JPS581103B2 - N↓-3↓-(cis↓-9↓-octadecenoyloxy)↓-2↓-hydroxypropylamine derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel N-3-(cis-9-octadecenoyloxy)-2-hydroxypropylamine derivatives.

The present invention is directed to N-3-(cis-9-octadecenoyloxy) represented by the general formula below, which has excellent surfactant ability and is extremely useful as a nonionic surfactant, emulsifier, and dispersant. The object of the present invention is to provide -2-hydroxyprobylamine derivatives having the general formula:

) N-3-(cis-9-octadecenoyloxy)-2-hydroxypropylamine derivative.

The N-3-(cis-9-octadecenoyloxy)-2-hydroxypropylamine derivative represented by the above general formula of the present invention is N-3-(cis-9-octadecenoyloxy)-2-hydroxy Glopyrdiethanolamine, N-
3-(cis-9-octadecenoyloxy)-2-hydroxypropyl-2-amino-2-methyl-1,3-propanediol, N-3-(cis-9-octadecenoyloxy)-2-hydroxy Propyltrimethylolaminomethane.

The compound of the present invention is produced by direct heating and addition reaction of glycidyl oleate with diethanolamine, 2-amino-2-methyl-1,3-propanediol, and trimethylolaminomethane, and the comparison is made without a catalyst. Since the addition reaction is completed in a short time even at extremely low temperatures, industrial implementation is extremely easy.

The compound represented by the above general formula of the present invention is usually 0.9 to 2.2% per mole of glycidyl oleate and glycidyl oleate.
70 to 120 times the mole of the above alkanolamine directly.
It is obtained by carrying out a heating reaction at ℃ for 3 to 4 hours.

To isolate a target product from a reaction mixture, usually, a large amount of petroleum ether or ligroin is added to the reaction mixture, stirred thoroughly, and left to stand, and the precipitated excess unreacted alkanolamine is removed by decantation or filtration. do.

Next, the solvent is distilled off from the petroleum ether solution (or ligroin solution), the residue is distilled under high vacuum, and the desired product is obtained by purifying the fraction by column chromatography, recrystallization, etc.

The compound of the present invention represented by the above general formula (obtained in the examples below) is a colorless to pale yellow viscous liquid or white crystal, hardly soluble in water, and easily soluble in alcohol, petroleum ether, chloroform, etc. It is melted.

Table 1 shows these physical property values.

However, the MS spectra were measured for the mono-TMS form of each compound.

The compound represented by the above general formula of the present invention has a high degree of surfactant ability and is extremely useful as an emulsifier, a dispersant, and as an intermediate for cationic surfactants, anionic surfactants, amphoteric surfactants, etc. be.

In particular, when applied as an emulsifier in the production of water-in-oil type (W/O type) emulsions (e.g., W/O type emulsified cosmetics such as vinyl polymer emulsions, milky lotions, creams, etc.), it is unique and remarkable. For example, the related compound N-3-(cis-9-octadecenoiroquine)-2
-Hydroxypropyldiethylamine, N-3-(cis-9-octadecenoyloxy)-2-hydroxypropyl tertiary butylamine, cis-9-octadecenoic acid diethanolamide, cis-9-octadecenoic acid-1,1-
A homogeneous W/W/ that exhibits excellent emulsifying properties, stability, and water-holding properties that are not found in dimethylolethylamide, cis-9-octadecenoic acid trimethylolmethylamide, etc., and has excellent storage stability and stability against temperature changes. An O-type emulsion can be obtained.

Furthermore, the compound of the present invention is also significantly superior to the above-mentioned related compounds in its ability to disperse pigments such as carbon black, and is extremely useful as a dispersant for pigments in paints and the like.

Examples of the present invention will be described in detail below.

In the examples, % means % by weight, and parts mean parts by weight.

