JPH0212137B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel surfactants. More specifically, the present invention relates to a polymer type surfactant having a quinone structure in its molecule and having a low degree of polymerization.

Conventionally, various surfactants have been known, including polymeric surfactants with a low degree of polymerization (hereinafter referred to as
(simply referred to as oligosoap) is also known. or,
As the fields of application of surfactants expand, the properties required of surfactants are also becoming more diverse.

According to the present invention, one of the maleic anhydride or maleic acid derivative monomer units of a copolymer of maleic anhydride or a maleic acid derivative and a polymerizable monomer having an olefin dipolymer bond at the terminal
A quinone structure was formed by condensing an aromatic hydroxy compound to the quinone structure. A polymeric surfactant having a quinone structure is provided.

In general, polycarboxylic acid type polymer activators play a major role as dispersants by imparting negative charges to fine particles (pigments, etc.). The anionic oligosoaps of the present invention also have a large number of dissociable carboxyl groups and phenolic hydroxyl groups in the polymer, so they have excellent properties such as adsorption to the pigment surface, wetting action by lowering the interfacial tension, and dispersibility in the pigment vehicle. This shows the surfactant.
In addition, it has a rigid dye structure within its molecule, so it has low foaming properties. Therefore, the anionic oligosoaps of the present invention are useful as an aqueous dispersant for fine particles or as a pigment surface modifier. In addition, in recent years, with the development of the information industry, various functional materials have been considered, and they are of great value when used in this field.

In the oligosoap of the present invention, the quinone-type dye structure portion can be a fluorescent fluorescein type, and it can also exhibit unique functions as a fluorescent dye oligomer. For example, fluorescent compounds have recently begun to be used in various fields such as electronic materials and medical detection agents (fluorescent reagents).
Fluorescent oligosoaps incorporating an amphiphilic structure according to the present invention can of course be detected when adsorbed to particles, and the pH of the system in contact at the interface can be detected.
It has properties such as its fluorescence spectrum changing depending on the temperature, and has interesting uses.

Among the surfactants of the present invention, resorcinol is condensed to a part of the acid anhydride group of a copolymer of maleic anhydride and a polymerizable monomer having an olefin double bond at the terminal, which is represented by the general formula below. Particularly preferred are fluorescent oligosoaps in which a fluorescein-type dye structure is formed.

In the formula, R represents a hydrogen atom or a lower alkyl group, and X represents an alkyl group, an aryl group, or an alkyl ether group. Examples of the alkyl group of this alkyl ether group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
Such as tert-butyl, dodecyl, hexadecyl, etc.
_C1 - _C18 alkyl is preferred. Moreover, Y is hydrogen or various cations, such as alkali metals, ammonium ions, and amines. m and n are integers, the sum of which is usually 4 to 1000
(average) range. Preferably m
+n is 4 to 100 (average). Also, m/(m+
The ratio n) usually ranges from 0.05 to 0.8.

The surfactant of the present invention is made from a copolymer of maleic anhydride or a maleic acid derivative and a polymerizable monomer having an olefin double bond at the end, and is reacted with an aromatic hydroxy compound to form a quinone-type structure. Manufactured by forcing.
Various copolymers can be used as the above-mentioned copolymers, for example, Oil Chemistry 26744; 781 (1977) and US Pat.
Copolymers prepared by the methods described in No. 3388106 and No. 3451979 can be used. Polyhydric phenols and their derivatives are usually used as aromatic hydroxy compounds to be reacted with this copolymer.
Dihydric phenols such as resorcinol, catechol, and hydroquinone are suitable. Practically speaking, it is better to use resorcinol. This is because among the triphenylmethane dyes, fluorescein dyes are
The objective is to express the strongest fluorescence through -0- bonds. The reaction is usually carried out by heating in the presence of a catalyst such as concentrated sulfuric acid or zinc chloride. An inert organic solvent is used if necessary.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Application Examples. The surface tension, foaming power, dispersing power, and emulsifying power of the aqueous solutions of each example were tested as follows.

