JPH0585210B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new emulsifying and dispersing agent composition. Conventionally, surfactants made by phosphoric acid esterification of higher alcohols and compounds obtained by adding ethylene oxide to higher alcohols and alkyl phenols have come to be widely used as dispersants for various substances in oil and water systems. As the objects of dispersion have expanded in recent years, there has been a demand for a dispersant with even higher performance. As a result of intensive research into improving the dispersion performance of phosphate ester type surfactants from this point of view, the present inventors found that when such conventionally known phosphate ester type surfactants are used in combination with nitrogen-containing surfactants, remarkable performance is achieved. The present invention was based on the discovery that an improvement in the following properties was observed. That is, the present invention relates to general formula (1) or general formula (2)

[Formula] (However, R ₁ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ₂ is OH or R ₁ O.)

[Formula] (However, R ₃ is a higher alcohol having an alkyl group or alkenyl group having 8 to 22 carbon atoms or a carbon number 4
Alkylphenol with ~12 alkyl groups 1
A residue with 1 to 100 moles of ethylene oxide or/and propylene oxide added to the mole,
R ₄ is OH or R ₃ O. ) At least one R ₅ CO (OR ₆ ) nN group per molecule per 100 parts by weight of at least one compound shown in (where R ₅ has 7 carbon atoms)
- 21 alkyl groups, alkenyl groups, R ₆ is ethylene or propylene, n is an integer of 1 to 50) A dispersant composition comprising 10 to 500 parts by weight of at least one compound. It is. The dispersant composition of the present invention can be obtained as follows. First, the phosphate ester type surfactants represented by general formulas (1) and (2) are decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, cetyl alcohol, myristyl alcohol, oleyl alcohol, and phosphoric acid surfactants from the oxo method. A nonionic surfactant prepared by adding 1 to 100 moles of ethylene oxide or/and propylene oxide to 1 mole of a mixed alcohol having 11 to 15 carbon atoms, a secondary alcohol having 12 to 13 carbon atoms, and these higher alcohols by a known method; Butylphenol, octylphenol,
Phosphorus oxychloride is added to 1 mole of these raw materials using a nonionic surfactant, etc., which is obtained by adding 1 to 100 moles of ethylene oxide or/and propylene oxide to 1 mole of nonylphenol, dodecylphenol, or dinonylphenol by a known method. It is obtained by reacting 0.3 to 1.0 moles of phosphorus pentoxide, preferably phosphorus pentoxide, by a known method, and is usually obtained as a mixture of a monoester and a diester. Preferred in terms of performance are lauryl alcohol, tridecyl alcohol, oleyl alcohol, mixed alcohols having 11 to 15 carbon atoms from the oxo method, octylphenol, and nonionic surfactants prepared by adding 5 to 15 moles of ethylene oxide to 1 mole of nonylphenol. It is preferable to use a phosphate ester type surfactant made from a surfactant. Next, at least one R ₅ CO (OR ₆ ) in one molecule
nN group (where R ₅ is an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ₆ is ethylene or propylene,
(n is an integer of 1 to 50) Aminoether ester type surfactants include triethanolamine, triisopropanolamine, ethylenediamine, propylene diamine, triethylenetetramine, diethylenetriamine, tetraethylenepentamine, aminoethyleneaminopropylamine, etc. polyachilene polyamine, decylamine,
Alkylamines such as dodecylamine, myristylamine, palmitylamine, oleylamine, cetylamine, stearylamine, behenylamine, dodecylaminoethylamine, tallow aminopropylamine, dodecylaminopropylamine,
Alkyl polyalkylene polyamines such as dodecyl diethylene triamine and tetradecyl diethylene triamine, laurylamide ethylamine,
A fatty acid amide amine such as stearylamide ethylethylenediamine, an alkylimidazoline derivative such as N-laurylhydroxyethylimidazoline, and N-oleylaminoethyl imidazoline are added with 1 to 50 moles of ethylene oxide or/and propylene oxide per amino group by a known method. After addition, 8 carbon atoms such as lauric acid, stearic acid, oleic acid, isostearic acid, palmitic acid, myristic acid, linoleic acid, etc.
~22 fatty acids with at least one R ₆ CO in each molecule
(OR ₆ )nN group can be obtained by reacting with a known method. Among these, preferred in terms of performance are oleic acid, isostearic acid, lauric acid monoester, decylamine, dodecylamine, myristylamine, and palmitylamine of triethanolamine and 5 to 20 mole adducts of ethylene oxide such as ethylenediamine and triethylenetetramine. , oleic acid, isostearic acid, and lauric acid mono-diesterized products of 5 to 20 moles of ethylene oxide such as oleylamine, cetylamine, stearylamine, dodecylaminopropylamine, and beef tallow aminopropylamine. The thus obtained phosphate ester type surfactant and aminoether ester type surfactant are 1:
They are used in a mixed ratio of 0.1 to 1:5, but preferably the acid value equivalent of the phosphate ester type surfactant and the amine value equivalent of the aminoether ester type surfactant are neutralized. It is preferable to mix them as much as possible, and the weight ratio is in the range of 1:0.3 to 1:2. The characteristic of the dispersant of the present invention is that it can be used as a dispersant in a wide range of applications and exhibits excellent effects, and can also provide rust prevention effects as a secondary effect. It is used as a dispersant for iron oxide, metal particles, carbon, ceramics, etc. in water and oil, and can also be used in the production of paints, inks, petroleum additives, magnetic materials, electromagnetic shielding agents, etc. Next, examples of the present invention will be shown. Example 1

[Synthesis of phosphate ester type surfactant (1)] 572 g of 1 mole of poly(8)oxyethylene nonyl phenyl ether, which is obtained by adding 8 moles of ethylene oxide to 1 mole of nonylphenol using a known method, was placed in a four-necked Kolben. , 57 g of 0.4 mol of phosphorus pentoxide was gradually added with stirring at room temperature, and then reacted at 90°C for 5 hours to form poly(8) in the form of a pale yellow viscous oil with an acid value of 120 measured using a phenolphthalene indicator. Oxyethylene nonyl phenyl ether phosphate was obtained.

