and 300 to 500 times. More preferably, it is 100 times, more preferably 400 to 100 times.
  • the specific conditions for measuring the amount of water absorption will be described in the Examples section below.
  • the water soluble component is preferably 0 to 1 8 weight 0/0 by weight of the polymer - one, and more preferably 0 to 5 wt 0/0, and particularly preferably 0-1 wt%.
  • the post-treatment of the crosslinked polyaspartic acid (salt) obtained as described above is not particularly limited.
  • neutralization, salt exchange, purification, etc. can be performed as required.
  • the carboxyl group of the crosslinked polyaspartic acid (salt) can be converted into a salt or a free carboxylic acid at an arbitrary ratio.
  • the cross-linked polyaspartic acid obtained by the cross-linking reaction can be shredded as necessary and used as it is, or can be subjected to an isolation step.
  • the isolation method include a method of discharging into a poor solvent for reprecipitation, a method of azeotropic dehydration, and a method of removing a reaction solvent such as water with a dryer.
  • drying can be performed using a known drying method.
  • the crosslinked polyaspartic acid (salt) obtained as described above can be further subjected to pulverization, granulation, sieving, and surface cross-linking treatment, if necessary.
  • Particle size is not particularly limited, use applications, Les be changed according to the intended use, have c example, when used as soil improving agent for agricultural or horticultural is considering the dispersibility of the soil Then, 100 to 100 000 ⁇ is preferable, 100 to 500 m is more preferable, and 500 to 100 m is preferable. 500 m is particularly preferred. When used for sanitary products, 1 to 500 ⁇ is preferred, 100 to 100 ⁇ is more preferred, and 100 to 500 ⁇ is particularly preferred.
  • the form of use of the crosslinked polyaspartic acid (salt) is not particularly limited, and may be used alone or in combination with other materials.
  • a method of kneading with a thermoplastic resin and molding by injection molding a method of mixing a monomer of another resin with a crosslinked polyaspartic acid (salt) and, if necessary, an initiator, and polymerizing with light or heat, etc.
  • resin and cross-linked polyaspartic acid (salt) in a solvent casting and removing the solvent, mixing of prepolymer and cross-linked polyaspartic acid (salt), cross-linking, polymer and cross-linked polyaspartic acid
  • an acid (salt) and crosslinking is a method of mixing an acid (salt) and crosslinking.
  • Molded articles of these resin compositions are not particularly limited, and can be used, for example, as solids, sheets, films, » nonwoven fabrics, foams, rubbers, and the like.
  • the molding method is not particularly limited.
  • the structure of the composite is not particularly limited. For example, a method of forming a sandwich structure by sandwiching pulp or nonwoven fabric, a method of forming a multilayer structure using a resin sheet or film as a support, a resin sheet To a two-layer structure.
  • the crosslinked polyaspartic acid (salt) may be used by mixing with another water-absorbing resin, if necessary.
  • Various active ingredients may be added, if necessary, within a range that does not substantially impair the desired properties of the crosslinked polyamino acid (salt).
  • an inorganic compound such as salt, colloidal silica, white carbon, ultrafine silica, titanium oxide powder, or an organic compound such as a chelating agent may be added.
  • an oxidizing agent, an antioxidant, a reducing agent, an ultraviolet absorber, an antibacterial agent, a bactericide, a fungicide, a fertilizer, a fragrance, a deodorant, a pigment, and the like may be mixed.
  • the crosslinked polyaspartic acid (salt) can be used as a gel or as a solid.
  • a cut flower life-promoting agent e.g., a cut flower life-promoting agent, a gel fragrance, a gel deodorant, etc.
  • a paper diaper absorber e.g., a paper diaper absorber
  • crosslinked polyaspartic acid is not particularly limited, and may be used for agricultural and horticultural purposes, It can be used for the same applications as conventional various water-absorbing resins that are known to be usable for applications such as medical use, food use, bath additives, and sanitary materials.
