JP4956111B2 - Production method of polysaccharide derivatives - Google Patents

Description

  The present invention relates to an efficient method for producing polysaccharide derivatives useful as thickeners, gelling agents, excipients, emulsion stabilizers, flocculants, etc. for cosmetics, toiletry products, external medicines, water-soluble paints, building materials, etc. About.

  A polysaccharide derivative in which a substituent is introduced into part or all of the hydroxy group of the polysaccharide is a useful compound used in various cosmetics, toiletries and the like. For example, a polysaccharide sulfonated product in which some or all of the hydrogen atoms of the hydroxy group of the polysaccharide are substituted with a long-chain alkyl glyceryl ether group and / or a long-chain alkenyl glyceryl ether group and a sulfonic acid group-containing substituent. It has been reported that it is excellent in water solubility, its aqueous solution exhibits stable and high viscosity at low concentration and excellent emulsification stabilization action, and has a good feeling when used in cosmetics and toiletry products ( Patent Document 1).

The above-mentioned polysaccharide sulfonated product can be produced by a polysaccharide hydrophobization (long-chain alkyl glyceryl etherification and / or long-chain alkenyl glyceryl etherification) reaction and sulfonation reaction. However, in these reactions, since solvolysis of the hydrophobizing agent and sulfonating agent can occur as a side reaction, the yield becomes low, so a large excess of hydrophobizing agent and sulfonating agent is required, In addition, since polysaccharides have low solubility in solvents, they generally require a large excess of organic solvent and water. These led to a decrease in productivity and an increase in the purification load of the product, and there were also problems from an economic viewpoint. Therefore, the amount of water used as a reaction solvent so far is set to the minimum necessary amount, and by reacting with a reactive agent having an epoxy group or a polyoxyalkylene agent without dissolving the polysaccharide, Solvent decomposition is suppressed and reaction selectivity is remarkably improved, and a method for solving these problems has been found (Patent Document 2).
JP 09-235301 A JP 2002-114801 A

However, after reacting under alkaline conditions, when adding an acid necessary for neutralization, an inorganic acid represented by hydrochloric acid or sulfuric acid, or an organic acid represented by acetic acid or succinic acid is used to increase the normal dispersibility. When dissolved in water and added, large aggregated polysaccharide aggregates are formed, and there is a problem that productivity is lowered.
An object of the present invention is to provide a method for producing a polysaccharide derivative efficiently and industrially advantageously from the initial stage of the reaction to the treatment after the reaction, and more efficiently and with high productivity.

  The present inventors completed the neutralization reaction by adding the acid in the form of powder or slurry in the addition of the neutralized acid after the completion of the reaction, utilizing the dissolution / dispersion by water existing in the reaction system. It was found that the yield after classification can be improved and the productivity of polysaccharide derivatives can be improved by suppressing the formation of large aggregated aggregates of polysaccharides.

That is, the present invention provides the following (a), (b), (c), (d), (e) and (f) to a polysaccharide or a lower alkyl or hydroxy lower alkyl substituted product thereof.
(A) Glycidyl ether having an alkyl group or alkenyl group having 10 to 40 carbon atoms (b) Epoxyalkanesulfonic acid or salt thereof (c) Epoxy fatty acid or salt thereof (d) Epoxyalkylamine or ammonium salt derived therefrom e) Epoxy alkyl phosphate ester or salt thereof (f) The following general formula (1):
E ^3- (OA) _n -E ² -R (1)
[Wherein E ³ is an epoxidized alkyl group having 3 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, or a carboxy group or a carboxyalkyl having 2 to 6 carbon atoms. A group or a derivative thereof, n represents a number of 8 to 300, n A are the same or different and represent a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and E ² represents an ether bond or Represents an oxycarbonyl group, and R represents an alkyl group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. In the reaction to obtain a polysaccharide derivative by reacting with one or more epoxy compounds or polyoxyalkylene agents selected from the polyoxyalkylene agents represented by the formula: The present invention provides a method for producing a polysaccharide derivative characterized in that an acid is used as a reaction solvent, and an acid is charged in powder form or slurry form for neutralization after completion of the reaction.

