JPS63183998A - Novel surfactant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel surfactant, and particularly to a sulfate ester type anionic surfactant having a polymerizable group.

Conventionally, surfactants have a wide range of properties such as emulsification, dispersion, cleaning, wetting, foaming, etc., and these properties are used to improve the production of fibers, paper, rubber, plastics, etc. It is used in all fields such as metals, paints, pigments, 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 countermeasures to these problems, efforts are being made to reduce the amount of surfactants blended and to 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 issues such as No. 84.

Various attempts have been made to use these surfactants mainly as emulsifiers for emulsion polymerization, but they have not been fully satisfactory and have not reached the 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 following general formula: OR2R! O(
A, O) n CH2CHCH20C-C=CH2■0 (AO)msOaM [However, in the above formula, R1 is an alkyl group having 8 to 30 carbon atoms,
Alkenyl group, alkylaryl group, aralkylaryl group, R2 is a hydrogen atom or methyl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, n is an integer from 0-Zoo, and 1m is 1 to 200 is an integer of , M is an alkali metal atom, NH4, or an alkanolamine residue].

In the general formula, R1 is an alkyl group, an alkenyl group, an alkylaryl group, or an aralkylaryl group having 8 to 30 carbon atoms, and examples of the alkyl group include octyl, nonyl, decyl, undecyl, dodecyl,
Examples include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oftadecyl, nonadecyl, eicosyl, and the like.

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

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

Aralkylphenols include monostyrylated 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 a fullkylene group or a 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 too; 1m 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 manufactured industrially, and can be manufactured, for example, as follows. That is, using nonylphenol or lauryl alcohol as a raw material, glycidyl methacrylate is heated and reacted in the presence of a catalyst, and alkylene oxide is further added to the resulting reaction composition in a conventional manner. The surfactant of the present invention can be obtained by sulfating with a sulfating agent such as an acid and neutralizing with a basic substance if necessary.

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 polymerization, a dye, a pigment dispersant, an emulsifier for wax, etc., a fiber post-processing agent, and an emulsifier 1 dispersant for agricultural chemicals. 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.

[51 parts refers to weight basis] Production Example: Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 220 g [1.0 mol] of nonylphenol and 1.5 g of triethylamine as a catalyst were charged, and then glycidyl methacrylate was added. 142g [1.0 mol] was added dropwise and stirred at 100°C for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. Adding 10 moles, 30 moles, and 100 moles of ethylene oxide to the reaction composition at a temperature of 130 ° C.
After obtaining the composition, 387 g [0.5 mol] of the 10 mol ethylene oxide adduct of the above reaction composition and 58.2 mol sulfamic acid were placed in a reaction vessel equipped with a PIl stirrer and a thermometer.
g [0.6 mol] was charged, the temperature was raised to 120°C, and the reaction was stirred for 3 hours to perform sulfation. The composition obtained by removing unreacted sulfamic acid on a daily basis is used as the surfactant of the present invention [
A), the sulfate ester ammonium salt of 30 mol ethylene oxide adduct obtained by the same operation as surfactant [B] of the present invention, and the sulfuric ester ammonium salt of 100 mol ethylene oxide adduct 1 as the surfactant of the present invention [B] This was designated as activator [C].

Production Example 2 A reaction vessel equipped with a stirrer, a thermometer, and a reflux tube was charged with 186 g [1.0 mol] of lauryl alcohol and 0.6 g of boron trifluoride ether complex as a catalyst, and then 142 g [l] of glycidyl methacrylate.

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 caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. The composition obtained by adding 5 mol, 20 mol, and 50 mol of ethylene oxide to the reaction composition at a temperature of 130°C was sulfated according to Production Example 1 to obtain ethylene oxide 5. The ammonium sulfate ester ammonium salt of the molar adduct, the surfactant of the present invention [D], the ammonium sulfate ester ammonium salt of the ha-form with 20 moles of ethylene oxide, the surfactant of the present invention [E], the sulfuric acid of the 50 mole ethylene oxide adduct. The ester ammonium salt was designated as the surfactant CF of the present invention.

Production Example 3 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 10 moles of distyrenated phenol ethylene oxide, 856 g [1,0 moles] of a 2 mole block adduct of propylene oxide, and 2 g of boron trifluoride ether complex as a catalyst were charged. Next, 142 g [L, O mol] of glycidyl methacrylate 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. The composition obtained by adding 15 mol and 40 mol of ethylene oxide to the reaction composition at a temperature of 130°C was sulfated according to Production Example 1, and 15 mol of the obtained ethylene oxide was added. The surfactant of the present invention [G], ethylene oxide 40
The ammonium sulfate ester salt of the molar adduct was designated as the surfactant [H] of the present invention.

