JPS63214336A - Novel surfactant - Google Patents

Abstract

PURPOSE:To rapidly stop the various functions of surface activity after surface active action in the manufacturing of a product, by preparing a sulfuric ester type anionic surfactant having a specific allyl group. CONSTITUTION:Alkylene oxide is added to a reaction composition, which is obtained by reacting allylglycidyl ether with nonylphenol or laurylphenol being a raw material in the presence of a catalyst under heating, according to a usual method. Next, the reaction composition is sulfated with a sulfation agent such as sulfuric acid and neutralized if necessary by a basic substance to obtain a surfactant being a compound represented by formula I (wherein R is a 8-30C alkyl group or an alkenyl group, A is a 2-4C alkylene group, n is an integer of 0-100, m is an integer of 1-200 and M is an alkali metal atom, NH4, or an alkanolamine residue).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel surfactant, and particularly to a sulfate ester type anionic surfactant having an allyl 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 have been made to reduce the amount of surfactants blended and to use polymeric surfactants, but these problems have not yet been fully resolved in terms of product stability, workability, etc. not present.

On the other hand, in order to provide a new type of surfactant, 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-50-98
There are issues such as No. 484.

Various attempts have been made to use these surfactants mainly as emulsifiers for emulsion polymerization that copolymerize with monomers.

The present invention is based on the general formula: RO(AO)ncHzcHcHzOcHzcII =
CHz0 (AO) msOaM [However, in the above formula, R is an alkyl group having 8 to 30 carbon atoms,
an alkenyl group, an alkylaryl group, an aralkylaryl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, n is an integer from θ to 100,
m is an integer from 1 to 200, M is an alkali metal atom,
NH4 is an alkanolamine residue. ] A novel surfactant for treating substances that does not react with the compound 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 the alkenyl group include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,
Examples include heptadecenyl and octadecenyl.

As the alkylaryl group, monobutylphenol,
dibutylphenol, 5ec-butylphenol, di5
Examples include ec-butylphenol, tert-butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, and didecylphenol.

Examples of aralkylphenols include styrenated phenol, benzylphenol, cumylphenol, etc. mono-, di-, and tri-single or a mixture thereof.
A mixture of these alkyl groups and the like may be used.

Further, A is an alkylene group or a 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 1-5o, 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, 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 obtained reaction composition in a conventional manner. and add it. Next, the surfactant of the present invention can be obtained by sulfating with a sulfating agent such as sulfuric acid or sulfamic 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.

Furthermore, the novel surfactant of the present invention reacts with other surfactants such as dyes, pigment dispersants, emulsifiers such as waxes, fiber post-processing agents, emulsifiers and dispersants for agricultural chemicals, and antistatic agents for synthetic resins. It can be used to treat substances that do not contain water, and can reduce the negative effects of surfactants that remain after use.

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

(% 1 part indicates weight basis.) Production Example 1 220 g (1.0 mol) of nonylphenol and 1.5 g of triethylamine as a catalyst were charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube. 114 g (1.0 mol) of glycidyl ether was added dropwise and stirred at 100° C. for 5 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 a pressure of 1.5 kg/cd and a temperature of 130°C at 10 mol, 30 mol, and 100 mol. A composition was obtained by molar addition. Next, 15 moles of ethylene oxide adduct 38 of the above reaction composition was placed in a reaction vessel equipped with a stirrer and a thermometer.
7g (0,5 mol), sulfamic acid 58.2g (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 daily was designated as the surfactant (A) of the present invention. The ammonium sulfate ester of an adduct of 30 moles of ethylene oxide obtained in the same manner was used as the surfactant of the present invention [B], and the ammonium sulfate of an adduct of 15 moles of ethylene oxide was used as the surfactant of the present invention ( C).

Production Example 2 Into a reaction vessel equipped with a stirrer, a temperature needle, and a reflux tube, 186 g (1.0 mol) of lauryl alcohol and 0.6 g of boron trifluoride ether complex as catalyst a were charged, and then 228 g (2,0 mol) of allyl glycidyl ether was charged. 0 mol) was added dropwise at 80°C.
After stirring for 5 hours, the reaction composition 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 heated to 1.5 kg using caustic potassium as a catalyst. /aj, 5% of ethylene oxide was added to the reaction composition at a temperature of 130°C.
The compositions obtained by addition of 5 moles of ethylene oxide and 5 moles of ethylene oxide were sulfated according to Production Example 1, and the resulting ammonium sulfate ester ammonium salt of 5 moles of ethylene oxide was added to the surfactant of the present invention [D ], the ammonium sulfate ester of an adduct of 20 moles of ethylene oxide was used as the surfactant of the present invention [E], and the ammonium sulfate ester of an adduct of 50 moles of ethylene oxide was used as the surfactant of the present invention (F).

