JPS63151345A - Novel surfactant - Google Patents

Abstract

PURPOSE:To provide a surfactant effectively acting in the manufacturing of paint and subsequently stopping various functions thereof rapidly, by preparing a succinic half ester sulfonic acid type anionic surfactant having a metallyl group. CONSTITUTION:A surfactant is prepared from a mixture of compounds represented by formulae, I, II (wherein R is a 8-30C alkyl group, an alkenyl group, an alkylaryl group or an aralkylaryl group, A is a 2-4C alkylene group or a substituted alkylene group, n is an integer of 0-100, m is an integer of 1-200, M1 is an alkali metal atom, an alkanolamine residue or NH4 and M2 is an alkali metal atom or NH4. This surfactant shows surface active function at the time of the manufacturing of paint or printing ink and at the time of the preservation of a product but can subsequently stop various functions as a surfactant rapidly.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel surfactant, and particularly to a succinic acid half ester sulfonic acid type anionic surfactant having a methallyl group.

Conventionally, surfactants have a wide range of properties such as emulsification, dispersion, cleaning, wetting, and foaming.Using these properties, surfactants can be used to improve materials such as fibers, paper, rubber, plastics, metals, etc.
It is used in various fields such as paints, pigments, and civil engineering and construction. Particularly recently, there has been an active movement toward improving the performance of end products using surfactants, and along with this, secondary drawbacks of surfactants have also been pointed out.

For example, paints, printing inks, adhesives, pressure-sensitive adhesives, and the like are indispensable in the production of products, product stability, and workability. When these products are used for coating, printing, adhesion, adhesive, etc., surfactants are not necessary; rather, the surfactants present are used to form coatings, printed surfaces, adhesive films, etc. It often deteriorates performance such as water resistance and oil resistance.

As a countermeasure to these problems, efforts are being made to reduce the amount of surfactants blended and use polymeric surfactants, but issues such as product stability and workability have yet to be fully resolved. Not yet reached.

On the other hand, in order to provide new types of surfactants, there are many patents for polymerizable, reactive, or degradable surfactants.

For example, as an anionic surfactant,
No. 12472, JP-A-54-14431, JP-A-1973
-34894, Japanese Patent Publication No. 56-29657, Japanese Patent Publication No. 56-2965
1-30285, JP-A No. 49-46291, JP-A-56-127697, etc., as nonionic surfactants, JP-A-56-28208, JP-A-50-984.
There are No. 84, etc.

Various attempts have been made to use these surfactants mainly as emulsifiers for emulsion polymerization, but they have not yet reached a fully satisfactory practical stage.

The reason for this is: (1) The surfactant described in the above patent has an extremely low manufacturing yield, or the raw materials used are extremely expensive, so the surfactant is very expensive. ■
Compared to conventional surfactants, various performances such as emulsification and dispersion are inferior. (2) Although it has polymerizable groups, it has various drawbacks such as not being well suited to the intended use.

The present inventors have arrived at the present invention as a result of intensive research in order to solve these problems. That is, the present invention has the general formula, CH3RO(
AO) ncH2CHCH20CH2C=CHO(A O
) mC-CH2 MI 0OC-CH ■ o 3M2 ・ φ −・ φ ・ (1) And, the general formula, CH8RO(A
O) ncH2CHCH20CH2C=CHMlooCC
H2 ・ ・ ・ φ ・ ・ (2) [However, in the above formula, R is an alkyl group having 8 to 30 carbon atoms, an alkenyl group, or an alkylaryl group, or an aralkylaryl group, and A is an alkylene group having 2 to 4 carbon atoms. , or a substituted alkylene group, n is an integer from O to 100, m
is an integer from 1 to 200, and M! is an alkali metal atom,
Alkanolamine residue or N Ha, M2
is an alkali metal atom or NH4. ] A novel surfactant consisting of a mixture of general formulas (1) and (2) represented by these is provided.

In the general formula, R is an alkyl group, alkenyl group, alkylaryl group, or aralkylaryl group having 8 to 30 carbon atoms, and examples of the alkyl group include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. , pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

Examples of alkenyl groups include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,
Examples include heptadecenyl, octadecenyl, and the like.