(1) Surface tension Measured at 30±1°C using a Wilhelmy type surface tension meter (Shimadzu ST-1 model). put it in a measuring container
Measurement was taken after 60min.

(2) Foaming power Semi-trace improved TK method [Yano, Kimura, Oil Chemistry 11,
138 (1962)]. Pour 5 ml of the sample solution into a foam container with a volume scale. Insert the glass tube so that the bottom end of the tube is at the bottom of the solution, and the top end is open to the outside air. Separately, a rubber tube is connected to the aspirator section to reduce the pressure inside the foam container. That is, when 300 ml of water is allowed to flow down to reduce the pressure in the foam container, air is blown into the solution from the lower end of the glass tube at the bottom of the solution, causing the sample solution to foam. The foam volume was read immediately after foaming (0 minutes), 1 minute later, and 5 minutes later. If the top of the bubble was not flat, I leveled it and read it. Bubbles that did not disappear after the measurement were removed by blowing air with a dropper, and the next measurement was carried out. The foam height was measured using the same procedure as the first one, and the measurements were taken as an average after three measurements.

Further, the defoaming rate (foam stability) was determined by the following formula.

Defoaming rate = Foam height at 0 minutes - Foam height after 5 minutes / Foam height at 0 minutes x 10
0 (3) Dispersion power 50mg of dispersoid such as α-copper phthalocyanine blue
Place in a 30 ml graduated test tube, add 20 ml of the sample solution, bring the temperature to 30°C, shake vertically with a shaker (120 times for 30 seconds, amplitude 25 cm), and leave at 30°C for 4 hours.
Next, insert the tip of the pipette up to the 5 ml graduation line from the liquid level in the test tube, draw up 2 ml from that area, and transfer it to another test tube. Add 25ml of water to this solution
(A) was measured using a colorimeter (Nippon Denshoku Integrating Sphere Hazemeter Model NDH-20D, compliant with JIS K-6714), and the dispersion force was determined according to the following formula.

Dispersion force=To−Ts/To×100 Where, To: Transmittance of an aqueous solution obtained by adding 25 ml of water to 2 ml of the test solution, Ts: Transmittance of (A) above.

(4) Emulsifying power 3 ml of activator aqueous solution and 2 oil in a 30 ml graduated test tube
ml and put it in 95℃ water to bring it to the same temperature. This was shaken using a shaker (with an amplitude of 25 cm for 30 seconds).
Immediately after shaking (120 times vertically), place in a constant temperature water bath at 95℃, and read the separated oil layer, emulsified layer, and separated water layer over time (from 5 minutes to 120 minutes after shaking). In this case, in the separated state, the liquid in the test tube is in the following order from the bottom: a separated water layer, an emulsified layer, and a separated oil layer.

On the other hand, before shaking, read the height of the boundary line of the oil-water layer, and create a graph with time as the horizontal axis and the height from that boundary line to the boundary of the separated oil layer of the emulsified layer as the vertical axis. Then, let (A) be the area surrounded by the curve thus drawn, the vertical axis, and the horizontal axis. Separately, on the same scale, create a graph by plotting time on the horizontal axis and the height of the boundary line of the first oil-water layer from the boundary between the emulsified layer and the separated water layer, and Let (B) be the area surrounded by the vertical and horizontal axes. Since the area (A) corresponds to the amount of emulsified oil in the oil, the percentage of the area of this emulsified layer in the oil layer was determined, and this was calculated as the emulsification rate (%).