  According to the present invention, from the initial reaction stage to the post-reaction treatment can be efficiently and industrially advantageously performed stably, and polysaccharide derivatives useful in various fields are produced efficiently and with high productivity. be able to.

  Examples of the polysaccharide used as a raw material in the method of the present invention or a lower alkyl or hydroxy lower alkyl substituted product thereof include natural polysaccharides such as cellulose, guar gum, starch, inulin, pullulan, curdlan, chitin, chitosan, etc., and lower levels of these natural polysaccharides. Examples include alkyl-substituted products and hydroxy-lower alkyl-substituted products of these natural polysaccharides. Here, examples of the lower alkyl group include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the hydroxy lower alkyl group include hydroxyalkyl groups having 4 to 6 carbon atoms such as a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

  Examples of these polysaccharides and substitution products thereof (collectively referred to as raw material polysaccharides) include, for example, cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, Preferred are ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, etc. Can be mentioned. Particularly preferred raw material polysaccharides include hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose and the like. Among these, hydroxyethyl cellulose is particularly preferable. Moreover, the substituent of the lower alkyl group or hydroxy lower alkyl group of these raw material polysaccharides may be substituted with a single substituent or may be substituted with a plurality of substituents. Further, the substitution degree per constituent monosaccharide residue is preferably from 0.1 to 10, and more preferably from 0.5 to 5. Moreover, the weight average molecular weight of these polysaccharides becomes like this. Preferably it is 10,000-10 million, More preferably, it is 50,000-5 million, More preferably, it is 100,000-2 million, Most preferably, it is the range of 200,000-1 million. The weight average molecular weight can be measured by GPC-LALLS method. One or more of these raw material polysaccharides can be used.

In the present invention, the epoxy compound selected from the above (a) to (e), or (f) the polyoxyalkylene agent, compound (a) = hydrophobizing agent, compound (b) = sulfonating agent, compound ( c) = carboxylating agent, compound (d) = aminating agent, compound (e) = phosphorylating agent, compound (f) = polyoxyalkylene agent. When these compounds are reacted with the raw material polysaccharide, some or all of the hydrogen atoms of the hydroxy group of the raw material polysaccharide are the following (A), (B), (C), (D), (E): And (F)
(A) an alkyl or alkenyl glyceryl ether group (B) a sulfoalkyl group having a hydroxy group or a salt thereof (C) a carboxyalkyl group having a hydroxy group or a salt thereof (D) an aminoalkyl group or an ammonium alkyl group having a hydroxy group E) An alkyl phosphate group having a hydroxy group or a salt thereof (F) The following general formula (2):
-E ^1- (OA) _n -E ² -R (2)
Wherein, E ¹ represents a divalent saturated hydrocarbon group, a carbonyl group, or an alkanoyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms which may be substituted with a hydroxy group, n represents 8-300 N is the same or different and represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, E ² represents an ether bond or an oxycarbonyl group, and R is substituted with a hydroxy group. An alkyl group having 4 to 30 carbon atoms which may be present. ] [The hydrogen atom of the hydroxy group of the substituent (F) may be further substituted with the substituent (F)]
A polysaccharide derivative substituted with one or more groups selected from is obtained.

