JP5024585B2 - Novel itaconic sugar derivative and process for producing the same - Google Patents

Description

  The present invention relates to a novel itaconic acid sugar derivative used for the production of a polymer having a sugar residue in the side chain, a production method thereof, and a polymer obtained therefrom.

  Synthetic polymers derived from petroleum are used in extremely diverse fields because of their convenience in daily life. However, in recent years, environmentally friendly biodegradable plastics and biomimetic materials using naturally derived raw materials have been demanded from the viewpoint of environmental problems and nature protection. Naturally occurring saccharides are the most produced organic substances on the earth. For example, cellulose is mostly decomposed by microorganisms and enzymes, and only a small part is utilized. In the future development of a recycling society, saccharides are considered to be useful as raw materials for biodegradable plastics and biomimetic materials.

As described in Non-Patent Document 1, a biodegradable sugar-containing polymer having a polyvinyl alcohol main skeleton obtained by an enzyme-catalyzed reaction between an oligosaccharide having a reducing end and divinyl adipate has been reported in the literature. In addition, an organic solvent such as dimethyl sulfoxide or dimethylformamide is required and the reaction takes a long time. Therefore, the operation is complicated and it is difficult to obtain a sugar chain polymer in a short time.
In addition, as sugar-containing polymers, polymers obtained by polymerizing amino sugars and amides composed of carboxylic acids having unsaturated groups as monomers are reported. Examples of such compounds include Patent Documents 1 and 2 and Non-Patent Documents 2 to 2. Although it is disclosed in US Pat. No. 4,697, it does not describe a compound in which the carboxylic acid having an unsaturated group is itaconic acid.
JP-A-3-236395 Japanese Patent Laid-Open No. 8-245568 Polymer Proceedings 2000, 57, 629 Makromol. Chem. 1987, 188, 1217 J. Carbohydr. Chem. 1989, 8: 597 Macromolecules 1997, 30, 2016

  The present invention provides a novel itaconic acid sugar derivative, a process for producing the same, and a polymer obtained by polymerizing them.

As a result of earnest research to solve such problems, the present inventors have found that an unsaturated bond capable of radical polymerization can be introduced into a sugar by reacting itaconic anhydride with an amino sugar, and the present invention has been developed. It came to be completed.
That is, the present invention firstly has the following general formula (I) (wherein R is general formula (II) or general formula (III) (wherein R ′ is a hydrogen atom, glucose residue or cellobiose residue). And X represents a hydrogen atom or an alkali metal atom.) It relates to a novel itaconic acid sugar derivative represented by the following formula:
Second, itaconic anhydride and general formula (IV) (wherein R represents general formula (II) or general formula (III) (
In the formula, R ′ represents a hydrogen atom, a glucose residue or a cellobiose residue. ) Represents a residue. The amino sugar represented by formula (I) is reacted in a water-containing organic solvent in the presence of an alkali.
Thirdly, it is represented by the general formula (V) (wherein R represents the general formula (II) or general formula (III) (wherein R ′ represents a hydrogen atom, a glucose residue or a cellobiose residue)). X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more.) Itaconic acid sugar derivative polymer.

  According to the present invention, an amino sugar having an amino group in a molecule such as naturally occurring glucosamine and cellobiosylamine is reacted with itaconic anhydride, thereby having an unsaturated bond capable of radical polymerization in a simple and high yield. A novel itaconic acid sugar derivative can be obtained. These itaconic acid sugar derivatives are those capable of obtaining an itaconic acid derivative polymer by radical polymerization.

Hereinafter, the present invention will be described in detail.
The itaconic acid sugar derivative provided by the present invention includes itaconyl-glucosamine or an alkali metal salt thereof (general formula (VI), X: hydrogen atom or alkali metal atom), itaconyl-glucosylamine or an alkali metal salt thereof (general formula (VI VII), R ′: hydrogen atom), itaconyl-cellobiosylamine or an alkali metal salt thereof (general formula (VII), R ′: glucose residue), itaconyl-cellotriosylamine or an alkali metal salt thereof (general formula (VII) VII), R ′: cellobiose residues).
Examples of the alkali metal include sodium and potassium.

