JP2857194B2 - New organic gelling agent - Google Patents

Description

The present invention relates to a novel and useful organic gelling agent. The gelling agent as referred to herein is a general term for compounds having the property of reducing or eliminating the fluidity of a low molecular weight liquid or high molecular substance by adding the substance to the substance by about 20% by weight or less.

[Prior art] As an organic gelling agent, 1,3: 2,4-dibenzylidene sorbitol and its alkyl nucleus-substituted products have been used so far.
Various compounds such as 12-hydroxystearic acid, N-acylamino acid derivatives, and fatty acid metal salts are known.

[Problems to be Solved by the Invention] However, although the conventional organic gelling agent sufficiently exerts its effect on the gelation of an organic solvent, there is still room for improvement in the gelation ability of water or an aqueous solution. In addition, even if the gel was kneaded, there was a problem that a uniform and smooth paste could not be obtained and seeding occurred.

The present inventors have widened the range of selection of drugs according to their uses as gelling agents and flow control agents, etc., and exerted a predetermined effect with a smaller amount of addition, and the above-mentioned conventional gelling agents As a result of intensive studies to develop a new and useful organic gelling agent that can solve the problems of having a 1,3: 2,4-dibenzal skeleton and having a specific structure of an ester group, It has been found that a diacetal having a structure in which an aromatic nucleus is also substituted has a desired effect, and the present invention has been completed based on such findings.

[Means for Solving the Problems] The organic gelling agent according to the present invention is a compound represented by the general formula (I).

[Wherein, R ¹ and R ² are the same or different and each is an alkenyl group,
Represents an alcohol residue of a polyoxyalkylene alkyl ether group, a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenyl ether, or a polyoxyalkylene benzoate;
Represents In the compound according to the general formula (I), the position of the ester group substituted on the aromatic nucleus may be any of o-, m-, and p-, and as R ¹ and R ² , more specifically, an alkyl group ( C21-C40), halogen-substituted alkyl group such as fluorine (C1-C30), alkenyl group (C3-C40), alkynyl group, alkadienyl group (C4-C40), alkapolyenyl group ( Poly = 3 to 6), polyoxyalkylene alkyl (C 1 to C 40) ether group, and poly (degree of polymerization =
1-100) oxyalkylenealkyl (C1-40)
Ether, poly (degree of polymerization = 1 to 100) oxyalkylenealkyl (1 to 40 carbon atoms) phenyl ether, poly (degree of polymerization = 1 to 100) oxyalkylenealkyl (1 carbon atom)
-20) ester, poly (degree of polymerization = 1-80) oxyalkylenealkyl (1-30 carbon atoms) amide, poly (degree of polymerization =
Examples are (1-100) oxyalkylene benzoate, polyester (Mn = 200-100,000), alcohol residue of poly (polymerization degree = 1-100) alkylene adduct of aliphatic or alicyclic tertiary amine, and the like. Is done. Here, as the oxyalkylene, ethylene oxide, propylene oxide or a co-adduct thereof is exemplified, and among them, an ethylene oxide adduct and an ethylene oxide-propylene oxide co-adduct are preferable.

As the carbon number of R ¹ and R ² increases, the melting point of the gelling agent tends to decrease, which not only results in a gelling agent having good solubility at low temperatures and easy to use,
When this gel is kneaded, it becomes a smooth paste, and the occurrence of seeding is suppressed. Further, diacetal having a polyoxyalkylene group is effective as a gelling agent for an aqueous medium.

These diacetals are synthesized, for example, as follows. That is, (1) Methyl formyl benzoate is reacted with methanol in the presence of an acidic catalyst to obtain dimethyl acetal of methyl formyl benzoate.

(2) Next, alcohol [ROH, where R has the same meaning as R ¹ and R ^{2 according} to formula (I). To give dimethyl acetal (A) of formyl benzoate.

(3) Further, about 2 moles of the above (A) and about 1 mole of a polyhydric alcohol (sorbitol, xylitol) are subjected to a condensation reaction in the presence of an acidic catalyst to obtain the desired diacetal in high yield and high selectivity. .