<Compound (a) = Hydrophobizing agent>
When the raw material polysaccharide is reacted with the compound (a), a hydrophobic polysaccharide in which the hydrophobic substituent (A) is introduced into the raw material polysaccharide can be obtained. The alkyl group and alkenyl group of the glycidyl ether (a) having an alkyl group or an alkenyl group used for the hydrophobization reaction preferably have 10 to 40 carbon atoms, and may be either linear or branched. The number and position of unsaturated bonds in the alkenyl group are not particularly limited. Specific examples of the alkyl group include a linear alkyl group such as n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n -Heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, n-hentriacontyl group, n-dotriacontyl group, n-tritriacontyl group, n-tetratriacontyl group, n-pentatria Contyl group, n-hexatriacontyl group, n-heptatriacontyl group, n-octatriacontyl group, n-no Triacontyl and n- tetracontyl group. As the branched alkyl group, methylundecyl group, methylheptadecyl group, ethylhexadecyl group, methyloctadecyl group, propylpentadecyl group, 2-hexyldecyl group, 2-octyldodecyl, 2-heptylundecyl group, 2-decyl Examples include a tetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecyloctadecyl group, and a 2-tetradecylbehenyl group. Specific examples of the alkenyl group include a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an icosenyl group, a heicocosenyl group, a dococenyl group, a tricosenyl group, Examples include a tetracocenyl group, a pentacocenyl group, a hexacocenyl group, a heptacocenyl group, an octacocenyl group, a nonacosenyl group, a triaconenyl group, an oleyl group, a linoleyl group, and a linolenyl group. Among these, an alkyl group and an alkenyl group having 12 to 36 carbon atoms, particularly 16 to 24 carbon atoms are preferable, and an alkyl group, particularly a linear alkyl group is preferable from the viewpoint of stability. One or more of these hydrophobizing agents (a) can be used.

<Compound (b) = sulfonating agent>
When the compound (b) is reacted with the raw material polysaccharide, the substituent (B) can be introduced into the raw material polysaccharide. As a C2-C5 epoxy alkanesulfonic acid which is a sulfonating agent (b), 1,2-epoxyethanesulfonic acid, 2,3-epoxypropanesulfonic acid, 3,4-epoxybutanesulfonic acid, 2, 3-epoxy-1-methylpropanesulfonic acid, 4,5-epoxypentanesulfonic acid, 3,4-epoxy-1-methylbutanesulfonic acid, 3,4-epoxy-2-methylbutanesulfonic acid, 2,3- Examples include epoxy-1,1-dimethylpropanesulfonic acid. Examples of these salts include alkali metal salts such as sodium salts and potassium salts, group 2 element salts such as calcium salts and magnesium salts, and ammonium salts. One or more of these sulfonating agents (b) can be used.

<Compound (c) = Carboxylating agent>
When the compound (c) is reacted with the raw material polysaccharide, the substituent (C) can be introduced into the raw material polysaccharide. Examples of the carboxylate (c) epoxy fatty acid having 3 to 6 carbon atoms include 2,3-epoxypropionic acid, 3,4-epoxybutyric acid, 4,5-epoxyvaleric acid, and 3,4-epoxy-2- Examples include methylbutyric acid, 5,6-epoxyhexanoic acid, 4,5-epoxy-2-methylvaleric acid, 4,5-epoxy-3-methylvaleric acid, 3,4-epoxy-2,2-dimethylbutyric acid, and the like. It is done. Examples of these salts include alkali metal salts such as sodium salts and potassium salts, group 2 element salts such as calcium salts and magnesium salts, and ammonium salts. These carboxylating agents (c) can use 1 or more types.

<Compound (d) = Aminating agent>
When the compound (d) is reacted with the raw material polysaccharide, the substituent (D) can be introduced into the raw material polysaccharide. Examples of the epoxyalkylamine having 2 to 5 carbon atoms as the aminating agent (d) include 1,2-epoxyethylamine, 2,3-epoxypropylamine, 3,4-epoxybutylamine, 2,3-epoxy-1- Examples include methylpropylamine, 4,5-epoxypentylamine, 3,4-epoxy-1-methylbutylamine, 3,4-epoxy-2-methylbutylamine, 2,3-epoxy-1,1-dimethylpropylamine, and the like. It is done. Examples of ammonium salts derived from these include those having a counter ion such as a halide ion such as fluoride ion, chloride ion, bromide ion, or iodide ion. One or more of these aminating agents (d) can be used.