Itaconic anhydride and amino sugar are used as raw materials for itaconic acid sugar derivatives.
Examples of the amino sugar used include glucosamine which is a 2-amino sugar, glucosyl amine which is a 1-amino sugar, cellobiosylamine, cellotriosylamine and the like. The 1-amino sugar can be easily produced from the corresponding sugar by a known method (for example, J. Carbohydr. Chem. 1989, 8: 597). For example, cellobiosylamine is obtained by amination of cellobiose which is a structural unit of cellulose.
The reaction is carried out by adding an alkali to an aqueous amino sugar solution to keep the solution alkaline, adding a solution in which itaconic anhydride is dissolved in an appropriate solvent at 0 ° C. to room temperature, and stirring at room temperature for about 3 to 12 hours. To be implemented.
Examples of the alkali include sodium hydroxide and potassium hydroxide. As a solvent that can be used, any solvent can be used as long as it can dissolve the raw materials itaconic acid and sugar, and does not inhibit the reaction. Examples thereof include water, acetone, methanol, ethanol, etc., and in particular, a mixed solvent of water and acetone. Is preferred.
After completion of the reaction, the itaconic acid sugar derivative reaction solution is concentrated to precipitate the product, or injected into a suitable organic solvent such as ethanol and then precipitated as a precipitate to isolate the itaconic acid sugar derivative. can do.

The polymer of the itaconic acid saccharide derivative provided by the present invention is an itaconyl-glucosamine polymer (general formula (VIII) (wherein X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more)). Itaconyl-glucosylamine polymer (general formula (IX) (wherein R ′ represents a hydrogen atom, X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more)).
), Itaconyl-cellobiosylamine polymer (general formula (IX) (wherein R ′ represents a glucose residue, X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more)), itaconyl -Cerotriosylamine polymers (general formula (IX) (wherein R 'represents a cellobiose residue, X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more)).
Examples of the alkali metal include sodium and potassium.

Examples of the polymerization method of the itaconic acid sugar derivative include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Solution polymerization is preferred, and the solvent used is itaconic acid represented by the formula (I). Examples of the sugar derivative-soluble polar solvent such as water, dimethylformamide, dimethyl sulfoxide and the like are exemplified, and water is particularly preferable. In the present invention, it can be copolymerized with other monomers within a range not impairing the object and effects of the present invention. Examples of other monomers that can be copolymerized include acrylic acid monomers and acrylamide monomers.
The reaction is carried out in the presence of a polymerization initiator. As the polymerization initiator used, those usually used can be used, for example, aliphatic azo compounds such as 2,2-azobisisobutyronitrile and azobisvaleronitrile, organic compounds such as benzoyl peroxide and lauroyl peroxide. Examples thereof include inorganic peroxides such as peroxides, ammonium persulfate, and potassium persulfate. However, since the itaconic acid derivative is an allyl compound, the polymerization reaction is unlikely to proceed with an initiator usually used as compared with other compounds, and a system using sodium hypophosphite and potassium persulfate as an initiator is particularly preferable.
After completion of the reaction, the polymer of itaconic acid sugar derivative can be isolated by dialysis using a cellulose tube or the like, molecular weight fractionation, or the like.

