JP3973823B2 - Production method of sulfonated polysaccharide - Google Patents

Description

【００２８】
表１から明らかなように、実施例１〜５では比較例よりもスルホン基の置換度の向上が見られる。これは、エポキシドの反応性の高さから多糖への選択的な反応が起こるためであると考えられる。更に反応終了時に副生塩が生成しない事等から精製工程における負荷の低減も可能であることから、炭素数1〜5のエポキシドを有するスルホン酸又はこれらの塩を用いてスルホン化反応を行なうことは、工業的にも好ましいといえる。
【００２９】
【発明の効果】
本発明によれば、水溶液としたとき透明性に優れ、しかも低濃度で優れた増粘性を示し、金属塩の共存や温度の変化が少なく、更に乳化安定性が極めて良好な多糖類スルホン化体を工業的に有利に提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention provides an efficient polysaccharide sulfonated product useful as a thickener, gelling agent, excipient, emulsion stabilizer, flocculant, etc. for cosmetics, toiletry products, external medicines, water-soluble paints, building materials, etc. It relates to the manufacturing method.
[0002]
[Prior art]
A polysaccharide derivative obtained by substitution with a long-chain alkyl glyceryl ether group and / or a long-chain alkenyl glyceryl ether group and a substituent containing sulfonic acid is excellent in water solubility, and its aqueous solution exhibits high viscosity at a low concentration, In addition, it is not easily affected by inorganic metal salts, organic metal salts, pH, temperature, etc., exhibits stable thickening, exhibits excellent emulsification stabilization, and has a good feeling when used in cosmetics and toiletry products. Have been reported (Japanese Patent Laid-Open No. 09-235301, etc.).
[0003]
The above-mentioned polysaccharide derivative containing a long-chain alkyl glyceryl ether group and / or a long-chain alkenyl glyceryl ether group and a sulfonic acid as a substituent is obtained by hydrophobizing a polysaccharide or a derivative thereof (long-chain alkyl glyceryl etherification and / or long-chain alkenyl). (Glyceryl etherification) reaction and sulfonation reaction. However, in general, polysaccharides are poorly soluble in solvents, and the yields in both the hydrophobing and sulfonation steps are low unless a compound with adequate reactivity with polysaccharides is selected for the hydrophobizing and sulfonating agents. Therefore, it becomes necessary to use a large excess of the hydrophobizing agent and sulfonating agent for the desired degree of substitution. In the sulfonation reaction, for example, when using a sulfonating agent selected from haloalkanesulfonic acids and salts thereof, which may be substituted with a hydroxyl group having 1 to 5 carbon atoms, it is possible to avoid the formation of inorganic salts as by-products. Absent. These have the problem of reducing productivity and increasing the purification load when the product needs to be purified, which contributes to an increase in production cost.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing the above polysaccharide derivative which is efficient and has improved productivity.
[0005]
[Means for Solving the Problems]
In the sulfonation reaction, the present inventors use a sulfonating agent selected from a sulfonic acid having an epoxide having 1 to 5 carbon atoms and a salt thereof to selectively select a polysaccharide from the high reactivity of the epoxide. It has been found that the reaction takes place, the amount of the sulfonating agent used can be reduced, and at the same time the inorganic salt produced as a by-product in the sulfonation reaction can be reduced, so that the purification load can be reduced.
[0006]
In the present invention, (a) a hydroxyl group may be substituted in the polysaccharide, and an oxycarbonyl group (—COO— or —OCO—) or an ether bond may be inserted. A part of the hydrogen atom of the hydroxyl group of the polysaccharide, in which a glycidyl ether having a linear or branched alkyl group or alkenyl group is reacted with (b) a sulfonic acid having an epoxide having 1 to 5 carbon atoms or a salt thereof. Or all provide the manufacturing method of the polysaccharide sulfonated body substituted by the following (A) and (B).