  • sanitary supplies disposable diapers, breast milk pads, sanitary articles such as disposable rags, dressings for wound protection
  • medical supplies such as medical care pads, cataplasms, pet sheets, portable toilets, gels Fragrances, gel deodorants, sweat-absorbing fibers, household items such as disposable warmers, shampoos, set jewelry, toiletries such as moisturizers, agriculture Water retention materials for horticulture, cut flower prolongation , Floral form (fixing material for cut flowers), nurseries for raising seedlings, hydroponic cultivation, vegetation sheets, seed tape, fluid seeding, agricultural sheets for preventing dew condensation, etc.
  • Food packaging materials such as preservatives, drip-absorbent sheets, etc., cold insulators, transport materials such as water-absorbent sheets for transporting fresh vegetables, building materials for preventing dew condensation, sealing materials for civil engineering and construction, shielding materials Materials for preventing sludge loss, concrete admixture, materials for civil engineering and construction such as gasket packing, sealing materials for electronic equipment such as optical fibers, waterproofing agents for communication cables, materials for electrical equipment such as ink jet recording paper, and soil.
  • Coagulant for mud dewatering of gasoline and oils, water treatment agent such as water removing agent, printing paste, water swelling toys, artificial snow, sustained release fertilizer, sustained release pesticides, sustained release chemicals, humidity control Materials, antistatic agents and the like.
  • the weight average molecular weight (Mw) of polyaspartic acid was measured by GPC (gel 'permeation' chromatography) using polyethylene oxide as a standard.
  • Aqueous solution concentration 0.1%
  • the amount of water absorption was measured using the tea bag method for distilled water and physiological saline.
  • about 0.05 part of the dry water-absorbent resin for distilled water and about 0.1 part of the dry water-absorbent resin for physiological saline are put into a nonwoven fabric bag (80 raraX 50 ⁇ ). After immersion in an excess of the corresponding solution at 20 ° C to swell the resin for 1 hour, pull up the tea bag and drain it for 1 minute to remove the tea bag containing the swollen resin. The weight was measured.
  • the saline solution is a 0.9% by weight aqueous sodium chloride solution.
  • Biodegradability was measured by the compost method.
  • the composting method was performed in accordance with ISOCD144485, which is an application of ASTMD-5 33 38.92. That is, first, the amount of carbon contained in the test sample was measured by elemental analysis.Next, 15 parts of the test sample were added to 800 parts of the inocula, and biodegraded at 58 ° C for 40 days. The amount of carbon dioxide generated was measured, and the amount of carbon dioxide generated relative to the amount of carbon dioxide contained in the test sample converted to carbon dioxide was expressed as the biodegradation rate ( ⁇ 1 ⁇ 2).
  • the biodegradation rate ⁇ 1 ⁇ 2
  • some of the samples that are easily biodegradable promote the decomposition of even the carbon content in the inocula, and in this case, the value of the sample exceeds 100%.
  • the water-soluble component in the polymer was measured by the following method. That is, the gel swollen with 200 parts of distilled water with respect to 1 part of the polymer is stirred when it can be stirred, and when it cannot be stirred, it is kept still for 20 hours, and after 20 hours on the filter paper. The filtrate was separated by filtration, washed with 200 parts of water, and the filtrate was evaporated to dryness, and the weight was measured. The weight is a percentage of the original polymer i (wt. / 0).
  • polysuccinimide obtained in Production Example A1 100 parts of the polysuccinimide obtained in Production Example A1 was dispersed in 230 parts of water, and 206 parts of a 20 wt% aqueous sodium hydroxide solution was added dropwise while maintaining the pH at 12 or less.
  • aqueous solution of polyaspartic acid 27 parts of 12N hydrochloric acid was added, and the mixture was discharged into 400 parts of methanol, filtered and dried to obtain polyaspartic acid having an Mw of 49,000.
  • the solids concentration (concentration of polyaspartic acid) was changed in the same manner as in Example A1, except that 3 mol of ethylene glycol diglycidyl ether was used per 100 mol of carboxyl groups of polyaspartic acid. weight. / 0 polyaspartic acid aqueous solution was obtained.
  • a water-absorbing polymer [crosslinked polyaspartic acid (salt)] was obtained in the same manner as in Example 1 except that this aqueous solution was used and the reaction time was changed to 18 hours. The water absorption of this polymer is 66 times higher than that of distilled water and 56 times higher than that of physiological saline, and the water-soluble component is 0.9 weight. / 0 and less.
  • Ethylene glycol diglycidyl ether is replaced with polyaspartic acid Except that the 1 0 Monore used for sill group 1 0 0 mole in the same manner as in Example A 1, polyaspartic acid aqueous solution having a solid concentration (concentration of polyaspartic acid) 4 4 weight 0/0 Obtained.
  • a water-absorbing polymer [crosslinked polyaspartic acid (salt)] was obtained in the same manner as in Example A1, except that the reaction time was changed to 9 hours.
  • the water absorption of this polymer was as high as 46 times that of distilled water and 50 times that of physiological saline, and the water-soluble component was as low as 0.3% by weight.
  • the solid content (the concentration of polyaspartic acid) was 47% by weight in the same manner as in Example A1, except that the pH of the aqueous solution was adjusted to 4.6. /.
  • a polyaspartic acid aqueous solution was obtained.
  • a water-absorbing polymer [crosslinked polyaspartic acid (salt)] was obtained in the same manner as in Example A1, except that the reaction time was changed to 5 hours.
  • the water absorption of this polymer was 52 times higher than that of distilled water and 53 times higher than that of physiological saline, and the water-soluble component was as low as 0.6% by weight.
  • aqueous polyaspartic acid solution was prepared in the same manner as in Example 1 except that the pH of the aqueous solution was adjusted to 8, and an attempt was made to obtain a water-absorbing polymer [crosslinked polyaspartic acid (salt)]. The liquid did not gel, and no water-absorbing polymer was obtained.
  • the resulting polyaspartic acid aqueous solution was adjusted to pH 8.7 with 2N hydrochloric acid, and after discharging to 4,000 parts of methanol, the precipitate was filtered, dried at 60 ° C, and dried at 60,000 Mw. There were obtained 152 parts of sodium polyaspartate.
  • the reaction was carried out in the same manner as in Production Example B1 except that L-aspartic acid was reacted at 220 ° C. for 10 hours to obtain 108 parts of a polysuccinic acid imide having an Mw of 1460,000. 100 parts of this polysuccinimide I Mi de dispersed in 230 parts of water was added dropwise while maintaining the 20 weight 0/0 water oxidation Natoriumu solution 206 parts of p H 1 2 or less. The resulting aqueous solution of polyaspartic acid was adjusted to pH 8.7 with 2 N hydrochloric acid, discharged into 4000 parts of methanol, and the precipitate was filtered and dried at 60 ° C. 154 parts of 50,000 sodium polyaspartate were obtained.
  • the obtained gel was chopped in a mixer, dried at 60 ° C., and dried to obtain 60 parts of crosslinked polyaspartic acid (sodium).
  • the water absorption of this polymer was 571 times higher than that of distilled water and 53 times higher than that of physiological saline, and the water-soluble component was as low as 0.3% by weight. Biodegradability was 109%.
  • Example B1 Using 60 parts of the sodium polyaspartate obtained in Production Example B1 and 40 parts of distilled water, 3.80 parts of ethylene glycol diglycidide / ether (to 100 moles of carboxyl groups of polyaspartic acid) The reaction was carried out in the same manner as in Example B1 except that the reaction time was 5 hours, and 59 parts of a polymer were obtained.
  • the concentration of salt other than polyaspartic acid in this case is 2. a 9 wt 0/0, polymers one concentration of Po Li aspartic acid aqueous solution 5 4. 1 wt. /. Met.
  • the reaction was carried out in the same manner as in Example B1, except that 60 parts of sodium polyaspartate obtained in Production Example B2 was used and reacted for 3 hours, to obtain 59 parts of a polymer.
  • the concentration of salt other than polyaspartic acid in this case is 2. a 9 wt 0/0, the polymer concentration of the aqueous solution polyaspartic acid 4. 9 wt. /. Met.
