JPS60187327A - Polymer type surface active agent having quinone structure - Google Patents

Abstract

PURPOSE:To manufacture a polymer type surface active agent of low polymerization degree having quinone structure by allowing copolymer of maleic anhydride and polymerizing monomer having olefin double bound in the terminal as raw material to react with an aromatic hydroxyl compound. CONSTITUTION:An aromatic hydroxyl compound (for example, resorcinol) is condensed for one part of maleic anhydride or maleic acid derivative monomer- unit of copolymer of the maleic anhydride or the maleic acid derivative and polymerizing monomer having olefin double bond in the terminal to form quinone structure. The obtained titled surface active agent shows excellent surface active properties such as adsorption to pigment surface, wetting action due to surface tension reduction and dispersibility into pigment vehicle. Since it has low bubbling properties, it is useful as dispersant for fine granules in water system or a reforming agent of pigment surface. Furthermore, the quinone type color structure part can be made fluorescent fluorescein type and also it is useful as fluorescent color oligomer.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel surfactants. For more details,
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,
Polymeric surfactants with a low degree of polymerization (hereinafter simply referred to as oligosoaps) are also known. Additionally, as the fields of application of surfactants expand, the properties of surfactants are also becoming more diverse.

According to the present invention, an aromatic hydroxy compound is added 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 dipolymer bond at the terminal. Provided is a polymeric surfactant having a quinone structure, which is formed by condensing the above to form a quinone structure.

In general, a polycarboxylic acid type polymer activator plays a major role as a dispersant by imparting a negative charge to fine particles (pigments, etc.).

Since the anionic oligosoaps of the present invention also have a large number of dissociable carboxyl groups and phenolic hydroxyl groups in the polymer, 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 molecules, 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 quinoline type dye structure portion can be made into a fluorescent fluorescein type, and it can also exhibit a unique function 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), but fluorescent oligosoaps incorporating amphiphilic structures, which are related to the present invention, are also adsorbed to particles. Not only can it be detected at the interface, but it has properties such as the fluorescence spectrum changing depending on the pH of the system in contact with it at the interface, so it 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 double olefin viscosity at the terminal, as shown by the general formula below. Particularly preferred are fluorescent oligosoaps in which at least 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, 5ec-butyl, tert-butyl, dodecyl,
C1-C18 alkyl such as hexadecyl and the like are preferred. Further, (2) represents hydrogen or various cations, such as alkali metals, ammonium ions, amines, etc. m and n are integers, the sum of which is usually 4 to 100
It is preferable to set it in the range of 0 (average). Preferably m +
n is 10 to 100 (average). Also, m/(m+n
) is usually in the range of 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 double olefin viscosity at the end, which is then reacted with an aromatic hydroxy compound. It is produced by forming a quinone type structure.

Various types of copolymers can be used as the above-mentioned copolymers, for example,
Copolymers prepared by the methods described in Yukagaku Nihon, 744; 781 (1977) and US Pat. Nos. 3,388,106 and 3,451,979 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 triphenylmethane dyes, fluorescein dyes exhibit 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 in each example were tested as follows.

-4= (1) Surface tension Measured at 30±1° C. using a Wilhe1my type surface tension meter (Shimadzu 5T-1 type). 60m1 in a measuring container
Measured after n.

(2) TK method with semi-trace improvement in foaming power [Arrow, Kimura, Oil Chemistry 11.138 (
1962)). Pour 5 mQ of the sample solution into a bubble 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 a portion of the aspirator in order to reduce the pressure within the foam volume.

That is, when 300 mQ of water is allowed to flow down to reduce the pressure in the bubble 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. Immediately after foaming (0 minutes), 1
After 5 minutes, the foam volume was read. 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 averaged three times.

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

50mg of dispersoid such as α-copper phthalocyanine blue
Take 0mQ in a graduated test tube, add 20mQ of sample solution, bring to 30℃, and shake vertically with a shaker (30s
c120 times, amplitude 25 cm) and left at 30°C for 4 hours. Next, insert the tip of the pipette from the liquid level of the test tube to the 5mQ graduation line, suck up 2TMΩ from that part, and
Transfer to another test tube. A solution to which 25mM of water was added (A
), colorimeter (Nippon Heavy Color Integrating Sphere Hazemeter)
NDH-200 type (based on JIS K-6714) was measured separately, and the dispersion force was determined according to the following formula.

Here, To: Transmittance of an aqueous solution obtained by adding 25 mQ of water to the test solution 2+++Q, Ts: Transmittance of the above (A).

Add 3mβ of activator aqueous solution and 2IIIQ of oil to a 30m+2 graduated test tube, and place in 95°C water to bring to the same temperature.