Example 1 6.2 g of an alternating low polymer of maleic anhydride and dodecyl vinyl ether (with an average repeating unit number of 22) and 5.5 g of resorcinol (1:2.5 molar ratio) were added to 30 ml of o-dichlorobenzene, and 80 ml of o-dichlorobenzene was added. After heating to a homogeneous mixture state, add 0.5g of concentrated sulfuric acid, and mix well to 165-170℃ for 5-10 minutes.
Heated for minutes. A similar reaction occurred when zinc chloride was used as a catalyst instead of sulfuric acid. The obtained dark red precipitate was collected, dissolved in acetone, and then poured into n-hexane to precipitate it. Even more ethanol
After washing with a water mixture (1:1), a reddish-orange prismatic oligomer (x200, light microscope) was obtained. mp189℃.
IR analysis showed that the absorption of the aromatic ring (resorcinol) was 1610 and 1520 cm ^-1 , and the absorption of the phenol group was 1610 and 1520 cm -1.
It was recognized at 3400cm ^-1 . In addition, absorptions of disubstituted aromatic nuclei were found at 840 and 720 cm ^-1 . Furthermore, nuclear magnetic resonance spectroscopy revealed that 60% of the acid anhydride residues in the oligomer were condensed with resorcinol.

The oligomers obtained as above were neutralized (saponified) with a predetermined amount of aqueous sodium hydroxide solution, and the monosodium salt of each corresponding oligosoap (hereinafter referred to as
C ₁₂ R−1Na), disodium salt (hereinafter C ₁₂ R
-2Na) and trisodium salt ( _C12R -3Na) were obtained. The interfacial tension lowering ability, foaming power, dispersibility for pigments, emulsifying power for solvents, fluorescence, etc. of these oligosoaps are shown below.

The surface tension value of a 1% aqueous solution of C ₁₂ R−3Na is
The value was 32.9 dyne/cm (value after standing for 1 hour).
The foam volume at 0 minutes of a 1% aqueous solution of C ₁₂ R−3Na is 70 ml.
14ml after 1 minute, 10ml after 5 minutes, defoaming rate after 5 minutes is 86
It was %. Sodium lauryl sulfate (manufactured by Eastman Kodak, SDS) used as a control experiment
A 1% aqueous solution of has a foam volume of 267 ml at 0 minutes, 267 ml after 1 minute,
After 5 minutes, the volume was 256 ml, and the defoaming rate was 4%. C ₁₂ R−
It can be seen that the 3Na aqueous solution has a very low foaming property and is easily defoamed even if it foams. α-Copper phthalocyanine blue (hereinafter α-
The dispersion power of a 1% aqueous solution of C ₁₂ R-3Na against PC (abbreviated as Cyanine Blue HB manufactured by Sumitomo Chemical) is 57%.
It was hot. SDS for α-PC as a control experiment
The dispersing power of a 1% aqueous solution of Aerosol 0T [sodium 1,2-bis(2-ethylhexyloxycarbonyl)-1-ethanesulfonate] was measured and found to be 26% and 45%. The emulsifying power of a 1% aqueous solution of C ₁₂ R-2Na against kerosene was 98%. The emulsifying power of a 1% aqueous solution of SDS against kerosene was 90%. C ₁₂ R−1Na and C ₁₂ R−2Na
Similarly, it had excellent surface activity such as surface tension lowering ability, dispersing power, and emulsifying power, and also had low foaming property. The maximum absorption wavelength of ultraviolet light for an aqueous solution of neutralized salt is 477
When fluorescence spectroscopy was performed using excitation light at ~483 nm, the maximum fluorescence absorption wavelength was 502 to 516 nm.

Example 2 Maleic anhydride and n-
Resorcinol was condensed to an alternating copolymer (average repeating unit number 72) with butyl vinyl ether. Neutralization salt of product with sodium hydroxide
The surface tension value of a 1% aqueous solution of C ₄ R−2Na is
It was 39.0 dyne/cm (after standing for 1 hour). The foaming power was 8 ml at 0 minutes, 0 after 1 minute, 0 after 5 minutes, and 100% defoaming after 5 minutes. The dispersion power of a 0.5% aqueous solution of C ₄ R-2Na against α-PC was 65%, and that of a 1% aqueous solution of C ₄ R-3Na was 78%.