  • the water absorption of the obtained gel was 102 times higher than that of distilled water and 71 times higher than that of physiological saline, and the water-soluble component was as low as 0.2% by weight. In addition, the raw sex angle was 108%.
  • the reaction was carried out in the same manner as in Example B4, except that 60 parts of sodium polyaspartate, a part of which was a carboxylic acid, obtained in Production Example B4 and 3 parts of sodium chloride were added. Parts of polymer were obtained. At this time, the concentration of salts other than polyaspartic acid was 2.8% by weight. /. The polymer concentration of the aqueous polyaspartic acid solution was 56.2% by weight. The water absorption of the obtained polymer was 508 times higher than that of distilled water and 50 times higher than that of physiological saline, and the water-soluble component was as low as 0.2% by weight. The biodegradability was 110%.
  • Example B4 The reaction was carried out in the same manner as in Example B4, except that 60 parts of sodium polyaspartate, a part of which was a carboxylic acid, obtained in Production Example B4 was used, and 3 parts of sodium p-toluenesulfonate was added. However, 57 parts of a polymer were obtained. At this time, the concentration of salts other than polyaspartic acid was 2.8% by weight. /. The polymer concentration of the polyaspartic acid aqueous solution was 56.2% by weight. When the water absorption of the obtained polymer was measured, it was 508 times higher than that of distilled water and 50 times higher than that of physiological saline. The soluble component was as low as 0.2% by weight. The raw corn keratility was 110%.
  • polysuccinic acid imide having a Mw of 96,000 obtained in Production Example B1 50 parts of polysuccinic acid imide having a Mw of 96,000 obtained in Production Example B1 was dispersed in 100 parts of distilled water, and the weight was 20%. /. 103 parts of an aqueous sodium hydroxide solution were added dropwise while maintaining the pH at 12 or less. 30 parts of polysuccinimide were dispersed in the obtained solution, and the weight was 20%. 62 parts of an aqueous 0 / sodium hydroxide solution were added dropwise while maintaining the pH at 12 or less. 20 parts by weight of polysuccinic acid imid was added. / 0 was added dropwise while maintaining the pH to 1 2 below hydroxide Natoriumu solution 4 1 part.
  • the resulting aqueous solution of polyaspartic acid was adjusted to pH 5 using 2N hydrochloric acid, and 9.0 parts of ethylene glycol diglycidyl ether was added to the polyaspartic acid, followed by a reaction at 40 ° C for 5 hours. did.
  • Polyaspartic concentration of salts other than acid 2. a 5 weight 0/0, polymers one concentration of Poriasupa Ragin aqueous acid solution 4 5.8 weight when this. / 0 .
  • the obtained gel was treated in the same manner as in Example B1, 97 parts of crosslinked polyaspartic acid were obtained.
  • the water absorption of the obtained polymer was 489 times higher than that of distilled water and 47 times higher than that of physiological saline, and the water-soluble component was as low as 0.5% by weight.
  • the biodegradability was 107 ⁇ 1 ⁇ 2.
  • Example B2 85 parts of the polyaspartic acid obtained in Production Example B2 was dissolved in 15 parts of distilled water, but was not dissolved. Ethylene glycol diglycidyl ether was added in the suspended state and treated in the same manner as in Example B1, but the obtained polymer was as small as 25 parts and the water absorption was 70 times that of distilled water. It was 20 times lower than that of physiological saline.
  • the water-soluble component is 25 weight. / 0 and very many.
  • a bioabsorbable resin having a high water absorption can be produced with high productivity and at low cost.
  • Specific effects of the present invention include, for example, the following items (1) to (6).
  • reaction can be controlled by heating, it is easy to realize an appropriate degree of crosslinking, and it is possible to produce a water-absorbent resin having a high level of water absorption.
  • a high water absorption can be realized by a crosslinking reaction in a homogeneous system.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne un procédé de production d'un acide (sel) polyaspartique réticulé possédant une excellente capacité d'absorption d'eau, consistant à réticuler un acide (sel) polyaspartique en solution aqueuse ayant une concentration de 41 à 70 % en masse avec un composé époxyde polyvalent.