Production Example 3 Into a reaction vessel equipped with a stirrer, a temperature needle, and a reflux tube, 856 g (1.0 mol) of a block adduct of 10 moles of distyrenated phenol ethylene oxide and 2 moles of propylene oxide, and 2 g of boron trifluoride ether complex as a catalyst were charged. Next, 228 g (2.0 mol) of allyl glycidyl ether 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 heated at a pressure of 1.5 kg/kg using caustic potassium as a catalyst.
cj, the composition obtained by adding 15 mol or 40 mol of ethylene oxide to the reaction composition at a temperature of 130°C was sulfated according to Production Example 1.

The sulfuric acid ester ammonium salt of the 15 mole ethylene oxide adduct obtained was added to the surfactant of the present invention [G]
, a sulfuric acid ester ammonium salt of a 40 mol ethylene oxide adduct was used as the surfactant of the present invention [1].

Production Example 4 1588 g of 30 mole adduct of oleyl alcohol ethylene oxide was placed in a reaction vessel equipped with a stirrer, temperature needle, and reflux tube.
(1.0 mol), 3 g of boron trifluoride ether complex as a catalyst, and then 228 g of allyl glycidyl ether.
(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 caustic potassium was used as a catalyst at a pressure of 1.
A composition obtained by randomly adding 40 moles of tyrene oxide and 10 moles of propylene oxide to the reaction composition under conditions of 5 kg/cd and a temperature of 130 ° C.
Sulfation is carried out using sulfamic acid according to Production Example 1, and caustic soda in an amount equivalent to the sulfamic acid is added to the obtained sulfate to remove ammonia, and the obtained sulfate ester sodium salt is used as the surfactant of the present invention. N).

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 allyl glycidyl ether 22
8 g (2.0 mol) was added dropwise, stirred at 80°C for 5 hours, then 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 2 moles and 5 moles of ethylene oxide were added using caustic potassium as a catalyst at a pressure of 1.5 kg/cII and a temperature of 130°C. According to Production Example 1, sulfation is carried out using sulfamic acid, monoethanolamine in an amount equivalent to sulfamic acid is added to the obtained sulfated product, and then ammonia is added to the obtained sulfamic acid. The ester monoethanolamine salt was used as the surfactant of the present invention [J], and the sulfuric acid ester monoethanolamine salt of a 5 mole ethylene oxide adduct was used as the surfactant of the present invention (K).

Production Example 6 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube,
Butylphenol butylene oxide 3 mole adduct 27
8 g (1.0 mol), 1 g of boron trifluoride ether complex as a catalyst, and then allyl glycidyl ether 22
8 g (2.0 mol) was added dropwise, stirred at 80°C for 5 hours, then 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 using caustic potassium as a catalyst, 2 moles of propylene oxide and 15 moles of ethylene oxide were added to the reaction composition at a pressure of 1.5 kg/i and a temperature of 130°C. The resulting composition was sulfated according to Production Example 1, and the obtained sulfate ester ammonium salt was used as the surfactant (L) of the present invention.

Production Example 7 20 mol of tribenzylphenol ethylene oxide adduct 12 was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube.
44 g (1.0 mol), 4 g of boron trifluoride ether complex as a catalyst, and then allyl glycidyl ether 2
28 g (2.0 mol) was added dropwise, stirred at 80°C for 5 hours, then 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 using caustic potassium as a catalyst, 5 mol of propylene oxide was added to the reaction composition at a pressure of 1.5 kg/cd and a temperature of 130°C. The resulting composition was sulfated according to Production Example 1, and the obtained sulfate ester ammonium salt was used as the surfactant (M) of the present invention.

Example 1 Surfactant (A) of the present invention obtained in Production Examples 1 to 7
~(M), the surface tension of its aqueous solution was measured.

In addition, 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. Note that 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.

1 g of surfactant in a measuring cylinder with a stopper in a 100-meter container for dispersing blood.
10 g of No. 1 carbon blank was added, dissolved and dispersed in water, and adjusted to 100 ae.

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 passing through a glass filter
The dispersibility of the residue on the glass filter was measured using the following formula.

Capacity 20In! Add 5 drops of 0.5% surfactant aqueous solution and 5 drops of kerosene to a stoppered test tube with a scale, and add 5 drops of 0.5% surfactant solution and 5 drops of kerosene to
After shaking 0 times, it was left standing at 25° C. for 1 hour. after that,
The volume fa(d) of the emulsified layer was measured, and the emulsifying property was measured using the following formula.

Example 3 Non-woven fabric made from polypropylene (2,5ell
10 cm) was immersed for 1 minute in a 1% aqueous solution of the surfactant shown in Table 3, taken out, and then dried with hot air at 120° C. for 30 minutes.

10ml of the above surfactant-treated nonwoven fabric in 50ml of water.
01ni hanging above the beaker, ILI from the bottom of the non-woven fabric.
J 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. The results (after washing) are shown in Table 3.

(Margin below)

Claims (1)

[Claims] There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula, R is an alkyl group having 8 to 30 carbon atoms,
an alkenyl group, an alkylaryl group, an aralkylaryl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, n is an integer from 0 to 100,
m is an integer from 1 to 200, M is an alkali metal atom,
NH_4, alkanolamine residue. ] A novel surfactant for treating substances that do not react with the compound.