As the alkylaryl group, monobutylphenol,
dibutylphenol, see, butylphenol, di-s
Examples include ec, butylphenol, tert., butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, and didecylphenol.

Aralkylphenols include styrenated phenol, benzylphenol, cumylphenol, etc.
Examples include di- and tri-alkyl groups alone or a mixture thereof, and a mixture of these alkyl groups may also be used.

Further, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, imbutylene, etc., and may be a single group or a block or random mixture thereof.

n is an integer from 0 to ioo, m is an integer from 1 to 200,
More preferably n is O or 1-50, m is 2-100
is within the range of

Furthermore, the surfactant of the present invention can be easily produced industrially, and can be produced, for example, as follows. That is, using nonylphenol or lauryl alcohol as a raw material, allyl glycidyl ether is heated and reacted in the presence of a catalyst, and the resulting reaction composition is further added with:
Alkylene oxide is added using a conventional method. Sixth step: React with maleic anhydride, half-esterify, and then sulfate with a sulfating agent such as Hashimoto neutralized with a basic substance or sodium bisulfite. The surfactant of the present invention can be obtained by this method.

The novel surfactant of the present invention effectively acts as a surfactant during manufacturing, storage, and processing of such products as paints, printing inks, adhesives, pressure-sensitive adhesives, etc., which are particularly problematic. Thereafter, it can meet the expectations of industries that demand that various functions as a surfactant be promptly stopped.

In this case, it is optional whether an appropriate polymerization accelerator is added before the painting, printing, or adhesion process, or whether polymerization is carried out by ultraviolet rays, solar heating (curing), etc. after processing.

In addition, the novel surfactant of the present invention can further be used as an emulsifier for emulsion polymerization, a dispersant for suspension polymerization, a pigment dispersant, an emulsifier for wax, etc., a fiber post-processing agent, an emulsifier for agricultural chemicals, a dispersant, etc. It can be used for applications such as antistatic agents for synthetic resins, and can reduce the adverse effects of surfactants remaining after use.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

[% and parts indicate weight basis. ] Production Example 1 220 g [1.0 mol] of nonylphenol and 1.5 g of triethylamine as a catalyst were placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, and then 128 g [1.0 mol] of methallyl glycidyl ether was added dropwise. 5 at 100℃
Stir for hours.

Next, the obtained reaction composition was transferred to an autoclave, and using caustic potassium as a catalyst, ethylene oxide was added to the reaction composition at 10 mol and 30 mol at a pressure of 1.5 kg/cm2 and a temperature of 130°C. , 100 mol was added to obtain one reaction composition.

Next, 10 moles of ethylene oxide adduct 3 of the above reaction composition was placed in a reaction vessel equipped with a stirrer and a thermometer.
94 g [0,5 mol], 49 g [0,5 mol] maleic anhydride
mol] was charged, heated to 80°C, stirred for 3 hours, and reacted to obtain maleic acid half ester. Next, 1400g of water
After adding and diluting, 41.7g of 48% caustic soda [0,
5 mol], then sodium sulfite water 57.2
g [0.55 mol] was charged and sulfated at 80'O for 3 hours. The obtained composition is used as the surfactant of the present invention [A]
And so. A sulfonated product of succinic acid half ester of 30 moles of ethylene oxide adduct obtained in the same manner was used as the surfactant of the present invention [B], 100 moles of ethylene oxide
The sulfonated molar adduct of succinic acid half ester was used as the surfactant [C] of the present invention.

Production Example 2 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 186 g [1.0 mol] of lauryl alcohol and 0.6 g boron trifluoride ether complex as a catalyst were charged, and then 128 g [1.0 mol] of methallyl glycidyl ether was charged. 0 mol] was added dropwise, a
The mixture was stirred at o'c for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and using caustic potassium as a catalyst, 5 mol, 20 mol, and 50 mol of ethylene oxide was added to the reaction composition at a pressure of 1.5 kg/Cm2 and a temperature of 130°C. The composition obtained by the addition was anionized according to Production Example 1, and the obtained sulfonated product of 5 moles of ethylene oxide adduct succinic butyric half ester was added to the surfactant [D] of the present invention, ethylene oxide A sulfonated product of a succinic acid half ester of a 20 mole adduct was used as the surfactant of the present invention [E], and a sulfonated product of a succinic acid half ester of a 50 mole adduct of ethylene oxide was designated as the surfactant of the present invention [F].