(A) A linear or branched alkyl group having 10 to 43 carbon atoms, which may be substituted with a hydroxyl group, and into which an oxycarbonyl group (—COO— or —OCO—) or an ether bond may be inserted Or an alkenyl group,
(B) A sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or a salt thereof.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The raw material polysaccharide used in the present invention is cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum Preferred are those selected from the group consisting of hydroxypropyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum and hydroxypropyl methyl starch. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group and the like of these raw material polysaccharides may be substituted with a single substituent, or may be substituted with a plurality of substituents. Well, the substitution degree per constituent monosaccharide residue is preferably 0.1 to 10, more preferably 0.5 to 5. These polysaccharides preferably have a weight average molecular weight in the range of 10,000 to 10,000,000, more preferably 100,000 to 5,000,000.
[0008]
The description will be divided into the hydrophobization reaction (reaction of hydrophobizing agent (a); substitution by group (A)) and the sulfonation reaction (reaction of sulfonating agent (b); substitution by group (B)). Either the hydrophobization reaction or the sulfonation reaction may be performed first or simultaneously, but it is preferable that the hydrophobization is followed by sulfonation.
[0009]
<Hydrophobic reaction>
The hydrophobization reaction of the polysaccharide or sulfonated polysaccharide is carried out by dissolving or dispersing the polysaccharide or sulfonated polysaccharide in an appropriate solvent and reacting with the hydrophobizing agent (a).
[0010]
The alkyl group and alkenyl group of the C10-C40 alkyl glycidyl ether and C10-C40 alkenyl glycidyl ether used in the hydrophobization reaction may be either linear or branched. The branch position in the case of branching, the unsaturated bond in the alkenyl group The number and position of are not particularly limited. Further, the C10 to C40 teralkyl or alkenyl group may be substituted with a hydroxy group, or an oxycarbonyl group or an ether bond may be inserted. 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-nonatriacontyl group and n-tetracontyl group are methylundecyl groups as branched alkyl groups. Group, methylheptadecyl group, ethylhexadecyl group, methyloctadecyl group, propylpentadecyl group, 2-hexyldecyl group, 2-octyldodecyl, 2-heptylundecyl group, 2-decyltetradecyl group, 2-dodecylhexa A decyl group, 2-tetradecyl octadecyl group, 2-tetradecyl behenyl group and the like can be mentioned. 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, A tetracocenyl group, a pentacocenyl group, a hexacocenyl group, a heptacocenyl group, an octacocenyl group, a nonacocenyl group, a triacontenyl group, an oleyl group, a linoleyl group, a linolenyl group, and the like can be given. 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. These hydrophobizing agents (a) can be used alone or in combination of two or more. The amount of the hydrophobizing agent (a) used can be appropriately adjusted depending on the desired amount of the hydrophobic substituent introduced into the polysaccharide or derivative thereof, but is usually per constituent monosaccharide residue of the polysaccharide or derivative thereof. , 0.0001 to 10 equivalents, particularly preferably 0.0003 to 1 equivalents.
[0011]
The hydrophobization 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 and potassium hydroxide. , Calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of alkali used is preferably 0.01 to 10 mol times, particularly 0.1 to 5 mol times the amount of the hydrophobizing agent (a) to be used.
[0012]
Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. In order to increase the reactivity with the hydrophobizing agent (a) by swelling the polysaccharide or the sulfonated polysaccharide, 1 to 50% by weight, more preferably 2 to 30% by weight of water is added to the lower alcohol. The reaction may be performed using a mixed solvent.
[0013]
The reaction temperature is 0 to 200 ° C, preferably 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. Moreover, the next reaction can also be performed without neutralizing on the way.
[0014]
When the thus obtained hydrophobized polysaccharide is subsequently used in the sulfonation reaction, it can be used as it is without being neutralized, and it can be separated by filtration or the like if necessary. It can also be used after washing with alcohol, hydrous acetone solvent or the like to remove unreacted hydrophobizing agents or salts by-produced by neutralization. In addition, when the sulfonation reaction has already been performed before the hydrophobization reaction, after separation by filtration, etc., after washing, neutralization, etc. as necessary, drying is performed to obtain a polysaccharide sulfonated product. Can do.
[0015]
<Sulfonation reaction>
The sulfonation reaction of the polysaccharide or hydrophobized polysaccharide is performed by dissolving or dispersing the polysaccharide or hydrophobized polysaccharide in an appropriate solvent and reacting with the sulfonating agent (b).
[0016]
Examples of the sulfonic acid having an epoxide having 1 to 5 carbon atoms as the sulfonating agent (b) include 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 -Epoxy-1,1-dimethylmethylpropanesulfonic acid and the like. Examples of these salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and ammonium salts. These sulfonating agents (b) can be used alone or in combination of two or more.
[0017]
In general, a sulfonic acid having an epoxide and a salt thereof have an advantage that the solubility in water is improved as compared with a haloalkanesulfonic acid having the same carbon number, so that it is easy to handle. For example, the solubility of sodium 3-chloro-2-hydroxypropanesulfonate in water is 30%, but the solubility of sodium 2,3-epoxypropanesulfonate in water is improved to 50% or more.
[0018]
The amount of the sulfonating agent (b) can be adjusted as appropriate depending on the amount of sulfonic acid groups introduced into the polysaccharide, but is usually preferably 0.01 to 5 equivalents per constituent monosaccharide residue of the polysaccharide or hydrophobized polysaccharide. More preferably 0.05 to 3 equivalents.
[0019]
The sulfonation reaction is preferably carried out in the presence of an alkali, and the alkali is the same as that used in the hydrophobization reaction, that is, an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The alkali is preferably used in an amount of 0.01 to 10 mole times, particularly 0.1 to 5 mole times the sulfonating agent (b) to be used.
[0020]
Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. In addition, for the purpose of increasing the reactivity between the polysaccharide or the hydrophobic polysaccharide and the sulfonating agent (b), 0.1 to 100% by weight, more preferably 1 to 50% by weight of water is added to the lower alcohol. The reaction may be performed using a solvent.
[0021]
The reaction temperature is preferably in the range of 0 to 150 ° C, particularly 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. The next reaction can also be carried out without neutralization.
[0022]
When the sulfonated polysaccharide thus obtained is subsequently used in a hydrophobization reaction, it can be used as it is without being neutralized, and it can be separated by filtration or the like as necessary, or with hot water or hydrous isopropyl. It can also be used by removing unreacted alkylating agent or by-produced salts by neutralization, etc. by washing with alcohol, hydrous acetone solvent or the like. If the hydrophobization reaction has already been carried out prior to the sulfonation reaction, after separation by filtration, etc., washing, neutralization, etc. are performed as necessary, followed by drying to obtain a polysaccharide sulfonated product. Can do.
[0023]
【Example】
In the following Examples, the degree of substitution of the substituent (A) of the polysaccharide derivative was calculated by decomposing a polysaccharide derivative of known weight with excess hydroiodic acid and quantifying the resulting stearyl iodide. The degree of substitution of the substituent (B) was determined by colloid titration method. In the examples below, “degree of substitution” indicates the average number of substituents per constituent monosaccharide residue.
[0024]
Comparative Example 1
An aqueous solution consisting of 20 g of hydroxyethyl cellulose (QP15000H LOT.W8077P manufactured by Union Carbide), 0.69 g of stearyl glycidyl ether (2.60 mol% to HEC) and 128 g of isopropyl alcohol and 32 g of ion-exchanged water was added to the flask to prepare a slurry liquid. . Under a nitrogen atmosphere, 1.33 g (20 mol%) of a 48% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the temperature was raised to 80 ° C., and a hydrophobization reaction was performed at 80 ° C. for 8 hours. After completion of the hydrophobization reaction, the solution was cooled to 50 ° C. and stirred with stirring. 10.5 g of sodium 3-chloro-2-hydroxypropanesulfonate (concentration 30%) (20 mol% vs. HEC) and 48% sodium hydroxide aqueous solution 1.33 g was added, and the sulfonation reaction was carried out at 50 ° C. for 5 hours. Thereafter, the mixture was cooled to room temperature, neutralized with 1.6 g of concentrated hydrochloric acid, and the product was filtered off. The product was washed 3 times with 340 g of 70% isopropyl alcohol and then twice with 120 g of isopropyl alcohol, and then dried at 70 ° C. for 1 day under reduced pressure to obtain 17.8 g of a hydroxyethyl cellulose derivative as a pale yellow powder.
The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group of the obtained hydroxyethyl cellulose derivative was 0.0031, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.098.