This was shaken with a shaker (amplitude 25 for 30 seconds).
After shaking vertically for 120 times (120 times), immediately place it in a thermostatic water bath at 95°C, and shake it for 120 m1 (after shaking Sm1n).
(until after n) and read the dispersed oil layer, emulsified layer, and dispersed water layer.

In this case, the liquid in the test tube is separated from the bottom,
The order is a separated water layer, an emulsified layer, and a separated oil layer.

On the other hand, before shaking, read the height of the oil-water layer boundary line and create a graph with time as the horizontal axis and the height from the boundary line to the boundary of the separated oil layer of the emulsified layer as the vertical axis. ,
The area of the portion surrounded by the curve thus drawn, the vertical axis, and the horizontal axis is defined as (A). Separately, on the same scale, create a graph by plotting time on the horizontal axis and the height of the initial oil-water layer boundary line from the boundary between the emulsified layer and the separated water layer, and compare this curve with Let (B) be the area of the part surrounded by the vertical axis and the horizontal axis. The area (A) corresponds to the amount of emulsified oil in the oil, so calculate the area percentage of this emulsified layer in the oil layer,
This was calculated as an emulsification rate (%).

Example 1 Maleic anhydride 7 in 30 m Q of 0-dichlorobenzene
- Add 6.2 g of an alternating copolymer (with an average repeating unit number of 22) and dodecyl vinyl ether and 5.5 g of resorcinol (1:2.5) and heat to 80°C until a homogeneous mixture is obtained. After that, 0.5 g of concentrated sulfuric acid was added, and the mixture was heated at 165 to 170°C for 5 to 10 minutes while stirring well.

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. Further washing with a large amount of ethanol-water mixture (1:1) gave a reddish-orange prismatic oligomer (X 200, first order). m
p189℃. IR analysis revealed that aromatic ring (resorcinol) absorption was observed at 1610 and 1520 cm', and phenol group absorption was observed at 3400 cm'. In addition, absorption of disubstituted aromatic nuclei was found in 840 and 7200I11-1. Further, 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 and saponified with a predetermined amount of aqueous sodium hydroxide solution), and the corresponding oligosoap and sodium salt (hereinafter Cl2R-
(abbreviated as INa), disodium salt (hereinafter referred to as C42R-2N
a) and the 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 42R-3Na is 32.9
dyne/cm (value after standing for 1 hour) aCl
The foam volume at 0 minutes of a 1% aqueous solution of 2R3Na is 70 m Q, 1
The defoaming rate after 5 minutes was 86% with a public service size of 14m Q and a 5 minute diameter of 10+n Q. A 1% aqueous solution of sodium lauryl sulfate (manufactured by Eastman Kodak Co., Ltd., 5O3) conducted as a control experiment had a foam volume of 267 rn Q at 0 minutes and 2 tl per injection.
i7+n (256 mA after 1.5 minutes, defoaming rate was 4%. It can be seen that the Cl2R3Na aqueous solution has a very low foaming property and easily defoams even if foamed.

α-Copper phthalocyanine blue (hereinafter abbreviated as α-PC), which has a hydrophobic surface and is difficult to disperse
The dispersing power of a 1% aqueous solution of Cl2R-3Na for B) was 57%. SD for α-PC as a control experiment
When the dispersion power of a 1% aqueous solution of S and aerosol 0T (sodium 1,2-bis(2-ethylhexyloxycarbonyl)-1-ethanesulfonate) was measured, it was found to be 26%.
The emulsifying power of a 1% aqueous solution of Cl2R2Na against kerosene was 98%.

The emulsifying power of a 1% aqueous solution of SNS for kerosene resin is 90
%Met. Cl2R-INa and C12R-2Na were similarly excellent in surface activity such as surface tension lowering ability, dispersing power, and emulsifying power, and also had low foaming properties. The maximum absorption wavelength of the aqueous solution of the neutralized salt in the ultraviolet region was 477 to 483 nm, and when fluorescence spectrometry was performed using excitation light of this wavelength, the maximum absorption wavelength of fluorescence was 502 to 516 nm.

Example 2 In the same manner as in Example 1, an alternating copolymer of maleic anhydride and n-butyl vinyl ether (average number of repeating units: 72) was condensed with resorcinol. The surface tension of a 1% aqueous solution of C4R-2Na, a product neutralized with sodium hydroxide, was 39.0 dyne/am (after standing for 1 hour).The foaming power was 8 mfl at 0 minutes, and after 1 minute. 0.5 minutes later 0
．． The defoaming rate was 100% after 5 minutes. The dispersion power of a 0.5% aqueous solution of C4R-2Na against α-pc is 65%,
That of a 1% aqueous solution of C4R-3Na was 78%.

Example 3 Copolymer of styrene and maleic anhydride (M = 600
0.

Copolymer set (styrene: maleic anhydride = 65 = 35
2.1 g of molar ratio) and 2.0 g of resorcinol were reacted by heating 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, an absorption (840-1) due to a disubstituted aromatic nucleus other than ``-'' was observed at 750 and 690 cm, which is the absorption of a monosubstituted styrene.
It was confirmed that a condensate of maleic anhydride copolymer resorcinol was produced. By neutralizing this with an alkali, a water-soluble surface active substance (oligosoap) was obtained.

Example 4 1.5 g of an alternating copolymer of maleic anhydride and isobutylene (manufactured by Kuraray, Isopan-04, molecular weight approximately 60,000) and 4.4 g of resorcinol were dissolved in dichlorobenzene,
2.4 g of concentrated sulfuric acid was added and reacted at 170°C for 20 minutes while 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 analysis were performed. It became water-soluble when neutralized 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 the maximum was 511 nm.

Application example 1 α-
Dilute the dispersion system in which PC is dispersed 13.5 times with water,
Fluorescence spectrometry was performed using excitation light of 489 nm, and it was found that the maximum wavelength of the fluorescence spectrum of the dispersion system was greater than the maximum wavelength of a 13.5-fold dilution of a 0.5% aqueous solution of C12R-3Na containing no dispersoids. , shifted by about 5 nm to the shorter wavelength side, indicating that the oligosoap strongly adsorbs to the α-20 surface and exhibits a large dispersion effect.

Application Example 2 15.0 parts of C1□-oligosoap obtained in Example 1 was dissolved in 75.0 parts of methyl ethyl ketone, 60.0 parts of magnetic powder (γ-Fe 203 ) was added thereto, and the mixture was dissolved. While stirring well, add 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 was dissolved in an aqueous solution or an organic solvent solution and sprayed on a metal body with cracks or pinholes on the surface or a relatively shallow part below the surface,
Even minute defects that cannot be seen with the naked eye could be 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 When a dilute solvent of alkaline earth metal and heavy metal (CD, Hg, Pb, etc.) ions is added to the oligosoap aqueous solution of C4R-Na (Example 3) and stirred, the metal ions precipitate and the metal trapping effect is activated. Indicated.

Patent applicant Hirobu Yoda, Director of the Agency of Industrial Science and Technology, Procedural Amendment (Jibon) Manabu Shiga, Commissioner of the Japan Patent Office 1, Indication of the case Patent Application No. 43242 of 1982, 2,
Title of the invention Polymeric surfactant with quinone structure 3
Address of patent applicant related to the person making the amendment: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo 'y'
4 (114) Director of the Agency of Industrial Science and Technology Kawa 1) Hirobe 15-8. Contents of amendment The following amendments are made to the specification of this application.

(1) Correct "quinoline dye" in lines 1 and 2 of page 6 to "quinone dye."

(h) Formula on page 4 [ Correct.

(3) Set r10 to 100J on page 4, line 11 to [4 to 10
I will correct it to 0J.

(4) Correct "volume scale" in line 7 of page 6 to "volume scale".

(5) “Foam content” on page 6, line 10 is “1 foam container”
I will correct it.

(6) On page 7, line 4, change “30- to scaled test tube” to “
Corrected to ``Test tube with 30 volume scale''.

(7) Separate and measure 1... on page 7, line 11.''
Correct it to "measured using...".

(8) “Dispersed oil layer, emulsified layer, dispersed water layer” on page 8, line 4
Correct it to "separated oil layer, emulsified layer, separated water layer".

(9) Page 9, line 6 [Nor 5.5 g (1: 2
-5)...'' to [5.5g of alcohol (1:2.5
molar ratio)...".

00) Correct "Sorezono" on the last line of page 9 to "1 each."

C1, l) Correct "oligosorb, -sodium salt" in the first line of page 10 to "1 oligosorb, monosodium salt."

(12) In page 11, line 15, "condense resorcinol with..." is corrected to "condense resorcinol with...".

(13) Correct "Surface tension" in line 17 of page 11 to "Surface tension value".

(14) Correct "copolymer set" in line 4 of page 12 to "copolymer."

05) Change r (840-1)J on page 12, line 11 to “(
84 [] cm-1)".

06) Correct "dispersed system and water" in line 12 of page 13 to "dispersed system is water".

0.7) Page 14, line 1 (7) rclp-O IJ
Correct "Nia"/-bu to "Cl2 = oligomer or oligosorb".

α8) Correct “dilute solvent” in line 6 of page 15 to “dilute solution”.

(19) "Representative agent" in line 9 of page 15 will be corrected to "designated agent."

Claims (1)

[Claims] (1) An aromatic hydroxy compound is condensed 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 polymer having double olefin viscosity at the end. A polymeric surfactant with a quinone structure that has at least formed a quinone structure.