Example 1 Synthesis of N-3-(cis-9-octadecenoyloxy)-2-hydroxypropyldiethanolamine 25 g of diethanolamine and 50 g of glycidyl oleate were placed in a 200 ml flask equipped with a stirrer, and the mixture was stirred vigorously for 70 min. The reaction is carried out for 4 hours at °C.

After the reaction is completed, the reaction mixture is cooled to room temperature, 100 ml of petroleum ether is added, thoroughly stirred, and then left to stand for about 2 hours.

Next, precipitated unreacted diethanolamine is removed by decanting, and the supernatant liquid is concentrated under reduced pressure.

The concentrated liquid was further distilled under high vacuum (70 mTorr),
A fraction of 150 to 180°C is collected.

Furthermore, this distillate was treated with silica gel as a filler, acetone/chloroform/n-hexane (50/30/20V/V%
) was purified by column chromatography using as an eluent to obtain 57 g (87%) of a slightly yellow viscous liquid.

The product obtained here exhibited remarkable emulsifying power, and was confirmed to be a highly pure target compound based on the physical property values listed in Table 1, analysis by gas chromatography (as a TMS compound), and elemental analysis values.

Example 2 N-3-(cis-9-octadecenoyloxy)-2-hydroxypropyl-2-amino-2-methyl-1.3-
Synthesis of propanediol In a reactor similar to Example 1, 2-
Amino-2-methyl-1,3-propanediol 25g
, 50 g of glycidyl oleate was added, and the reaction was carried out at 110° C. for 4 hours with vigorous stirring.

After the reaction was completed, the same treatments as in Example 1 (decantation, distillation) were performed to obtain a pale yellow paste-like substance.

Next, this product was recrystallized twice with acetone, resulting in white crystals with 55%
．． 7g (85%) was obtained.

The obtained product was also subjected to the physical property values shown in Table 1 and the same analysis as in Example 1, and was confirmed to be a highly pure target compound.

Example 3 Synthesis of N-3-(cis-9-octadecenoyloxy)-2-hydroxypropyltrimethylolaminomethane 25 g of trimethylol aminomethane and 50 g of glycidyl oleate were placed in the same reactor as in Example 1. The reaction was carried out at 120° C. for 4 hours with vigorous stirring.

After completion of the reaction, the same treatments as in Example 1 (decantation, distillation) were carried out to obtain a pale yellow semi-solid.

Next, this material was recrystallized twice with Ascent, resulting in a white crystal of 59
g (87%).

The obtained product was also subjected to the physical property values shown in Table 1 and the same analysis as in Example 1, and was confirmed to be a highly pure target compound.

Application example 1 Application as an emulsifier N-3-(cis-9-octadecenoyloxy) of the present invention
-2-hydroxypropyldiethanolamine (A),
N-3-(cis-9-octadecenoyloxy)-2-hydroxypropyl-2-amino-2-methyl-1,3-
Propanediol (B), N-3-(cis-9-octadecenoyloxy)-2=hydroxypropyltrimethylolaminomethane (C), N-3- as a related compound
(cis-9-octadecenoyloxy)-2-hydroxypropyldiethylamine [)), N-3-(cis-9-
octadecenoyloxy)-2-hydroxypropyl'
5 parts each of tertiary butylamine (E), cis-9-octadecenoic acid diethanolamide (F), and sorbitan sesquioleate (G) as emulsifiers and 30 parts each of liquid paraffin were mixed and heated to 70°C. While vigorously stirring, 65 parts of water at 70°C was added to disperse and emulsify.

Next, each emulsion was slowly cooled to 30° C. while being gently stirred to obtain a W/O type emulsion.

Next, each emulsion was diluted 2000 times with liquid paraffin, and the absorbance of each sample at 450 nm was measured.

The results are shown in Table 2. However, the values in the table are converted values based on sorbitan sesquioleate (G) as 100.

Table 2 Sample Absorbance (ratio) A 128 B 124 C 223 D 73 E 65 F 80 G 100 Generally, it is known that within a certain range, the finer the emulsion particles, the greater the absorbance of the emulsion. As is clear from Table 2, the compounds of the present invention (A, B, C
) has a higher absorbance than those using related compounds (D to G), and microscopic observation also shows that the compounds of the present invention give emulsions with extremely fine particles. It has been found that it is useful as an emulsifier, especially as a W/O type surfactant.

