JPH0222695B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a surfactant, and particularly to a phosphate ester type anionic surfactant having an allyl group. Conventionally, surfactants have a wide range of properties such as emulsification, dispersion, cleaning, wetting, and foaming, and these properties have been used to improve materials such as fibers, paper, rubber, plastics, metals, and paints. It is used in various fields such as pigments, civil engineering and architecture. 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, etc. are used during the manufacturing of the product, or during product stabilization.
Furthermore, it is indispensable in terms of workability and the like. When these products are used in applications such as coating, printing, adhesion, and adhesion, surfactants are not necessary; rather, the surfactants present are responsible for forming coatings, printed surfaces, and adhesive films. In many cases, performance such as water resistance and oil resistance may be deteriorated. 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. I haven't reached it yet. 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. 34894, Special Publication No. 56-29657, Japanese Patent Publication No. 51-30285
No., JP-A-49-46291, JP-A-56-127697, etc., and as a nonionic surfactant, JP-A-56-
No. 28208, JP-A-50-98484, 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 that the surfactant described in the above patent has an extremely low production 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. Although it has polymerizable groups, it has various drawbacks such as not being well suited for 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: general formula, [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 100 , m is an integer from 1 to 200, and M is an alkali metal atom, NH ₄ , an alkanolamine residue, or hydrogen. ] It provides a surfactant characterized by containing a mixture of compounds represented by the following. 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. ,
Examples include pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and the like. Examples of alkenyl groups include octenyl,
Examples include nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like. Examples of the alkylaryl group include monobutylphenol, dibutylphenol, sec.butylphenol, disec.butylphenol, tert.butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol,
Examples include didecylphenol. Examples of aralkyl phenols include styrenated phenols, benzyl phenols, cumyl phenols, and the like, mono-, di-, and tri-single or mixtures thereof, and may be mixtures of these alkyl groups. Further, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, isobutylene, etc., and may be a single group or a block or random mixture thereof. n is an integer of 0 to 100, m is an integer of 1 to 200, more preferably n is 0 or 1 to 50, m is 2
~100 range. Furthermore, the surfactant of the present invention can be easily manufactured industrially, and can be manufactured, for example, as follows. That is, nonylphenol or lauryl alcohol is used as a raw material, alkylene oxide is added if necessary, allyl glycidyl ether is heated and reacted in the presence of a catalyst, and alkylene oxide is further added to the resulting reaction composition by a conventional method. Add it at . Next, the surfactant of the present invention can be obtained by phosphoric acid esterification using a phosphorylating agent such as phosphoric anhydride or phosphorus oxychloride, and neutralization with a basic substance if necessary. The surfactant of the present invention can be applied to paints with particular problems,
After acting effectively as a surfactant during the manufacturing, storage, and processing of products such as printing inks, adhesives, and pressure-sensitive adhesives, it is desirable to immediately stop their various functions as a surfactant. We can meet the expectations of the demanding industry. In this case, it is optional whether a suitable 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. The surfactant of the present invention can also be used as a dispersant for suspension polymerization, a dye, a pigment dispersant, an emulsifier for wax, etc., a fiber post-processing agent, an emulsifier for agricultural chemicals, a dispersant, an antistatic agent for synthetic resins, etc. It can be used for various purposes 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 114 g [1.0 mol] of allyl glycidyl ether was added dropwise to 100 g.
The mixture was stirred at ℃ for 5 hours. Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst to
10 mol, 30 mol, and 100 mol of ethylene oxide were added to the reaction composition under conditions of cm ² and temperature of 130° C. to obtain reaction compositions. Next, 387 g [0.5 mol] of the 10 mol ethylene oxide adduct of the above reaction composition and 22.7 g [0.16 mol] phosphoric anhydride were placed in a reaction vessel equipped with a stirrer and a thermometer, and the temperature was raised to 80°C while stirring. and carry out the phosphorylation reaction for 5 hours,
The obtained composition was designated as the surfactant [A] of the present invention. Ethylene oxide obtained by similar operation
The phosphoric acid ester of the 30 mole adduct was used as the surfactant of the present invention [B], and the phosphoric acid ester of the 100 mole ethylene oxide adduct was used as the surfactant of the present invention [C]. Table 1 shows the monoester and diester contents of the products of the present invention. Production Example 2 Into a reactor equipped with a stirrer, a thermometer, and a reflux tube, 186 g [1.0 mol] of lauryl alcohol and 0.6 g of boron triboride ether complex as a catalyst were charged, and then 228 g [2.0 mol] of allyl glycidyl ether was added dropwise. After stirring at 80°C for 5 hours, the mixture was heated to 120°C and excess allyl glycidyl ether was removed under reduced pressure. Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst.