Production Example 4 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, add 30 moles of oleyl urea 9 oleyl ethylene oxide adduct 1588.
g [1.0 mol], 3 g of boron trifluoride ether complex as a catalyst, and then glycidyl methacrylate 14
2 g [1.0 mol] was added dropwise and stirred at 80°C for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. According to Production Example 1, a composition obtained by randomly adding 40 moles of ethylene oxide and 10 moles of propylene oxide to the reaction composition at 130 ° C.
M-oxidation was carried out using sulfamic acid, and an amount of caustic soda equivalent to the sulfamic acid was added to the obtained sulfate to remove ammonia, and the obtained sulfate ester sodium salt was designated as the surfactant [I] of the present invention.

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], 1.5 g of boron trifluoride ether complex as a catalyst, and then glycidyl methacrylate 14
2 g [1.0 mol] was added dropwise and stirred at 80° C. for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. A composition obtained by adding 2 moles or 5 moles of ethylene oxide at a temperature of 130°C is sulfated using sulfamic acid according to Production Example 1, and the obtained sulfate is added with sulfamic acid and sulfamic acid. Add an equivalent amount of monoethanolamine,
Ethylene oxide 2 obtained by removing ammonia
The sulfuric acid ester monoethanolamine salt of the molar adduct was used as the surfactant of the present invention [J], and the sulfuric acid ester monoethanolamine salt of the ethylene oxide 5 molar adduct was used as the surfactant of the present invention [K].

Production Example 6 Di-SeC,
Butylphenol butylene oxide 3 mole adduct 27
8 g [1,0 mol], 1 g of trifluoride trifluoride ether complex as a catalyst, and the first glycidyl methacrylate.
) 142g [1.0 mol] was added dropwise at 80°C.
Stir for hours.

Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. At a temperature of 130°C, 2 moles of propylene oxide and 15 moles of ethylene oxide were added to the reaction composition, and the resulting composition was sulfated according to Production Example 1 to obtain the sulfate ester ammonium salt. was designated 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 mol], 4 g of boron trifluoride ether complex as a catalyst, and then glycidyl acrylate) 12
8 g [1.0 mol] was added dropwise and stirred at 80° C. for 5 hours.

Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. At a temperature of 130°C, 5 mol of propylene oxide was added to the reaction composition, and the resulting composition was prepared in Production Example 1.
The sulfate ester ammonium salt obtained by sulfation according to the method 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 Example 1.2.3.4.5.6.7 was measured.

In addition, the surface tension of a conventional surfactant is also shown as a comparative amount. [Surface tension was measured by the Traube method. ] The results are shown in Table 3.

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

Note that the performance of a conventional surfactant was also measured in the same manner as a comparative amount. The results are shown in Table 4.

The test method is as follows.

[Dispersion performance test method] Surfactant 1 in a 100m1 graduated cylinder with a stopper.
g and carbon black log were added and dissolved and dispersed in water to adjust the volume to 100ml.

Next, shake the graduated cylinder 100 times per minute,
It was left standing at 25°C for 1 hour. After that, 30c from the top of the liquid.
105℃ after filtration with a glass filter
The dispersibility was measured from the weight of the afterflame on the glass filter using the following formula.

Dispersion performance (%) = Afterflame weight of glass filter (g) [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 a (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 aid 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 lo
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.
Hang it over a 00m1 beaker, 1cm from the bottom of the nonwoven fabric.
The sample was immersed in water, and the height of water penetration after 5 minutes was measured. [
Before washing] In order to further observe washing resistance, the nonwoven fabric after treatment and drying was washed with running water for 1 minute, dried, and subjected to the same water permeability test as above. [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 mixed in 200 g of toluene with 0.5 g of benzoyl peroxide as a catalyst at 80°C for 10 minutes.
The mixture was heated and stirred for a period of time 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.

Table 3 Table 4

Claims (1)

[Claims] There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula, R_1 is an alkyl group having 8 to 30 carbon atoms, an alkenyl group, or an alkylaryl group, and R_2 is an aralkylaryl group. hydrogen atom or methyl group,
A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is an integer of 0 to 100, and m is 1 to 200.
is an integer of , M is an alkali metal atom, NH_4, or an alkanolamine residue.] A novel surfactant comprising a compound represented by the following.