PCT/JP2000/009292 1999-12-28 2000-12-27 Procede de production d'acide (sel) polyaspartique reticule WO2001048056A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP37431299A JP3933359B2 (ja) 1999-12-28 1999-12-28 架橋ポリアスパラギン酸（塩）の製造方法
JP11/374312 1999-12-28
JP37431499A JP2001181392A (ja) 1999-12-28 1999-12-28 架橋ポリアスパラギン酸（塩）の製造方法
JP11/374314 1999-12-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113201801A (zh) * 2021-04-15 2021-08-03 上海工程技术大学 一种氨基酸螯合锌修饰莱麻天丝纤维的制备方法和应用
WO2023155060A1 (fr) * 2022-02-16 2023-08-24 Dic Corporation [titre de l'invention]

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0859821A (ja) * 1994-08-26 1996-03-05 Ajinomoto Co Inc ポリアスパラギン酸塩の製造方法
JPH09241378A (ja) * 1996-03-14 1997-09-16 Mitsubishi Chem Corp ポリアスパラギン酸およびその塩の製造方法
EP0856539A1 (fr) * 1997-01-30 1998-08-05 Mitsui Chemicals, Inc. Polymère réticulé
EP0881247A1 (fr) * 1997-05-29 1998-12-02 Rohm And Haas Company Acides polyaminés réticulés et leur méthode de préparation
JP2000063511A (ja) * 1997-02-07 2000-02-29 Mitsui Chemicals Inc 架橋ポリアミノ酸の製造方法
JP2000281915A (ja) * 1999-03-30 2000-10-10 Dainippon Ink & Chem Inc 吸水性材料
JP2000290370A (ja) * 1999-04-07 2000-10-17 Dainippon Ink & Chem Inc 吸水性材料
JP2000290381A (ja) * 1999-04-08 2000-10-17 Dainippon Ink & Chem Inc 吸水性樹脂の製造方法
JP2000290373A (ja) * 1999-04-08 2000-10-17 Dainippon Ink & Chem Inc 吸水性複合体の製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0859821A (ja) * 1994-08-26 1996-03-05 Ajinomoto Co Inc ポリアスパラギン酸塩の製造方法
JPH09241378A (ja) * 1996-03-14 1997-09-16 Mitsubishi Chem Corp ポリアスパラギン酸およびその塩の製造方法
EP0856539A1 (fr) * 1997-01-30 1998-08-05 Mitsui Chemicals, Inc. Polymère réticulé
JP2000063511A (ja) * 1997-02-07 2000-02-29 Mitsui Chemicals Inc 架橋ポリアミノ酸の製造方法
EP0881247A1 (fr) * 1997-05-29 1998-12-02 Rohm And Haas Company Acides polyaminés réticulés et leur méthode de préparation
JP2000281915A (ja) * 1999-03-30 2000-10-10 Dainippon Ink & Chem Inc 吸水性材料
JP2000290370A (ja) * 1999-04-07 2000-10-17 Dainippon Ink & Chem Inc 吸水性材料
JP2000290381A (ja) * 1999-04-08 2000-10-17 Dainippon Ink & Chem Inc 吸水性樹脂の製造方法
JP2000290373A (ja) * 1999-04-08 2000-10-17 Dainippon Ink & Chem Inc 吸水性複合体の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113201801A (zh) * 2021-04-15 2021-08-03 上海工程技术大学 一种氨基酸螯合锌修饰莱麻天丝纤维的制备方法和应用
CN113201801B (zh) * 2021-04-15 2022-07-22 上海工程技术大学 一种氨基酸螯合锌修饰莱麻天丝纤维的制备方法和应用
WO2023155060A1 (fr) * 2022-02-16 2023-08-24 Dic Corporation [titre de l'invention]
WO2023155523A1 (fr) * 2022-02-16 2023-08-24 Dic Corporation Produit poly (acide aspartique) réticulé et son procédé de production

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