The compositions obtained by adding 5 mol, 20 mol, and 50 mol of ethylene oxide to the reaction composition under the conditions of 1.5 Kg/cm ² and a temperature of 130°C were subjected to phosphoric acid esterification according to Production Example 1. The phosphoric acid ester of 5 moles of ethylene oxide adduct, the surfactant of the present invention [D], the phosphoric acid ester of 20 moles of ethylene oxide adduct, the surfactant of the present invention [E], and ethylene A phosphoric acid ester of a 50 mole oxide adduct was used as the surfactant [F] of the present invention. Table 1 shows the monoester and diester contents of the products of the present invention. Production Example 3 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, add 10 moles of distyrenated phenol ethylene oxide and 2 moles of propylene oxide block adduct.
856 g [1.0 mol] and 2 g of boron trifluoride ether complex as a catalyst were added, and then 228 g [2.0 mol] of allyl glycidyl ether was added dropwise, and at 80°C, 5 g of boron trifluoride ether complex was added.
After stirring for an hour, the mixture was heated to 120°C and excess allyl glycidyl ether was removed under reduced pressure. 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/cm ² and a temperature of 130°C.
The composition obtained by adding 15 mol or 40 mol of ethylene oxide to the reaction composition at ℃ conditions was subjected to phosphoric acid esterification according to Production Example 1,
The obtained phosphoric acid ester of 15 moles of ethylene oxide adduct, the surfactant [G] of the present invention, the phosphoric acid ester of 40 moles of ethylene oxide adduct,
The surfactant of the present invention was referred to as [H]. Table 1 shows the monoester and diester contents of the products of the present invention. Production Example 4 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 1588 g [1.0 mole] of 30 mole adduct of oleyl alcohol ethylene oxide and 3 g boron trifluoride ether complex as a catalyst were charged, and then 228 g [1.0 mole] of allyl glycidyl ether was charged. 2.0 mol] was added dropwise at 80℃.
After stirring for 5 hours, the mixture was heated to 120°C and excess allyl glycidyl ether was removed under reduced pressure. 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/cm ² and a temperature of
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.
Phosphoric acid esterification was carried out according to the method described in 1. Next, the sodium phosphate salt obtained by adding caustic soda (40% aqueous solution) in an amount equivalent to the acid value and neutralizing it was used as the surfactant of the present invention []. Table 1 shows the monoester and diester contents of the products of the present invention. Production Example 5 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 385 g [1.0 mol] of a 2-mol adduct of stearyl alcohol propylene oxide and 1.5 g of boron trifluoride ether complex as a catalyst were charged, and then 228 g of allyl glycidyl ether was charged. [2.0 mol] was added dropwise to 80℃.
After stirring for 5 hours, the mixture was heated to 120°C, and excess allyl glycidyl ether was removed under reduced pressure. Next, the obtained reaction composition was transferred to an autoclave, and a pressure of 1.5 kg/kg was added using caustic potassium as a catalyst.