Example 1 Preparation of Glucosamine Derivative of Itaconic Acid 20.0 g (92 mmol) of glucosamine hydrochloride was dissolved in 100 ml of water (pH 4). 2
46 ml (92 mmol) of M KOH solution was added (pH 10). Add 6 ml of 2M KOH (
12 mmol) was added to bring the pH of the reaction solution to 11. 10.76 g (96 mmol) of itaconic anhydride was dissolved in 50 ml of acetone and added dropwise to the reaction solution. The mixture was stirred for 6 hours in a water bath (5 ° C.). After completion of the reaction, vacuum concentration was performed to about 50 ml. The precipitated white crystals were filtered and washed with 50 ml of acetone. Further, it was washed with 50 ml of diethyl ether and dried under reduced pressure to obtain white crystals.
Yield 10.3g
When the infrared absorption spectrum of the resulting glucosamine derivative product of itaconic acid was measured (FIG. 1), a peak derived from N—H stretching vibration was observed near 1650 cm ⁻¹ , and C═O stretching was observed near 1690 cm ^−1. Each peak derived from vibration was confirmed. Two products (a) and (b) were isolated in a 38:62 ratio by HPLC of the product (FIG. 2).
The HPLC conditions are as follows.
-Column used: Grand120-STC 18-5
Column size: 4.6 mm D. × 150mm
Eluent: H ₂ O (TFA 0.1%)
・ Temperature: 35 ℃
Detector: RI (differential refractive index), UV (wavelength 210 nm)
The biodegradability test of the obtained glucosamine derivative of itaconic acid was performed using ISO14851, JIS.
When performed based on K6950, a biodegradability of 11.1% was obtained in 28 days.
Fractions corresponding to the peaks of (a) and (b) of FIG. 2 are collected, and the eluent is distilled off, followed by lyophilization, whereby both fractions are represented by general formula (X) and general formula (XI). Β-type and α-type glucosamine itaconate derivates derived from an anomer of the sugar skeleton represented were obtained in a ratio of 38:62. The proton nuclear magnetic resonance spectrum (D ₂ O) of the compound obtained from each fraction is shown in FIG. 3 and FIG.

Example 2 Preparation of Cellobiosylamine Derivative of Itaconic Acid 1.0 g (2.1 mmol) of cellobiosylamine (purity 70%) was dissolved in 20 ml of water (pH 10). The pH was adjusted to 11 by adding 0.2 ml (0.4 mmol) of 2M KOH solution. Itaconic anhydride 0.26 g (2.3 mmol) was dissolved in 8 ml of acetone and added dropwise to the reaction solution. The mixture was stirred for 6 hours in a water bath (5 ° C.). After completion of the reaction, vacuum concentration was performed to about 10 ml. Reprecipitation was performed twice using 100 ml of ethanol. Ethanol was distilled off from the obtained reprecipitate, followed by lyophilization.
Yield 0.2g
When the infrared absorption spectrum of the obtained cellobiosylamine derivative product of itaconic acid was measured (FIG. 5), a peak derived from NH stretching vibration and C = O stretching vibration was observed near 1650 cm ⁻¹ . It was. The product peak was isolated by HPLC of the product (FIG. 6).
The HPLC conditions are as follows.
-Column used: Grand120-STC 18-5
Column size: 4.6 mm D. × 150mm
Eluent: H ₂ O (TFA 0.1%)
・ Temperature: 35 ℃
Detector: RI (differential refractive index), UV (wavelength 210 nm)
A fraction of the peak of the main product in FIG. 6 is collected, and the eluent is distilled off, followed by lyophilization, whereby general formula (VII) (wherein R ′ is a glucose residue, X is a hydrogen atom) The cellobiosylamine derivative of itaconic acid represented by the following formula was obtained.
FIG. 7 shows the proton nuclear magnetic resonance spectrum (D ₂ O) of the cellobiosylamine derivative of itaconic acid obtained by HPLC fractionation.
When the biodegradability test of the obtained cellobiosylamine derivative of itaconic acid was performed based on ISO148851, JIS K6950, a biodegradability of 49.5% was obtained in 28 days.