The diacetal thus obtained can be used for oil spills, adhesives,
As a gelling agent for fluid systems such as fragrances, pharmaceuticals, and polymers, and because it also has a function as a thixotropic agent, the fluidity of FRP, paints, inks, adhesives, etc. It is suitable as a regulator.

In addition, the application amount can be appropriately selected according to the application, and is generally 20% by weight based on the gelation target.
Or less, preferably 5% by weight or less.

The diacetal according to the present invention is a compound that functions as a gelling agent for various flowable substances and is useful as a nucleating agent for crystalline resins such as polyolefin resins and polyethylene terephthalate, like the conventionally known diacetals. Specifically, when a compound having a low melting point as described above is used as a nucleating agent, it is effective in lowering the molding temperature, and a compound having a polyoxyalkylene chain can prevent or prevent charging of a molding resin. The compound having a fogging effect and having a halogen-substituted alkyl chain has characteristics such as imparting antifouling property to a molding resin.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples.

Production Example 1 In a 1 L four-necked flask equipped with a stirrer, a decanter and a thermometer, 32.8 g (0.2 mol) of methyl p-formylbenzoate, 36.4 g (0.2 mol) of sorbitol, cyclohexane (200 ml), methanol 80 ml and m -Toluenesulfonic acid (1.2 g) was charged and reacted for 4.5 hours while heating and refluxing, and methanol and produced water were drawn out of the system. As a result of analysis by liquid chromatography, the target 1,3: 2,4-bis (p-methoxycarbonylbenzylidene) sorbitol (compound 1) (48.2 g) was obtained at a selectivity of 95% and a reaction rate of 90%.
I got

Production Example 2 In a four-necked flask similar to that of Production Example 1, 16.4 g (0.1 mol) of methyl p-formylbenzoate and 50 ml of methanol were added.
-Dimethyl acetal (A) of methyl p-formylbenzoate was quantitatively obtained by mixing at 50 ° C. for 1 hour in the presence of toluenesulfonic acid. 21 g of this compound (A)
(0.1 mol), 37.9 g (0.14 mol) of stearyl alcohol, 100 ml of tetrahydrofuran (solvent) and 1.05 g of potassium hydroxide (catalyst) were mixed at 65 ° C. for 2.5 hours, and dimethyl acetal of stearyl p-formylbenzoate (B) Four
2.5 g (95% yield) was obtained. Hereinafter, the target 1,3: 2,4-bis (p-stearyloxycarbonylbenzylidene) sorbitol (compound 2) was prepared in the same manner as in Production Example 1 except that the compound (B) was used in place of methyl p-formylbenzoate. 80.8 g (85% yield).

Production Example 3 21 g (0.14 mol) of compound (A) and 18.2 g (0.1 mol) of a 10 mol adduct of octyl alcohol with ethylene oxide were transesterified according to Production Example 2 to obtain 28.5 g of dimethyl acetal (C). (92.5% yield). Hereinafter, 127 g (83% yield) of the target diacetal (compound 3) was obtained in the same manner as in Production Example 1 except that the compound (C) was used instead of methyl p-formylbenzoate.

Production Example 4 21 g (0.1 mol) of compound (A) and 16.5 g (0.14 mol) of ethylene glycol monobutyl ether were subjected to a transesterification reaction according to Production Example 2 to give dimethyl acetal of butoxyethyl p-formylbenzoate (D). 26.6g
I got Also, 26.6 g of dimethyl acetal (E) of butoxyethyl p-formylbenzoate was obtained by the same reaction as described above between compound (A) and hexanol. Hereinafter, a target mixed diacetal, that is, a compound represented by the general formula (I), in the same manner as in Production Example 1 except that an equimolar mixture of the compound (D) and the compound (E) is used instead of methyl p-formylbenzoate:
R ¹ = R ² = C ₄ H ₉ (C ₂ H ₄ O)-, R ¹ = C ₄ H ₉ (C ₂ H ₄ O)-, R ² = n-hexyl-, R ¹ = n-hexyl _{^{-, R 2 = C 4 H}} 9 (C 2 H 4 O) -, · R 1 = R 2 = n- hexyl - approximately equimolar mixture of (compound 4) 55 g (87% yield) Obtained.