The composition obtained by adding 2 moles or 5 moles of ethylene oxide at a temperature of 130° C. was subjected to phosphoric acid esterification according to Production Example 1, and then an amount of monoethanolamine equivalent to the acid value ^was added. The phosphoric acid ester monoethanolamine salt of 2 moles of ethylene oxide adduct obtained by adding and neutralizing the surfactant [J] of the present invention, and the phosphoric acid ester monoethanolamine salt of 5 moles of ethylene oxide adduct obtained by adding and neutralizing the surfactant [J]. The surfactant of the present invention was referred to as [K]. Table 1 shows the monoester and diester contents of the products of the present invention. Production Example 6 A reaction vessel equipped with a stirrer, a thermometer, and a reflux tube was
sec. 278 g [1.0 mol] of a 3-mole adduct of butylphenol butylene oxide and 1 g of boron trifluoride ether complex as a catalyst were charged, then 228 g [2.0 mol] of allyl glycidyl ether was added dropwise, and the mixture was stirred at 80°C for 5 hours. After that, the mixture was heated to 120°C and excess allyl glycidyl ether was removed under reduced pressure.
Next, the obtained reaction composition was transferred to an autoclave, and a pressure of 1.5 Kg/cm ² was applied using caustic potassium as a catalyst.
At a temperature of 130℃, propylene oxide 2
The composition obtained by adding 15 moles of ethylene oxide to the reaction composition was subjected to phosphoric acid esterification according to Production Example 1, and the obtained phosphoric ester was used as the surfactant [L] of the present invention. did. Table 1 shows the monoester and diester contents of the products of the present invention. Production Example 7 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 1244 g [1.0 mole] of a 20 mole adduct of tribenzylphenol ethylene oxide and 4 g of boron trifluoride ether complex as a catalyst were charged, and then 228 g of allyl glycidyl ether was charged. [2.0 mol] was added dropwise, and after stirring at 80°C for 5 hours, the mixture was heated to 120°C, and excess allyl glycidyl ether was removed under reduced pressure.
Next, the obtained reaction composition was transferred to an autoclave, and a pressure of 1.5 Kg/cm ² was applied using caustic potassium as a catalyst.
At a temperature of 130°C, 5 mol of propylene oxide was added to the reaction composition, and the resulting composition was phosphoric esterified according to Production Example 1. This was designated as invention surfactant [M]. Table 1 shows the monoester and diester contents of the products of the present invention. Example 1 The surface tensions of the aqueous solutions of the surfactants [A] to [M] of the present invention obtained in Production Examples 1, 2, 3, 4, 5, 6, and 7 were measured. The surface tension of a conventional surfactant is also shown as a comparative product. [Surface tension was measured by the Traube 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] 1 g of surfactant and 10 g of carbon black were placed in a 100 ml measuring cylinder with a stopper, and dissolved and dispersed with water to adjust the volume to 100 ml. Next, the graduated cylinder was shaken 100 times per minute and left at 25° C. for 1 hour. Thereafter, 30 c.c. of the liquid was extracted from the upper surface of the liquid and filtered through a glass filter, and then dried at 105° C., and the dispersibility was measured from the weight of the residue on the glass filter using the following formula. Dispersion performance (%) = Residual weight of glass filter (g) / 3 (g) x 100 [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. The mixture was shaken 100 times per minute, and then left 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. Emulsification performance (%) = emulsification layer (ml) / 10 (ml) x 10
0 Example 3 Nonwoven fabric made from polypropylene (2.5cm x
10 cm) was immersed for 1 minute in a 1% aqueous solution of the surfactant shown in Table 3, taken out, and dried with hot air at 120° C. for 30 minutes. The nonwoven fabric treated with the surfactant was suspended over a 100 ml beaker containing 50 ml of water, and 1 cm from the bottom of the nonwoven fabric was immersed in water, 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] The results are shown in Table 3. Example 4 5 g of the surfactant shown in Table 4 and 50 g of acrylic acid methyl ester were placed in a flask in 200 g of toluene using 0.5 g of benzoyl peroxide as a catalyst.
The mixture was heated and stirred at 80°C 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 constant temperature oven at 80°C for 3 hours to form a film.
The condition, water resistance and surface resistivity of the film were measured. The results are shown in Table 4.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 General formula, general formula, [However, in the above formula, R is an alkyl group, alkenyl group, or alkylaryl group having 8 to 30 carbon atoms, 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 100 m is an integer of 1 to 200, M is an alkali metal atom, NH ₄ , an alkanolamine residue, or a hydrogen atom. ] A surfactant characterized by containing a mixture of compounds represented by the following.