Example 3 Copolymer of styrene and maleic anhydride (M=
6000 (styrene:maleic anhydride = 65:35 molar ratio) and 2.0 g of resorcinol were heated and reacted at 170 to 180° C. for 30 minutes while stirring in the presence of 0.5 g of a zinc chloride catalyst. The product was purified by repeatedly dissolving it in acetone and then pouring it into hexane for precipitation. From the IR spectrum, absorption by the disubstituted aromatic nucleus (840 cm ^-1 ) other than 750 and 690 cm ^-1 , which is the absorption of the monosubstituted styrene, was observed.
It was confirmed that a condensate of styrene/maleic anhydride copolymer resorcinol was produced. By neutralizing this with an alkali, a water-soluble surface active substance (oligosoap) was obtained.

Example 4 Alternating copolymer of maleic anhydride and isobutylene (manufactured by Kuraray Co., Ltd., Isoban-04, molecular weight approximately 60,000)
1.5 g of resorcinol and 4.4 g of resorcinol were dissolved in dichlorobenzene, 2.4 g of concentrated sulfuric acid was added, and the mixture was reacted at 170°C for 20 minutes with stirring. The acetone-soluble portion of the reaction mixture was poured into hexane to obtain a precipitate. After repeated purification using an acetone-hexane system, the precipitate was thoroughly washed with water to obtain a reddish brown powder. IR analysis and NMR were performed. It became water-soluble after neutralization with sodium hydroxide. The absorption maximum of these neutralized salts in the ultraviolet region was 481 to 485 nm, and when the fluorescence spectrum was examined using excitation light of this wavelength, the wavelength at which the fluorescence intensity showed a maximum was 511 nm. The surface tension of a 0.1% aqueous solution (30℃) is determined by the Wilhelmy method.
It was 39.3mN/m.

Application example 1 α in the 0.5% aqueous solution of C ₁₂ R−3Na obtained in Example 1
- When the dispersion system in which PC was dispersed was diluted 13.5 times with water and fluorescence spectrometry was performed using excitation light of 489 nm, the maximum wavelength of the fluorescence spectrum of the dispersion system was found to be C ₁₂ which does not contain dispersoids. of 0.5% aqueous solution of R−3Na
Approximately on the shorter wavelength side than the maximum wavelength of the 13.5 times diluted solution.
The 5 nm shift indicates that oligosoap strongly adsorbs to the α-PC surface and exerts a large dispersion effect.

Application Example 2 15.0 parts of the C ₁₂ -oligomer or oligosoap obtained in Example 1 was dissolved in 75.0 parts of methyl ethyl ketone, 60.0 parts of magnetic powder (γ-Fe ₂ O ₃ ) was added thereto, and while stirring the mixture well, Heat methyl ethyl ketone under reflux (79-80 °C) for approximately 20 minutes. After recovering methyl ethyl ketone under reduced pressure, the obtained magnetic powder is milled in a ball mill for 30 minutes. When the same sample was added to water or alcohol, it was partially dispersed, but it was well dispersed in a dilute alkaline aqueous solution, and the dispersion system was stable for a long time. In this way, the magnetic powder coated with oligosoap has a lipophilic and hydrophobic surface and is well dispersible in magnetic paint for recording media.

Application example 3 When the fluorescent oligosoap of the present invention dissolved in an aqueous solution or an organic solvent solution was sprayed on a metal object with cracks or pinholes on the surface or at a relatively shallow depth below the surface, fine particles that were invisible to the naked eye were found. defects were also easily discovered. The inspection method used ultraviolet irradiation (black light). The fluorescent color was orange to green, making it easy to observe. In this case, it was confirmed that a binder such as an epoxy resin could be used.

Application example 4 Adding alkaline earth metals and heavy metals (CD, Hg, Pb, etc.) to the oligosoap aqueous solution of C ₄ R-Na (Example 3)
When a dilute solution of ions was added and stirred, the metal ions precipitated, showing a metal-trapping effect.

Claims (1)

[Claims] 1 A quinone structure is obtained by condensing an aromatic hydroxy compound to a part of the maleic anhydride or maleic acid derivative monomer unit of a copolymer of maleic anhydride or a maleic acid derivative and a polymerizable monomer having an olefin double bond at the terminal. A polymeric surfactant with a quinone structure that has formed a quinone structure.