JPH08188549A - Glycerol derivative and its production - Google Patents

Abstract

PURPOSE: To obtain a novel glycerol derivative which is useful as a builder for washing because it is readily soluble in water and biodegradable and has high metal ion-blocking ability. CONSTITUTION: This glycerol derivative is represented by formula I (R is a 1-3C alkyl, CH2 COOM; X, Y are each H, an organic group of formula II; R<1> is H, a 1-8C alkyl, carboxyl; R<2> , R<3> are each H, a 1-8C alkyl; M is a salt- forming cation where X and Y are not H simultaneously), for example, sodium salt of methylglycerol disuccinic acid ether. The compound of formula I is obtained by reaction of a glycerol monosubstituted derivative of formula III with an α,β-unsaturated carboxylic acid of formula IV or a reactive derivative thereof in the presence of a basic catalyst (e.g. calcium hydroxide) in a solvent (e.g. water) at 50 deg.C to the refluxing temperature for 30 minutes - 24 hours. Since the compound of formula I has a high capability of chelate formation in a wide pH range, it can be suitably used as a chelating agent for neutral detergents and further can be used as a preventive against periodontal diseases because it can prevent the formation of dental calculus and inhibit the deposition of dental plaque due to its high chelating capability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel glycerin derivative and a method for producing the same.

[0002]

2. Description of the Related Art Sodium tripolyphosphate (STPP) and ethylenediaminetetraacetic acid (EDTA) have been widely used as sequestering compounds. However, STP
Since P causes eutrophication of lake water and the like, while EDTA has low biodegradability and causes environmental problems, its use is in the direction of regulation. Further, zeolite, acrylic acid oligomer and the like have been proposed as substitutes for STPP and EDTA, and zeolite is widely used. However, zeolite has a drawback that it is insoluble in water, while acrylic acid oligomer has a drawback that biodegradability is low. As water-soluble and biodegradable sequestering compounds, decyl glycoside / succinic acid ether Na and 3-decyloxy-2-hydroxypropyl glyceryl ether / succinic acid ether N
a, dodecyl glyceryl ether / succinic acid ether N
a, succinic acid ether salts such as ethylene glycol monododecyl ether / succinic acid ether Na have been proposed (JP-A-6-157400). However, the sequestering properties of these ether salts of succinic acid are not yet satisfactory.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel glycerin derivative having excellent water-solubility and biodegradability and high sequestering property, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a glycerin derivative represented by the following general formula (1) is provided.

Embedded image (In the formula, R represents a saturated or unsaturated alkyl having 1 to 3 carbon atoms or —CH ₂ COOM, X and Y are each hydrogen or a formula

Embedded image Represents an organic group represented by the above R ¹ is hydrogen, carbon number 1
~ 8 alkyl group or a neutralized carboxyl group, R ² and R ³ represent hydrogen or an alkyl group having 1 to 8 carbon atoms, M represents a salt-forming cation, X and Y Is not hydrogen at the same time) Further, according to the present invention, the following general formula (1)

Embedded image (In the formula, R represents a saturated or unsaturated alkyl having 1 to 3 carbon atoms or —CH ₂ COOM, and X and Y are each hydrogen or a formula.

Embedded image Represents an organic group represented by the above R ¹ is hydrogen, carbon number 1
~ 8 alkyl group or a neutralized carboxyl group, R ² and R ³ represent hydrogen or an alkyl group having 1 to 8 carbon atoms, M represents a salt-forming cation, X and Y In the production method of the glycerin derivative represented by the following general formula (3)

Embedded image (Wherein R has the same meaning as described above), and a glycerin mono-substituted product represented by the following general formula (4)

[Chemical 4] (Wherein R ¹ , R ² and R ³ have the same meaning as described above)
The above-mentioned method is provided, which comprises reacting an α, β-unsaturated carboxylic acid represented by or with a reactive derivative thereof in the presence of a basic catalyst.