Example 1 An object to be gelled (water, ethyl acetate and butanol) was placed in a test tube, and a gelling agent (compound 3) was added thereto at 2% by weight.
Each was added and heated for 15 minutes in an oil bath at 130 ° C., and then the presence or absence of fluidity of the system when cooled with water for 30 minutes was determined by a test tube inverted method.

：: no fluidity Δ: slight fluidity X: fluidity The results obtained are shown in Table 1.

Comparative Example 1 Instead of the diacetal according to the present invention, 1,3: 2,4-dibenzylidenesorbitol (hereinafter abbreviated as “DBS”).
The presence or absence of fluidity of the gelled object was determined according to Example 1 except that was added. Table 1 shows the obtained results.

Example 2 0.7 g of the diacetal (compound 6) according to the general formula (I) having a substituent of R ¹ = R ² = oleyl was added to 100 g of rapeseed oil at 130 ° C., and the mixture was stirred for 5 minutes. The fluidity of the composition when cooled to room temperature was determined according to Example 1. Table 1 shows the obtained results.

Comparative Example 2 The gelation target was the same as in Example 2 except that 1,3: 2,4-ditoluylidene sorbitol (hereinafter abbreviated as “Me-DBS”) was added instead of the diacetal according to the present invention. The fluidity of the material was determined. Table 1 shows the obtained results.

Example 3 0.7 g of a diacetal (compound 9) according to the general formula (I) having an alcohol residue of R ¹ = R ² = poly (degree of polymerization = 5) oxyethylene benzoate as a substituent was added to 100 g of glycerin at 130 ° C. In addition, it was stirred for 5 minutes. The flowability of the composition when cooled to room temperature was determined according to Example 1. Table 1 shows the obtained results.

Example 4 Example 3 except that a diacetal (compound 10) according to the general formula (I) having an alcohol residue of R ¹ = R ² = poly (degree of polymerization = 12) oxyethylene oleyl ether was used as a substituent. The presence or absence of fluidity of the gelling object was determined according to the above. Table 1 shows the obtained results.

Example 5 Diacetal (compound) according to the general formula (I) having an alcohol residue of R ¹ = R ² = poly (degree of polymerization = 12) oxyethylene / poly (degree of polymerization = 4) oxypropylene octyl ether as a substituent Except where 11) was used, the presence or absence of fluidity of the gelled object was determined according to Example 3. Table 1 shows the obtained results.

Example 6 As a substituent, R ¹ RR ² CC ₈ H ₁₇ -phenyl-O- (C ₂ H ₄
O) Except for using the diacetal (compound 12) according to the general formula (I) having an alcohol residue of ₉ C ₂ H ₄ −, the presence or absence of fluidity of the gelation target was determined according to Example 3. Table 1 shows the obtained results.

Comparative Example 3 Except for adding DBS in place of the diacetal according to the present invention, the presence or absence of fluidity of the gelled object was determined according to Example 3 except that DBS was added. Table 1 shows the obtained results.

Comparative Example 4 Except that Me-DBS was added instead of the diacetal according to the present invention, the presence / absence of fluidity of the gelled object was determined in accordance with Example 3. Table 1 shows the obtained results.

Reference Example 0.3 g of Compound 4 was converted to an acrylic resin (Mn = 83,000, Mw / Mn =
7) Compounded into 100 g, kneaded at 180 ° C, and press-formed to form a 0.5 mm thick sheet. After the sheet was rubbed with a cotton cloth 10 times to be charged, the sheet was approached at a distance of 1 cm from the wood ash.

Although wood ash adhered to the sheet obtained from the acrylic resin alone, in the above case, there was no adhesion of the wood ash, and the antistatic effect obtained by blending the diacetal was recognized.

Similar antistatic effects were also observed when the diacetal according to the general formula (I) having R ¹ = R ² = C ₈ F ₁₇ C ₂ H ₄ − was blended.

[Effects of the Invention] The diacetal according to the present invention is a novel and useful organic gelling agent having excellent performance when added in a small amount.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 3/00 103 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A novel organic gelling agent represented by the general formula (I) [Wherein, R ¹ and R ² are the same or different and each is an alkenyl group,
And represents an alcohol residue of a polyoxyalkylene alkyl ether group, a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenyl ether, or a polyoxyalkylene benzoate. p represents 0 or 1. ]