Example 3 Polymerization of Itaconic Acid Glucosamine Derivative Itaconic acid glucosamine derivative (general formula (VI), X: hydrogen atom) 3.0 g (10 mmol) and sodium hypophosphite monohydrate 1.3 g (12 mmol) In addition to 8 ml of water, the temperature was raised to 95 ° C. under nitrogen flow, 0.35 g (1.3 mmol) of potassium peroxodisulfate was added in three portions, and the mixture was reacted at 95 ° C. for 12 hours under nitrogen flow. After completion of the reaction, it was placed in a cellulose tube having a molecular weight cut off of 1000 and purified by dialysis for 3 days, followed by lyophilization to obtain 0.1 g of a polymer represented by the general formula (VIII).
The proton nuclear magnetic resonance spectrum of the obtained polymer is shown in FIG.

Example 4 Polymerization of a cellobiosylamine derivative of itaconic acid 1.00 g (2.2 mmol) of itaconic acid cellobiosylamine derivative (general formula (VII), R ′: glucose residue, X: hydrogen atom) and hypophosphorous acid Sodium sulfate monohydrate 0.26 g (2.4 mmol) was added to 8 ml of water, the temperature was raised to 95 ° C. under nitrogen flow, and 0.07 mg (0.3 mmol) of potassium peroxodisulfate was divided into three portions. In addition, it reacted for 12 hours. After completion of the reaction, the mixture was put into a cellulose tube having a molecular weight cut off of 1000 and purified by dialysis for 3 days, and then lyophilized to obtain 0.1 g of a polymer represented by the formula (IX).
The proton nuclear magnetic resonance spectrum of the obtained polymer is shown in FIG.

  As described above, according to the present invention, a novel itaconic acid sugar derivative having an unsaturated bond having a sugar residue can be easily produced. These polymers are used as raw materials for paper chemicals, water treatment agents, cosmetics, concrete admixtures, sanitary materials, etc., or as raw materials for electronic material cleaners as metal ion collectors, or as raw materials for household cleaners. There is a possibility that it can be utilized.

It is an infrared absorption spectrum of a glucosamine derivative product of itaconic acid. It is a HPLC chromatogram of the product of the glucosamine derivative of itaconic acid, (a) using a RI (differential refractive index) detector, and (b) using a UV detector. It is a proton nuclear magnetic resonance spectrum of the compound obtained from fractions of HPLC chromatogram of FIG. _{2 (a) (D 2 O} ). It is a proton nuclear magnetic resonance spectrum of the compound obtained from the fraction (b) of the HPLC chromatogram of FIG. ₂ (D 2 O). It is an infrared absorption spectrum of the cellobiosylamine derivative product of itaconic acid. It is a HPLC chromatogram of the cellobiosylamine derivative product of itaconic acid, (A) is using a RI (differential refractive index) detector, (A) is using a UV detector. Is a proton nuclear magnetic resonance spectrum of the compound obtained from the product fractions HPLC chromatogram of FIG. 6 (D ₂ O). It is a proton nuclear magnetic resonance spectrum of a polymer of a glucosamine derivative of itaconic acid. It is a proton nuclear magnetic resonance spectrum of a polymer of a cellobiose derivative of itaconic acid.

Claims (3)

Itaconyl-glucosylamine represented by the general formula (VII) (wherein X represents a hydrogen atom or an alkali metal atom and R ′ represents a hydrogen atom) or an alkali metal salt thereof, or a compound represented by the general formula (VII) ( In the formula, X represents a hydrogen atom or an alkali metal atom, and R ′ represents a glucose residue.) Itaconic sugar derivative which is an itaconyl-cellobiosylamine or an alkali metal salt thereof .

Itaconic anhydride and the general formula (IV) (wherein, R has the general formula (III) (wherein, R 'represents. A residue represented by represents.) A hydrogen atom or a glucose residue) represented by The method for producing an itaconic acid sugar derivative according to claim 1, wherein the amino sugar is reacted in a water-containing organic solvent in the presence of an alkali.


General formula (IX) (wherein R ′ represents a hydrogen atom, X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more), or general formula (IX) (wherein R 'Represents a glucose residue, X represents a hydrogen atom or an alkali metal atom, and n represents an integer of 2 or more.)