In the general formula (1), R is 1 carbon atom.
3 to 3 saturated or unsaturated alkyl groups are shown. Specific examples thereof include methyl, ethyl, propyl, inpropyl, vinyl and the like. R is CH ₂ CO
OM may be used, but in this case the salt-forming cation M
As, alkali metals such as Na, K, L, Ca, Mg
Alkaline earth metals such as ammonium, organic ammonium derived from amine, and the like. In the organic group represented by the general formula (2), which represents X and / or Y, R ¹ represents hydrogen, an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, or —COOM. Examples of the group include methyl, ethyl, propyl, isopropyl, butyl, octyl, and the like, and specific examples of the salt-forming cation M include those shown for M above.

The reaction in the present invention is as follows.

Embedded image In the above formula, R, X, Y, R ¹ , R ² and R ³ have the same meanings as described above. p represents the number of 1 or 2.

The above reaction proceeds according to a Michael addition type reaction in the presence of a basic catalyst. The reaction time may be a temperature of 50 ° C. or higher, and the upper limit thereof is the reflux temperature of the reaction mixture. The reaction time is 30 minutes to 24 hours, preferably 2 to
15 hours. A solvent may be used in this reaction, in which case water or a mixture of water and an organic solvent is used as the solvent. Any organic solvent can be used as long as it can dissolve the reaction raw materials, and examples of such an organic solvent include dimethyl sulfoxide, dimethylformamide, pyridine, picoline, t-butyl alcohol, diacetone alcohol. Etc. These reaction solvents are
The amount is 0.1 to 300 times, preferably 0.5 to 10 times (weight) that of the α, β-unsaturated carboxylic acid.

As the basic catalyst, alkaline earth metal hydroxides and alkali metal hydroxides are preferably used. As alkaline earth metal hydroxides, beryllium,
Included are hydroxides of magnesium, calcium, strontium, barium and radium. In addition, these alkaline earth metal hydroxides include lithium, sodium,
It can also be used together with hydroxides of alkali metals such as potassium, rubidium, cesium and francium. Further, ammonia or organic amine can also be used.
These basic catalysts are used in 1.05 to 3 times the equivalent number of the α, β-unsaturated carboxylic acid used. Examples of the glycerin mono-substituted product represented by the formula (3) used as a reaction raw material in the present invention include methylglycerin, ethylglycerin, propylglycerin, isopropylglycerin, vinylglycerin, carboxymethylglycerin and the like. Examples of the α, β-unsaturated carboxylic acid represented by the above formula (4) or its reactive derivative used as the other reaction raw material in the present invention include α, β-unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their derivatives. Besides salts and acid anhydrides are preferably used, acrylic acid, methacrylic acid,
An α, β-unsaturated monocarboxylic acid such as crotonic acid or 2-hexenoic acid, a salt thereof, or an acid anhydride is used. The ratio of the α, β-unsaturated carboxylic acid and the reactive derivative to be used may be equimolar or more than the molar number with respect to the glycerin mono-substituted product represented by the formula (3).

The compound of the present invention obtained by the above reaction is
It can be obtained in the form of a neutralized salt neutralized with an alkaline substance, but if necessary, this salt can be converted to the acid form or directly treated with another alkaline substance to give a salt-forming cation. You can convert it to something else. As the alkaline substance in this case, various substances such as alkaline earth metal hydroxides, alkali metal hydroxides, ammonia and organic amines are used. Practically, it is better to use sodium salt.