Production Example 3 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 110 mol of distyrenated phenol ethylene oxide, 856 g [1.0 mol] of a 2 mol block adduct of propylene oxide, and 2 g of boron trifluoride ether complex as a catalyst were added. After charging, 128 g [1.0 mol] of methallyl glycidyl ether was added dropwise, and the mixture was stirred at 80° C. for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and the pressure was 1.5 kg/cm 2 using caustic potassium as a catalyst.
．． 15 moles of ethylene oxide was obtained by anionizing the composition obtained by adding 15 moles and 40 moles of ethylene oxide to the reaction composition at a temperature of 130 ° C according to Production Example 1. The sulfonated product of the succinic acid half ester of the adduct was designated as the surfactant of the present invention [G], and the sulfonated product of the succinic acid half ester of the 40 mole ethylene oxide adduct was designated as the present invention surfactant [H].

Production Example 4 1588 g of 30 mole adduct of oleyl alcohol ethylene oxide was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube.
[1.0 mol], 3 g of boron trifluoride ether complex as a catalyst, and then 128 g of methallyl glycidyl ether
g [1.0 mol] was added dropwise, and the mixture was stirred at 80° C. for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and a pressure of 1.5 kg/Cm2 was applied using caustic potassium as a catalyst. A composition obtained by randomly adding 40 moles of ethylene oxide and 10 moles of propylene oxide to the reaction composition at a temperature of 130°C was prepared according to Production Example 1.
% Caustic soda was used instead of neutralizing with monoethanolamine, and otherwise anionization was performed using the same procedure, and the obtained sulfonated product of succinic acid half ester was used as the surfactant [I] of the present invention. did.

Production Example 5 385 g of stearyl alcohol propylene oxide 2 mol adduct was placed in a reaction vessel equipped with a stirrer, thermometer, and reflux tube.
[1.0 mol] and 1.5 g of boron trifluoride ether complex as a catalyst were charged, and then 128 g [1.0 mol] of methallyl glycidyl ether was added dropwise, followed by stirring at 80°C for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and using caustic potassium as a catalyst, 2 moles of ethylene oxide, 5
A composition obtained by molar addition was obtained. Next, 314 g [0.5 mole] of the 2 mole ethylene oxide adduct of the above reaction composition and 49 g [0.5 mole] of anhydrous maleic milk were charged into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and the temperature was raised to 80°C. The mixture was heated and stirred for 3 hours to react and obtain maleic acid half ester. Next, after diluting with 1400 g of water, neutralized with 25 g [0.5 mol] of 28% aqueous ammonia, and then adding 55 g [0.55 mol] of ammonium hydrogen sulfite.
Sulfation was carried out for 3 hours at °C. The resulting composition was designated as the surfactant of the present invention [J], and the succinic acid half ester sulfonated product of a 5-mole ethylene oxide adduct obtained in the same manner was designated as the surfactant of the present invention [K].

Production Example 6 DiS'e was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube.
C, 278 g [1.0 mol] of butylphenol butylene oxide 3 mol adduct and 1 g of boron trifluoride ether complex as a catalyst were added, then 128 g [1.0 mol] methallyl glycidyl ether was added dropwise, and the mixture was heated to 80°C. 5
Stirred for 4W.

Next, the obtained reaction composition was transferred to an autoclave, and using caustic potassium as a catalyst, 2 mol of propylene oxide,
The composition obtained by adding 15 moles of ethylene oxide to the reaction composition was anionized according to Production Example 1, and the obtained succinic acid half ester sulfonated product was used as the surfactant [L] of the present invention. .