<Compound (e) = Phosphorylating agent>
When the compound (e) is reacted with the raw material polysaccharide, the substituent (E) can be introduced into the raw material polysaccharide. Examples of the phosphoric acid ester (e) having 2 to 5 carbon atoms include phosphoric acid 1,2-epoxyethyl ester, phosphoric acid 2,3-epoxypropyl ester, phosphoric acid 3,4-epoxybutyl ester 2,3-epoxy-1-methylpropyl ester of phosphoric acid, 4,5-epoxypentyl ester of phosphoric acid, 3,4-epoxy-1-methylbutyl phosphate, 3,4-epoxy-2-methyl phosphate Examples thereof include butyl ester and phosphoric acid 2,3-epoxy-1,1-dimethylpropyl ester. Examples of these salts include alkali metal salts such as sodium salts and potassium salts, group 2 element salts such as calcium salts and magnesium salts, and ammonium salts. These phosphorylating agents (b) can use 1 or more types.

<Compound (f) = Polyoxyalkylene agent>
When the compound (f) is reacted with the raw material polysaccharide, the substituent (F) can be introduced into the raw material polysaccharide. As a compound of the said General formula (1) which is a polyoxyalkylene agent (f), the following compounds are mentioned, for example.
Among the groups represented by E ³ in the general formula (1), as the epoxidized alkyl group having 3 to 6 carbon atoms, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl Group, a 5,6-epoxyhexyl group, and the like. Examples of the linear or branched alkyl halide group having 1 to 6 carbon atoms which may be substituted with a hydroxy group include a 2-chloroethyl group, a 3-chloropropyl group, a 4-chlorobutyl group, a 6-chlorohexyl group, Examples include 2-bromoethyl group, 2-hydroxy-3-chloropropyl group, 1-hydroxymethyl-2-chloroethyl group and the like. Examples of the carboxyalkyl group having 2 to 6 carbon atoms include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, and a carboxypentyl group. Examples of these carboxyalkyl groups or carboxy group derivatives include methyl esterified products, ethyl esterified products, acid halides, tosylated products, mesylated products, and anhydrides. Of the groups represented by E ³ , 2,3-epoxypropyl group; 2-chloroethyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group; carboxymethyl group, carboxyethyl group and Examples thereof include methyl esterified products and acid halides.
These polyoxyalkylene agents (f) can be used alone or in combination of two or more.

  By selecting one or more compounds from these compounds (a) to (f) according to the purpose of use and reacting them with the raw material polysaccharide, one or more compounds selected from the substituents (A) to (F) that are the target compounds are used. A polysaccharide derivative having a group can be obtained, and it is possible to obtain a polysaccharide derivative having two or more substituents corresponding to these by reacting two or more compounds selected from the compounds (a) to (f). preferable. Among these, a hydrophobic agent (a) is used as one of the two or more compounds, a compound selected from the compounds (b) to (f) is used as the other compound, and the hydrophobic substituent (A) and It is preferable to obtain a polysaccharide derivative having a group selected from the substituents (B) to (F), and in particular, using the hydrophobizing agent (a) and the sulfonating agent (b), the hydrophobic substituent (A And a polysaccharide derivative having a sulfonic acid group (B). In addition, it is also preferable to obtain a polysaccharide using the polyoxyalkylene agent (f). In addition, reaction with 2 or more types of compounds (a)-(f) and raw material polysaccharide may be performed first, and may be performed simultaneously, but when a hydrophobization reaction is included, More preferably, this is done first.

  The amount of the compounds (a) to (f) used can be appropriately adjusted depending on the desired amount of the substituents (A) to (F) introduced into the raw polysaccharide, but is usually a constituent monosaccharide of the raw polysaccharide. Hydrophobizing agents (a) and (f) per residue are preferably in the range of 0.0001 to 10 equivalents, particularly 0.0003 to 1 equivalents, and compounds (b) to (e) are preferably 0.01 to 10 equivalents, The range of 0.05-3 equivalent is especially preferable.

  The reaction between the raw material polysaccharide and the compounds (a) to (f) is from 5 to 150% by weight, preferably 10%, based on the raw material polysaccharide as a reaction solvent, from the viewpoint of improving productivity, reducing purification load, and economical viewpoint. It is carried out using a solvent containing -80% by weight, in particular 20-70% by weight of water. In addition, 5-300 weight with respect to raw material polysaccharide with water at the point which can improve the solubility of compound (a)-(f) and can introduce substituent (A)-(F) into raw material polysaccharide efficiently. %, Preferably 20 to 80% by weight, particularly 30 to 70% by weight, in a mixed solvent using an aliphatic alcohol having 1 to 5 carbon atoms. Here, the mixing ratio of water and the aliphatic alcohol is preferably 5:95 to 90:10, particularly preferably 10:90 to 60:40. The total amount of water and aliphatic alcohol is 10 to 300% by weight, more preferably 30 to 200% by weight, particularly 50 to 150% with respect to the raw material polysaccharide, from the viewpoint of improving productivity, reducing purification load, and economical viewpoint. % By weight is preferred. In the present invention, the amount of solvent to be used is the minimum necessary for the reaction of the polysaccharide, and thus a high reaction selectivity can be obtained. It is preferable to use a kneader used for mixing a body and a high-viscosity substance as a reaction apparatus. Here, the kneader is a kneader having a stirring blade and a stirring blade, and a commercially available kneader can be used.

  Each reaction is preferably carried out in the presence of an alkali. Examples of such an alkali include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, etc., among which sodium hydroxide, potassium hydroxide, Calcium hydroxide and magnesium hydroxide are preferred. The amount of alkali used is from 0.1 to 300 mol times, more preferably from 1 to 100 mol times, particularly from 1 to 50 mol times the amount of the hydrophobizing agents (a) and (f) used in the hydrophobization reaction. However, in the reaction of the compounds (b) to (e) with the raw material polysaccharide, the compound (b) to (e) is 0.01 to 300 mole times, more preferably 0.1 to 100 mole times, An amount of 1 to 50 mole times is preferable because it gives good results.

The reaction temperature is preferably in the range of 0 to 200 ° C, particularly 30 to 100 ° C for any reaction. After completion of the reaction, it is necessary to neutralize the alkali with an acid. In this addition of the neutralized acid, the acid is present in the reaction system by charging the powder in a powder or slurry and mixing with heating. It is possible to complete the neutralization reaction efficiently by using dissolution and dispersion with water. Examples of the powdered or slurry acid include succinic acid, citric acid, malic acid, oxalic acid, and adipic acid. Of these, succinic acid and citric acid are particularly preferable because the neutralization reaction can be performed quickly and easily. For the same reason, the average particle diameter of the powdered acid is preferably 0.01 to 5 mm, particularly preferably 0.1 to 1 mm. Here, the average particle size can be measured by, for example, LA-910 manufactured by Horiba. As the slurry acid, an acid C ₁ -C ₅ aliphatic alcohol slurry or the like is used. The weight ratio of the acid to the C ₁ -C ₅ aliphatic alcohol in the slurry is preferably 5: 1 to 1: 5, particularly 3: 1 to 1: 3. Neutralization by addition of powdered or slurry-like acid can suppress the formation of large massive polysaccharide aggregates that occur when an acid aqueous solution is added, and the productivity is greatly improved. Moreover, the next reaction can also be performed without neutralizing on the way. In addition, you may use acid aqueous solution together in the range which does not impair the effect of this invention.

  The polysaccharide derivative obtained in each reaction can be used as it is without being neutralized when used in the next reaction, and can be separated by filtration or the like as necessary, or with hot water or hydrous isopropyl alcohol. It is also possible to use the product by washing with a water-containing acetone solvent or the like to remove unreacted hydrophobizing agent or salts by-produced by neutralization or the like. Moreover, when drying, drying can also be performed within a kneader. After all the reactions are completed, the target polysaccharide derivative can be obtained by performing washing, neutralization, and the like as necessary, followed by drying.

  In the following examples and comparative examples, the substitution degree of the substituents (A) and (F) of the polysaccharide derivative is determined by decomposing the polysaccharide derivative of known weight with excess hydroiodic acid, and converting the resulting alkyl iodide. It calculated by quantifying (Analytical Chemistry, 1979, Vol..51, No.13, 2172). Further, the substitution degree of the substituents (B), (C), (D) and (E) was determined by a colloid titration method (colloidal titration method “1969 Junichi Chite, Nankodo”). Here, the “degree of substitution” indicates the average number of substituents per constituent monosaccharide residue.

Example 1
In a 5 L table type kneader equipped with a cooling tube, 1000 g of hydroxyethyl cellulose (SE390, manufactured by Daicel Chemical Industries, Ltd., hereinafter referred to as “HEC”) having a weight average molecular weight of 200,000 and a hydroxyethyl group substitution degree of 2.5 is added and stirred. 500 g of isopropyl alcohol (hereinafter “IPA”), 50.65 g of compound A shown in Table 1, 61.21 g of 48% aqueous sodium hydroxide, and 68.2 g of water were added. After reducing the pressure to 13.3 kPa, the operation of returning to normal pressure with nitrogen was repeated three times to replace the interior with nitrogen, and the temperature was raised to 76 ° C. and stirred and reacted for 10 hours. After completion of the reaction, the mixture was cooled to 50 ° C. or less, 43.38 g of succinic acid powder was added to the mixture, the temperature was raised again to 75 ° C., and a neutralization reaction was performed for 3 hours. After completion of neutralization, the solvent was distilled off at 75 ° C. under reduced pressure (26.6 kPa) to obtain 1055 g of a polyoxyalkylenated HEC derivative (polysaccharide derivative (1)).
The substitution degree of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (1) was 0.0144.
Furthermore, the polysaccharide derivative (1) was classified with a wire mesh having an aperture of 0.85 mm to obtain 930 g of a pass product.

Example 2
1050 g of HEC derivative (polysaccharide derivative (2)) in the same manner as in Example 1 except that the mixture after the reaction was cooled to 50 ° C. or less and neutralized by adding a slurry consisting of 43.38 g of succinic acid and 30 g of IPA. Got.
The substitution degree of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (2) was 0.0143.
Furthermore, the polysaccharide derivative (2) was classified with a wire mesh having an aperture of 0.85 mm to obtain 920 g of a pass product.

Example 3
To a 5 L table type kneader equipped with a cooling pipe, 1000 g of hydroxyethyl cellulose (NATROSOL 250HHX, manufactured by HERCULES, hereinafter “HEC”) having a weight average molecular weight of 1.5 million and a hydroxyethyl group substitution degree of 2.5 and 6.57 g of stearyl glycidyl ether were added. Prepared. After reducing the pressure to 13.3 kPa, the operation of returning to normal pressure with nitrogen was repeated three times to replace the inside with nitrogen, and oxygen in the reaction system was removed. After substitution with nitrogen, 500 g of isopropyl alcohol was added at room temperature while stirring the powder, and after 5 minutes, a mixed solution of 33.6 g of 48 wt% aqueous sodium hydroxide and 385 g of ion-exchanged water was gradually added while stirring the powder. Added to. After reducing the pressure to 13.3 kPa again, the operation of returning to normal pressure with nitrogen was repeated three times to replace the inside with nitrogen, the temperature was raised to 76 ° C., and the mixture was stirred and mixed for 9 hours to perform a hydrophobic reaction. Thereafter, the mixture was cooled to 50 ° C., and 370 g of a separately prepared aqueous sodium 2,3-epoxypropanesulfonate (purity = 29%) 370 g was slowly added while continuing stirring, and the sulfonation reaction was carried out at 50 ° C. for 8 hours. . After completion of the sulfonation reaction, the mixture was cooled to 30 ° C. or lower, 23.8 g of succinic acid powder was added to the mixture, the temperature was raised again to 75 ° C., and a neutralization reaction was performed for 3 hours. After completion of neutralization, the solvent was distilled off at 75 ° C. under reduced pressure (26.6 kPa) to obtain 1110 g of an HEC derivative (polysaccharide derivative (3)).
In the obtained polysaccharide derivative (3), the degree of substitution of the substituent containing 3-stearyloxy-2-hydroxypropyl group was 0.0037, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.118. .
Furthermore, the polysaccharide derivative (3) was classified with a wire mesh having an aperture of 0.85 mm to obtain 910 g of a pass product.