[0010]

[Detergent composition]

 Alpha sodium olefin sulfonate 12% Linear alkylbenzene sulfonate sodium 12% Sodium silicate 10% Sodium carbonate 10% Carboxymethyl cellulose 0.6% Sodium sulfate 40.4% Sample (Na salt) 10% Moisture 5%

[Detergent conditions] Washing device: Terg-O-Tometer Washing concentration: 0.133% Washing temperature: 25 ° C Washing time: 10 minutes Bath ratio: 30 (using artificial dirt cloth) Water used: 3 ° DH rinse Temperature: 25 ° Rinse time: 3 minutes x 2 times [Washing power] Rf₀: Reflectance of original fabric Rf₁: Reflectance Rf of cloth before washing₂: Reflectance of cloth after washing (4) Evaluation method for tartar formation inhibitory effect [Evaluation method for calcification inhibiting ability (pH retention ability)] * Calcification reaction liquid composition CaC1₂ 0.7 mmol KH₂PO_Four 2.59 mmol NaCl 50 mmol 20 ppm of the sample in 100 ml of the calcification reaction liquid of the above composition
Was added. Then, heat the test solution to 37 ° C.
And adjust to pH 7.42. In addition, the test solution
Roxyapatite 60mg (4m2, central glass
(Manufactured by 50 mMol, soaked in NaCl overnight)
After the treatment at 37 ° C. for 8 hours, the pH retention ability is evaluated. * When calcification progresses and tartar is formed, hydroxy
OH during apatite crystal growth^-P to take in ions
Lower development of H is observed.

Example 1 Synthesis of sodium salt of disuccinic acid ether of methylglycerin 26.2 g (0.267 mol) of maleic anhydride in 40 parts of water
g was added and the mixture was heated to 80 ° C. with stirring to dissolve it. Then,
7.2 g (0.068 mol) of methylglycerin was added to the reaction solution and dissolved. Furthermore, 7.0 g (0.095 mol) of calcium hydroxide and 32.0 g (0.4 mol) of 50% sodium hydroxide aqueous solution were added to this solution, and they were reacted for 10 hours. After the reaction was completed, 80 g of water was added and filtered, and concentrated sulfuric acid was further added to the filtrate until pH 1 was reached, and the precipitated Ca
SO ₄ was filtered off. Water was distilled off, 50 ml of methanol was added, and insoluble Na ₂ SO ₄ was filtered off. Methanol was distilled off, 50 ml of water was added, the sodium salt was converted to sodium salt, and then 300 ml of methanol was added for decantation. The white solid obtained is dried,
20.6 g (yield 71%) of the compound represented by the following formula was obtained.

[Chemical 6] When the proton-NMR of this compound was measured, it was as follows and was confirmed to be the target. NMR. δ (ppm, D ₂ O): 2.76 to 2.89
(4H), 3.28 (3H), 3.51 to 3.60 (3
H), 3.78 (1H), 3.88 (1H), 4.33
(1H), 4.53 (1H) This compound has a calcium trapping ability at pH 10 of 21
It was 6mg-CaCO ₃ / g- builder. In addition, when sodium citrate is evaluated for comparison, it is 210 mg.
It was -CaCO ₃ / g- builder. The calcium ion chelate stability constant was evaluated and found to be log
K _Ca was 4.4 (pH 10) and 4.2 (pH 7). When evaluating sodium citrate for comparison, the lo
The gK _Ca was 3.4 (pH 10) and 3.3 (pH 7). Thus, the compound of the present invention has an excellent ability to sequester calcium ions. Next, the detergency was evaluated to be 78%, and the detergency of sodium citrate was 7%.
Excellent compared to 1%. Furthermore, the effect of inhibiting calculus formation was evaluated by its ability to suppress calcification (pH retention ability). As a result, sodium alginate, which is a comparative model, had a pH of 6.
Although it decreased to 5, the pH value maintained the initial value of 7.4, and a remarkable pH retention ability was recognized.

Example 2 Synthesis of Sodium Salt of Disuccinic Acid Ether of Ethylglycerin A compound represented by the following formula was reacted in the same manner as in Example 1 except that ethylglycerin was used in place of methylglycerin of Example 1. 20.3 g was obtained (68% yield).

[Chemical 7] The calcium ion-capturing ability of this compound is 209 mg-C.
aCO ₃ / g-builder (pH 10), calcium ion chelate stability constant log Kca is 4.3 (pH 1)
0) and 4.0 (pH 7), the detergency was 77%, which had an excellent calcium ion sequestering ability. In addition, this product had a high pH-retaining ability and exhibited a tartar formation inhibitory effect.

Comparative Example 1 A sodium salt of a disuccinic acid ether of hexyl glycerin was obtained by carrying out the same reaction as in Example 1 except that hexyl glycerin was used in place of the methyl glycerin of Example 1. The calcium ion trapping ability of this compound is 158 m
g-CaCO ₃ / g-builder (pH 10), its calcium ion chelate stability constant is 3.6 (pH 10)
And the ability to sequester calcium ions was inferior to the compounds of the present invention.

Example 3 Synthesis of Sodium Salt of Disuccinic Acid Ether of Carboxymethylglycerin Reaction was carried out in the same manner as in Example 1 except that carboxymethylglycerin was used in place of methylglycerin of Example 1, and represented by the following formula. Compound 26.8 g (yield 80
%) Was obtained.

Embedded image The calcium ion-capturing ability of this compound is 192 mg-C.
aCO ₃ / g-builder (pH 10), its calcium ion chelate stability constant log K _Ca is 4.5 (pH 1
0) and 3.9 (pH 7), its detergency is 79%, and it has an excellent ability to sequester calcium ions. Also pH
The retention ability was high and the effect of inhibiting tartar formation was shown.

[0016]

INDUSTRIAL APPLICABILITY The glycerin derivative of the present invention is excellent in water solubility and biodegradability, has a high sequestering ability (chelating ability), and is suitable as a washing builder. Since the glycerin derivative of the present invention has a high chelating ability in a wide pH range (neutral to alkaline), it is also suitable as a chelating agent for a neutral detergent, and due to its high chelating ability, a tartar formation preventing property. Since it is also excellent in the inhibitory effect on adhesion of dental plaque, it can be advantageously used as a periodontal disease preventive agent. Furthermore, the glycerin derivative of the present invention can be advantageously used as a chelating agent in the textile / dyeing industry, the metal plating industry and the like. The method for producing a glycerin derivative according to the present invention can be carried out safely and easily.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location // C07B 61/00 300 (72) Inventor Shigeyuki Ueda 1-3-3, Honjo, Sumida-ku, Tokyo No. Lion Co., Ltd.

Claims (2)

[Claims] 1. A glycerin derivative represented by the following general formula (1). Embedded image (In the formula, R represents a saturated or unsaturated alkyl having 1 to 3 carbon atoms or —CH ₂ COOM, X and Y are each hydrogen or a compound represented by the formula: Represents an organic group represented by the above R ¹ is hydrogen, carbon number 1
~ 8 alkyl group or a neutralized carboxyl group, R ² and R ³ represent hydrogen or an alkyl group having 1 to 8 carbon atoms, M represents a salt-forming cation, X and Y And shall not be hydrogen at the same time) 2. The following general formula (1): (In the formula, R represents a saturated or unsaturated alkyl having 1 to 3 carbon atoms or —CH ₂ COOM, X and Y are each hydrogen or a compound represented by the formula: Represents an organic group represented by the above R ¹ is hydrogen, carbon number 1
~ 8 alkyl group or a neutralized carboxyl group, R ² and R ³ represent hydrogen or an alkyl group having 1 to 8 carbon atoms, M represents a salt-forming cation, X and Y Is not hydrogen at the same time) in the method for producing a glycerin derivative represented by the following general formula (3) (In the formula, R has the same meaning as described above), a glycerin mono-substituted product represented by the following general formula (4): (Wherein R ¹ , R ² and R ³ have the same meaning as described above)
The method as described above, which comprises reacting the α, β-unsaturated carboxylic acid represented by or with a reactive derivative thereof in the presence of a basic catalyst.