[0025]
Example 1
To the flask was added 20 g of hydroxyethyl cellulose (Union Carbide QP15000H LOT.W8077P), 0.69 g of stearyl glycidyl ether (2.60 mol% to HEC) and 128 g of isopropyl alcohol and 32 g of ion-exchanged water to prepare a slurry solution. . Under a nitrogen atmosphere, 1.33 g (20 mol%) of a 48% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the temperature was raised to 80 ° C., and a hydrophobization reaction was performed at 80 ° C. for 8 hours. After completion of the hydrophobization reaction, cooling to 50 ° C, adding 8.53 g (20 mol% vs. HEC) of sodium 2,3-epoxypropanesulfonate aqueous solution (concentration 30%) with stirring, sulfonation reaction at 50 ° C for 5 hours Was done. Thereafter, the mixture was cooled to room temperature, neutralized with 1.6 g of concentrated hydrochloric acid, and the product was filtered off. The product was washed 3 times with 340 g of 70% isopropyl alcohol and then twice with 120 g of isopropyl alcohol, and then dried at 70 ° C. for 1 day under reduced pressure to obtain 18.5 g of a hydroxyethyl cellulose derivative as a pale yellow powder.
In the obtained hydroxyethyl cellulose derivative, the degree of substitution of 3-stearyloxy-2-hydroxypropyl group was 0.0031, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.114.
[0026]
Examples 2-5
The same procedure as in Example 1 was performed except that the hydrophobizing agent and sulfonating agent were changed.
The results of Comparative Examples and Examples 1 to 5 are shown in Table 1.
[0027]
[Table 1]

[0028]
As is clear from Table 1, in Examples 1 to 5, the degree of substitution of the sulfone group is improved as compared with the comparative example. This is thought to be due to the selective reaction to polysaccharides due to the high reactivity of epoxides. Furthermore, since a by-product salt is not generated at the end of the reaction, it is possible to reduce the load in the purification process. Therefore, a sulfonation reaction using a sulfonic acid having 1 to 5 carbon atoms or an epoxide thereof or a salt thereof is performed. Can be said to be industrially preferable.
[0029]
【The invention's effect】
According to the present invention, a polysaccharide sulfonated product which is excellent in transparency when made into an aqueous solution, exhibits excellent thickening at a low concentration, has little coexistence of metal salts and changes in temperature, and has very good emulsification stability. Can be advantageously provided industrially.

Claims (5)

The polysaccharide may be substituted with (a) a hydroxyl group, and an oxycarbonyl group (—COO— or —OCO—) or an ether bond may be inserted. A part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide, in which the glycidyl ether having a chain alkyl group or alkenyl group is reacted with (b) a sulfonic acid having a epoxide having 1 to 5 carbon atoms or a salt thereof, The manufacturing method of the polysaccharide sulfonated body substituted by the following (A) and (B).
(A) A linear or branched alkyl group having 10 to 43 carbon atoms, which may be substituted with a hydroxyl group, and into which an oxycarbonyl group (—COO— or —OCO—) or an ether bond may be inserted Or an alkenyl group,
(B) A sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or a salt thereof. Sulfonating agents are 1,2-epoxyethanesulfonic acid, 2,3-epoxypropanesulfonic acid, 3,4-epoxybutanesulfonic acid, 2,3-epoxy-1-methylpropanesulfonic acid, 4,5-epoxy Pentanesulfonic acid, 3,4-epoxy-1-methylbutanesulfonic acid, 3,4-epoxy-2-methylbutanesulfonic acid, 2,3-epoxy-1,1-dimethylmethylpropanesulfonic acid or their alkali metals The process according to claim 1, wherein the salt is an alkaline earth metal salt or an ammonium salt. The production method according to claim 1 or 2, wherein the substitution degree per constituent monosaccharide residue by methyl group, ethyl group, hydroxyethyl group and hydroxypropyl group of the raw material polysaccharide is 0.1 to 10.0. The production method according to any one of claims 1 to 3, wherein the raw material polysaccharide has a weight average molecular weight of 10,000 to 10,000,000. The raw material polysaccharide is cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch 5. The production according to claim 1, which is selected from the group consisting of hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum and hydroxypropyl methyl starch. Law.