Comparative Example 1
The method of Example 1 except that after completion of the reaction, the mixture was cooled to 50 ° C. or lower, an aqueous solution obtained by dissolving 43.38 g of succinic acid in 174 g of hot water was added to the mixture, and the mixture was mixed at 30 ° C. for 6 hours to carry out a neutralization reaction Thus, 1010 g of a polyoxyalkylenated HEC derivative (polysaccharide derivative (4)) was obtained.
The substitution degree of the substituent containing the polyoxyalkylene group of the obtained polysaccharide derivative (4) was 0.0144.
Furthermore, the polysaccharide derivative (4) was classified with a wire mesh having an aperture of 0.85 mm to obtain 655 g of a pass product.

Comparative Example 2
The method of Example 3 except that after completion of the reaction, the mixture was cooled to 30 ° C. or lower, an aqueous solution in which 23.8 g of succinic acid was dissolved in 95 g of hot water was added to the mixture, and the mixture was mixed at 30 ° C. for 1 hour for neutralization reaction Thus, 1090 g of HEC derivative (polysaccharide derivative (5)) was obtained.
The degree of substitution of the substituent containing 3-stearyloxy-2-hydroxypropyl group of the obtained polysaccharide derivative (5) was 0.0037, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.115. .
Furthermore, the polysaccharide derivative (5) was classified with a wire mesh having an aperture of 0.85 mm to obtain 761 g of a pass product.

  Table 1 shows the results of Examples 1 to 3 and Comparative Examples 1 and 2.

  As is clear from Table 1, in Examples 1 to 3, the yield and yield improved through a wire mesh of 0.85 mm compared to Comparative Examples 1 and 2. This is because succinic acid necessary for neutralization was added in powder, and the amount of water in the reaction system could be kept smaller than when added with a conventional aqueous solution. It originates from the fact that it was able to be suppressed. This increase in yield was also observed when succinic acid dispersed with isopropyl alcohol that does not dissolve the polysaccharide was added. Usually, when neutralizing with a solid acid, there is a problem that the dispersibility is poor and it is difficult to neutralize, but in the present invention, dissolution / dispersion with water that was previously present in the reaction system by heating and mixing is used. It was found that the neutralization reaction can be completed. Along with this increase in yield, the method of the present invention makes it possible to produce polysaccharide derivatives efficiently and with high productivity.

Claims (4)

The following (a), (b), (c), (d), (e) and (f) are added to the polysaccharide or its lower alkyl or hydroxy lower alkyl substituted product.
(A) Glycidyl ether having an alkyl group or alkenyl group having 10 to 40 carbon atoms (b) Epoxyalkanesulfonic acid or salt thereof (c) Epoxy fatty acid or salt thereof (d) Epoxyalkylamine or ammonium salt derived therefrom e) Epoxy alkyl phosphate ester or salt thereof (f) The following general formula (1):
E ^3- (OA) _n -E ² -R (1)
[Wherein E ³ is an epoxidized alkyl group having 3 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, or a carboxy group or a carboxyalkyl having 2 to 6 carbon atoms. A group or a derivative thereof, n represents a number of 8 to 300, n A are the same or different and represent a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and E ² represents an ether bond or Represents an oxycarbonyl group, and R represents an alkyl group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. In the reaction to obtain a polysaccharide derivative by reacting with one or more epoxy compounds or polyoxyalkylene agents selected from the polyoxyalkylene agents represented by the formula: A method for producing a polysaccharide derivative, comprising using a solvent containing a succinic acid or citric acid as a reaction solvent for neutralization after completion of the reaction in a powder form or a slurry form.   The manufacturing method of Claim 1 which uses a kneader as a reaction apparatus.   The production method according to claim 1 or 2, wherein the raw material polysaccharide has a weight average molecular weight of 10,000 to 10,000,000. The production method according to any one of claims 1 to 3, wherein succinic acid or citric acid is charged in powder form or slurry form for neutralization after completion of the reaction and heated and mixed.