Application example 2 Application as an emulsifier in the production of acrylic resin emulsion 50 parts each of the compounds A, B, C and related compounds D to G of the present invention used in application example 1 as emulsifiers, 350 parts of heavy oil, and methacrylic acid. 150 parts of methyl, 60 parts of ethyl acrylate
400 parts of water was added thereto at 60° C. while stirring to uniformly emulsify the mixture.

Next, 0.25 parts of azobisisobutyronitrile was added as a polymerization initiator, and emulsion polymerization was carried out at 60°C for 2.5 hours to form a W/O emulsion of methyl methacrylate-ethyl acrylate copolymer. I got it.

These emulsions were left in a constant temperature room at 45°C to examine their stability over time.

As a result, compounds A and B of the present invention represented by the above general formula
．． Each emulsion using each of C as an emulsifier is
Both are fine homogeneous emulsions of polymer particles,
Moreover, even after being left for 12 months, no abnormalities were observed, and the storage stability was extremely good.

On the other hand, each emulsion using each of the related compounds (D to G) as an emulsifier has coarse polymer particles, and in the emulsion using G, the oil separates after 1 month and after 3 months. Later the water separated.

In addition, in each emulsion using D, E, and F, oil separated after 10 days and water separated after 3 months, and like G, they were extremely unstable and had poor emulsifying and stabilizing ability. There are also significant differences.

As described above, the compounds (A, B, and C) of the present invention are all extremely useful as emulsifiers during the production of acrylic polymer emulsions (during emulsion polymerization of acrylic monomers).

Application example 3 Application as a pigment dispersant One part each of the compounds A, B, C of the present invention used in application examples 1 and 2 and D to G as related compounds were dissolved in 98 parts of liquid paraffin, and further fine particle oxidation was performed. One part of titanium (average particle size approximately 30 mμ) was added and stirred vigorously at room temperature to prepare a uniform dispersion.

After each of these dispersions was allowed to stand at room temperature for 20 hours, the upper layer liquid was mixed with 0. 5 g was collected and diluted with the same liquid paraffin.
The sample was diluted 00 times and the absorbance at 300 nm was measured.

The results are shown in Table 3. In addition, the table shows converted values with sorbitan sesquioleate (G) as 100.

Table 3 A 134 B 200 C 146 D 87 E 72 F 89 G 100 As is clear from the above, compounds A, B, and C of the present invention all have better dispersion power for titanium oxide than related compounds D to G. Almost the same tendency was observed in experiments using other pigments.

It has been recognized that the compounds of the present invention can also be used with good results as pigment dispersants in paints and the like.

As mentioned above, the compounds represented by the above general formula (A, B, and C in the application examples) all have excellent emulsifying ability that is not seen in the above-mentioned related compounds (D to G in the application examples). It has the ability to disperse pigments, and its effects are highly specific due to differences in its chemical structure.

Claims (1)

[Claims] 1. There is a general formula. ) N-3-(cis-9-octadecenoyloxy)-2-hydroxypropylamine derivative. 2 N-3-(cis-9-octadecenoyloxy)-2
The N-3-(cis-9-octadecenoyloxy)-2-hydroxypropylamine derivative according to claim 1, which is -hydroxypropyldiethanolamine. 3 N-3-(cis-9-octadecenoyloxy)-2
-Hydroxypropyl-2-amino-2-methyl-1.
N-3-(cis-9-octadecenoyloxy)-2- according to claim 1, which is 3-propanediol.
Hydroxypropylamine derivative. 4 N-3-(cis-9-octadecenoyloxy)-2
The N-3-(cis-9-octadecenoyloxy)-2-hydroxypropylamine derivative according to claim 1, which is -hydroxypropyltrimethylolaminomethane.