[Synthesis of aminoether ester type surfactant (1)] 1 mol 60 g of ethylene diamine was placed in an autoclave, 0.1 g of sodium acetate was added, and 20 mol 880 g of ethylene oxide was gradually added at 160°C under a pressure of 3 atm.
It was added under _N2 gas and the reaction was completed in 4 hours. Next, 1 mol 940 g of the obtained poly(20)oxyethylene ethylenediamine was placed in a four-necked colben, 1.5 mol 423 g of oleic acid was added, and N ₂ gas was introduced.
Dehydration reaction was carried out at 180° C. for 8 hours to obtain reddish brown oily N-,N-polyoxyethylene ethylene diamine sesquioleate having an amine value of 84.

[Production of dispersant of Example 1] Poly(8) oxyethylene nonyl phenyl ether phosphate (phosphate ester type surfactant (1)
) and 70 g of N-,N-poly(20)oxyethylenediamine sesquioleate (aminoether ester type surfactant (1)) at 60°C.
and mixed to obtain Example 1 in the form of a yellowish brown paste.
Example 1 will be subjected to the test described below.

[Production of Comparative Examples 1, 2, and 3] Poly(8) oxyethylene nonyl phenyl ether phosphate (phosphate ester type surfactant (1)
Comparative Example 1 was obtained by neutralizing 100 g with 32 g of triethanolamine. Comparative Example 2 was prepared by neutralizing 100 g of poly(8)oxyethylene nonyl phenyl ether phosphate with 21.5 g of 40% caustic soda and then dehydrating it. Comparative Example 3 was prepared using N-,N-polyoxyethylene ethylene diamine sesquioleate alone.

[Dispersion test 1] 100g of industrial gasoline No. 4, 1.2μ red iron
10 g and 0.3 g of the dispersant were placed in a 200 c.c. beaker, stirred for 1 hour using a magnetic stirrer, then transferred to a cylinder and left to stand at room temperature for 48 hours, and the volume of the upper transparent portion was measured. The dispersion effect of Example 1 was excellent, with 0.4 cc in Example 1, 2.5 cc in Comparative Example 1, 2.3 cc in Comparative Example 2, and 5.6 cc in Comparative Example 3. Examples 2 to 20

[Synthesis of phosphate ester type surfactants (2) to (9)] Synthesize phosphate ester type surfactants (2) to (8) in the same way as the synthesis of phosphate ester type surfactant (1). 1st
The results shown in the table were obtained.

【table】

[Synthesis of aminoether ester type surfactants (2) to (11)] Aminoether ester type surfactants (2) to (11)
was synthesized and the results shown in Table 2 were obtained.

【table】

[Synthesis of Examples 2 to 20] Examples 2 to 20 were prepared in the same manner as Example 1 as shown in Table 3.

【table】

【table】

[Comparative Examples 4 to 7] Comparative Example 4: Monoethanolamine salt of phosphate ester type surfactant (5) Comparative example 5: K salt of phosphate ester type surfactant (7) Comparative example 6: Aminoether ester type surfactant
(8) Comparative Example 7: Sorbitan Sesquioleate

[Dispersion test (2)] 5g of 1.5μ aluminum nitride, 30g of methyl ethyl ketone,
Pour 10g of n-butanol and 0.1g of dispersant into a 100cc beaker, and stir using a magnetic stirrer.
After stirring for an hour, the mixture was transferred to a centrifuge tube and left at room temperature for 8 hours, and the amount of sediment was observed to obtain the results shown in Table 4.

【table】

[Dispersion test (3)] 100g of No. 4 gasoline, 0.5μ carbon magnesium
5g of dispersant and 0.2g of dispersant were mixed and treated with an attritor for 5 hours, and the resulting dispersion was left at 40℃ for 1 month.
The state of separation was then observed. Examples (5), (9), (7), (10), (1
When using 1), (12), (14), (16), and (20), the dispersion was stable and no sedimentation was observed, but comparative examples (3), (5), and (7) were used. ), a large amount of sediment was observed in all cases.

Claims (1)

[Claims] 1 General formula (1) or general formula (2) [Formula] (R ₁ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, R ₂ is OH or R ₁ O) [ Formula】 (However, R ₃ is a higher alcohol having an alkyl group or alkenyl group having 8 to 22 carbon atoms or a carbon number 4
Alkylphenol with ~12 alkyl groups 1
A residue with 1 to 100 moles of ethylene oxide or/and propylene oxide added to the mole,
R ₄ is OH or R ₃ O. ) At least one R ₅ CO(OR ₆ )nN group per molecule per 100 parts by weight of at least one compound shown in (However, R ₅ has 7 carbon atoms)
A dispersant composition comprising 10 to 500 parts by weight of at least one compound having an alkyl group or an alkenyl group of -21, _R6 is ethylene or propylene, and n is an integer of 1 to 50.