Production Example 7 Tribenzylphenol ethylene oxide 20 mol adduct 124 was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube.
4 g [1.0 mole] and 4 g of boron trifluoride ether complex as a catalyst were charged, and then 128 g [1.0 mole] of methallyl glycidyl ether was added dropwise, followed by stirring at 80° 0 for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and 5 mol of propylene oxide was added to the reaction composition under conditions of a pressure of 1.5 kg/Cm2 and a temperature of 130°C using caustic potassium as a catalyst.

The obtained composition was anionized according to Production Example 1, and the obtained succinic acid half ester sulfonated product was designated as the surfactant [M] of the present invention.

Example 1 The surface tension of the aqueous solution of the surfactants [A] to [M] of the present invention obtained in Production Examples 1.2 and 3.4.5.6.7 was measured.

The surface tension of a conventional surfactant is also shown as a comparative product. [Surface tension was measured by the Tranabe method. ] The results are shown in Table 1.

Example 2 The carbon black dispersion performance and toluene emulsification performance of the surfactants of the present invention shown in Table 2 were measured.

The performance of a conventional surfactant was also measured in the same manner as a comparative product. The results are shown in Table 2.

The test method is as follows.

[Dispersion performance test method] Surfactant 1 in a graduated cylinder with a stopper of 100ml capacity
g and carbon black Log were added and dissolved and dispersed in water to adjust the volume to 100 ml.

Next, shake the graduated cylinder 100 times per minute,
The head was kept at 25°C for 1 hour. Then, 3 from the 2nd side of the liquid.
After filtering with 0cc sampling glass filter, 10
It was dried at 5°C, and the dispersibility was measured from the weight of the residue on the glass filter using the following formula.

Dispersion performance (%) = Residual weight i (g) of glass filter [Emulsification performance test method] Add 5 ml of 0.5% surfactant aqueous solution and 5 ml of kerosene to a 20 ml capacity test tube with a graduated stopper, and add 5 ml of kerosene for 1 minute. 1
After shaking 00 times, the mixture was allowed to stand at 25°C for 1 hour. Thereafter, the volume (ml) of the emulsified layer was measured, and the emulsifying property was measured using the following formula.

Emulsifying layer (ml) Emulsifying performance (%) = X10
00g and stirred while heating to dissolve. Using 1 g of ammonium persulfate as an initiator, 240 g of vinyl acetate was added dropwise in a conventional manner, and emulsion polymerization was carried out to obtain an emulsion composition.

30 g of dibutyl phthalate was added as a film-forming agent to this emulsion composition, and the adhesive strength was measured. The results are shown in Table 3.

Example 4 Non-woven fabric made from polypropylene (2.5 cm x 10
cm) was immersed for 1 minute in a 1% aqueous solution of the surfactant shown in Table 4, and after taking it out, it was dried with hot air at 120° C. for 30 minutes.

Add the above surfactant-treated nonwoven fabric to 50ml of water.
The nonwoven fabric was suspended over a 00 ml beaker and immersed in water 1 cm from the bottom of the nonwoven fabric, and the height of water penetration after 5 minutes was measured. [Before washing] In order to further observe the washing resistance, the nonwoven fabric after treatment and drying was washed with running water for 1 minute, dried, and the same water permeability test as above was conducted. [After washing] Check the results in the fourth
Shown in the table.

Example 5 5 g of the surfactant shown in Table 5 and 50 g of acrylic acid methyl ester were placed in 200 g of toluene at 80°C using 0.5 g of benzoyl peroxide as the M medium. ,
The mixture was heated and stirred for 10 hours to react.

Next, this reaction product was poured onto a glass plate to a film thickness of 0.5 mm, and dried at room temperature for 1 day and then in an electric thermostatic oven at 80°C for 3 hours to form a film. Condition, water resistance and surface resistivity were measured. The results are shown in Table 5.

Claims (1)

[Claims] There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼...
・・・(1) And, ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2
) [However, in the above formula, R is an alkyl group having 8 to 30 carbon atoms, an alkenyl group, an alkylaryl group, or an aralkylaryl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, and n is 0 to is an integer of 100, m
is an integer from 1 to 200, M_1 is an alkali metal atom, an alkanolamine residue, or NH_4, and M
_2 is an alkali metal atom or NH_4. ] A novel surfactant consisting of a mixture of general formulas (1) and (2) represented by: