JPS5953448A - Fluorine-containing sulfato betaine and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [Rf is 3-18C saturated or unsaturated fluorinated aliphatic group; Z is -SO2-, -CO-, etc.; R1 is H, 1-12C alkyl, etc.; R2 and R3 are 1-18C alkyl, alkenyl, hydroxy-substituted alkyl, etc.; Y is -(CH2)e- or -(CH2)p-O-; e is 2-12; p is 2-3]. USE:A sulfatobetaine-type amphoteric surface active agent. It is superior to the known betaine-type amphoteric surface active agents in various properties such as the ability to lower the surface tension, frothability, hard water resistance, solubility, etc. PROCESS:The compound of formula I can be prepared by reacting the compound of formula II [Q1 is -(CH2)j-, etc.; j is 2-12; X<-> is inorganic or organic anion] with sulfating agent (e.g. chlorosulfonic acid), and if necessary, neutralizing the product. The reaction is preferably carried out in an inert solvent such as acetonitrile in the presence of a tertiary organic amine such as pyridine at -20- +150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a bifurcated formula [wherein R2, Z, R,, Y, R,, R3 and HQ, in which they are], in the molecule. The present invention relates to a novel fluorinated sulfatobetaine characterized by containing a fluorinated aliphatic group R7 and a zulfatobetaine group, and a method for producing the same.

Amphoteric surfactants have attracted attention in recent years as versatile surfactants because of their excellent compatibility with other types of surfactants having different ionic properties.

Among amphoteric surfactants containing perfluoroalkyl groups as fluorine-containing aliphatic groups, for example, amphoteric surfactants containing hydrocarbon alkyl groups are considered effective in terms of surface active properties such as the ability to lower the surface tension of aqueous solutions and foaming properties. It has become known that this material is superior to other materials, and efforts are being made to overcome the economic disadvantage of high price and apply it to glue applications.

Known fluorine-containing amphoteric surfactants can be classified as betaine type surfactants containing a nitrogen atom quaternized by a methyl group, ethyl group, or hydroxyethyl group in the molecule.

These known betaine-type amphoteric surfactants have sufficient surface-active properties, such as surface tension lowering ability, foaming properties, water solubility, and water hardness, at a pH near the isoelectric point. It was impossible for him to demonstrate his constant abilities.

The inventors of the present invention have conducted extensive research from the above point of view and found that the sulfatobemain type amphoteric surfactant represented by the general formula [1] has various surfactants! 1- properties, such as surface tension lowering ability, foaming tt, cutting water hardness, and solubility, are superior to known betaine-type amphoteric surfactant compounds beyond expectations. Discovered 1. , which led to the completion of the present invention.

That is, the present invention relates to fluorine-containing sulfatopetaine represented by the general formula IJ, and its 'J
”j quasi fh.

In the general formula ET], J6KeroR7 is a group containing a saturated or unsaturated fluorinated aliphatic group having 5 to 18 carbon atoms, preferably 4 to 12 carbon atoms, and examples of preferred ones among the few include 6 carbon atoms. ~1B perfluoroalkyl group or non-fluoroalkenyl group, ia button-shaped monobranched, cyclic (
(for example, a group such as -fluorocyclohexyl) or a combination thereof, but preferably a linear one. Furthermore, the main chain may contain an oxygen atom, such as (CF, ), CFOCF, CF, -, etc.

-(cttz) co- (where a represents an integer of 1 to 10), R1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, -(cn,)bORs, and nu is -(
CH2CR20) dR.

(However, b is an integer from 1 to 10, d is 1 to 20σ 42, R
34-t-Lower alkyl group also includes 1. < represents alkoxy A (preferably t also represents an alkyl group having 1 to 3 carbon atoms; < represents an alkoxy group).

Y is -(CR2) e-1-(-C)12→, o-(C
xI2-)10(-Ctt2)-, or-(CIb
) g O(CIh) h(IQl, r+ is 2 to 12
5b g, p, q should be 2, g, h should be 1 to 6
It is σ paralysis.

R3 and R8 may be the same or different, and have 1 carbon number.
~1B is preferably an alkyl group or an alknyl group having 1 to 6 carbon atoms, preferably a hydroxy-substituted alkyl group or an aromatic group-substituted argyl group having 1 to 18 carbon atoms, or an L-J-substituted alkyl group having an alkali of 11°. is 1 to 6, and -(CH2CH20)iH (where 1 represents an integer of 2 to 20), or R1 and R1 are connected to each other to form a ring with adjacent nitrogen atoms, such as a morpholino group,
It may also be a piperidino group.

0)k-CHICH,- (where j is an integer of 2 to 12, k is 1 to 50, preferably 1
Represents an integer between ~20. ).

The fluorine-containing sulfatopetaine of the present invention can be produced by various synthetic methods, but in the present invention, the general formula [11] [RZ, Y, R,, R2, R3, Q, has the same meaning as above and 1% be. X is an inorganic or organic anion. ] Or the general formula CIIO [R,, Z, Y, R,, R2, R5, Ql? 1i
It has the same meaning as ltj. ] Two types of production methods are provided which are characterized in that the compound represented by the above is used in equimolar or more amounts of a sulfating agent such as chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, or the like.

For example, 3, which can be synthesized by the following reaction example,
θ Here, X is an inorganic or organic anion, for example θ
eeee we eO)], C1%R
r, T, ClO4, Hso4, C113SO
Examples include 4, θ, Nos, C1l, COO, and a phosphoric acid group.

In the production method of the present invention, the reaction can be carried out in an inert solvent such as acetonitrile, dioxane, tetrahydrofuran, chloroform and the like. In addition, a reaction accelerator may be used (for example, the reaction may be carried out in the coexistence of an organic tertiary amine such as pyridine, triethylamine, tributylamine, tripropylamine, N-methylpyrrolidine, etc., or by using these amines as a solvent. The desired fluorine-containing sulfatopetaine can be obtained in high yield.

The reaction temperature is -20° to 150°C, preferably 0° to 1
], and the appropriate reaction time is usually about 5 to 20 hours.

According to this method, the yield of the target compound can be reduced to 70% or more, and by selecting the above-mentioned condition f1, it is also possible to reduce the yield to 1f1oB.

In the present invention, the sulfating agent has the general formula [
Old (→ Arike [110 terminal hydroxy group to -080, 1
As long as it can be replaced with ``example-1'' without particular limitation, it can be used as an example. Suitable sulfating agents include chlorosulfonic acid, #sulfuric acid, fuming sulfuric acid, and sulfur trioxide.

The sulfating agent usually has the general formula [F, t, [, +
17 equimole to the compound of 111 is used, but 11.
When is, for example, a -CII, CII, or OII group, two sulfate groups can be introduced into the molecule by using at least twice the molar amount. Like this (however, Q+
It has already been found by the present inventor that it has an excellent surfactant effect as represented by '' (representing the same or different Ql) and is useful as an amphoteric surfactant.

In the present invention, the general formula [
It can be easily converted into the compound of general formula [I] by neutralization treatment with a basic compound such as bone alkali, ammonia, triethylamine, monoethanolamine, triethanolamine, pyridine, or morpholine.

Specific examples of typical fluorine-containing sulfatopetaine compounds thus obtained include the following.

(Jll) The 1'J+JJt6 fluorine sulfatobetaine of the present invention has excellent properties similar to those of persimmons, as shown in the examples below.

If the acidity is lower than 80, the interfacial activity 't'□-□' will phase separate from the aqueous phase, making it impossible to maintain homogeneous solubility and significantly deteriorating the interfacial fη1 activity characteristics. Therefore, during use, the pH must be maintained on the alkaline side, which poses a practical obstacle. In contrast, the compounds of the present invention have p
It completely dissolves in water even under the strong acidity of H2, and has the property of not reducing its surfactant properties even in acidic, neutral, and basic pH ranges. The compound of the present invention has excellent dissolution stability against pH changes and is extremely useful in practice.

Then, the compound of the present invention has a hardness of 5.0 at pH 8.0.
It is completely dissolved and maintains a homogeneous solution even at a concentration of 000 ppm (Ca COs n) or higher, demonstrating excellent hard water resistance. In addition, synthetic seawater (Ca C4・2I (!0
: 0.16 俤, MgC1, -61120'.

1.10%, Na, SO,: 0.40%, NaCl
: 2.50% dissolved in #distilled water), the surface active properties of the W-cure/rl~ are completely maintained and the surface active properties of the molten metal are not diminished in the slightest.

In contrast, known betaine-type compounds e.g.
θ Ca FIB 502NH (Cit2)s N (CI
Is )t CHz Coo is 1.300ppm (
CaCOs begins to undergo phase separation in hard water with a dilution of 9,000 ml, and cannot be dissolved in synthetic seawater.

Although it is difficult to theoretically elucidate such excellent surfactant properties of the compounds of the present invention, it is possible to explain the balance between the hydrophobic effect based on the fluorinated aliphatic group and the hydrophilic effect based on the sulfatopetaine group. This is also supported by the fact that the structural difference in the divalent bridging group connecting the fluorinated aliphatic group and the sulfatopetaine group has a small effect.

As is clear from the above points, the fluorine-containing sulfatopetaine of the present invention has excellent interface properties such as dissolution stability against pH, hard water resistance, seawater resistance, foaming property, and reduction in surface blood tension. Taking advantage of its active properties, it can be used for foam fire extinguishing agents, foaming agents, cleaning agents, and moist temperature.
] Particularly suitable for machining applications. It is also suitable for application to leveling agents, paint additives, antifouling IL oil repellents, plastic additives, belt 11) inhibitors, 1liil;7 (1, 1 agents, etc.). Examples are shown for concrete explanation.
.

[Example 1] 400 g of acetonitrile and 400 g of acetonitrile were collected from 1 e, including a cooling condenser and a stirrer.
(11) Stir and heat to dissolve. Chlorsulfone F1,1.9 was slowly added dropwise to the mixture at 60° C. while stirring at +W while being careful not to generate heat.

After dropping, stir at 40°C for 4 hours to complete the reaction.
child. Next, add 2B Chi↑JaOCI + 3 methanol solution to 4
62g of neutralized V, acetonitrile and methanol were reduced and 11'1 was removed downstream.

The yellowish brown solid residue was dried under reduced pressure at 50°C and purified by recrystallization from ethanol to obtain the desired substance 1':I.

IR spectrum 1370 cm' (-8O2N(νaa) 1240 rho' (-=O8O3νas) NMR spectrum (D,
O/CI), OD = 1/1 fluoride, DSS standard) 2, 10 ppm (m, 2H), 3.20 ppnt
(a, 611) 3, 50 ppm (m, 611), 6
80 ppm (t, 2IT) [Example 2] 400 g of pyridine was charged into a reactor similar to Example 1, and chlorsulfone (
+'414.9 Slowly drop 1, being careful not to generate heat.
The reaction was allowed to proceed for 7.5 hours. After the reaction is completed, 28'IrN
a0CII, add 462g of methanol solution and make enough]
After neutralization with W stirring, pyridine Jd and methanol were distilled off under reduced pressure. The desired substance was obtained by recrystallizing the brown solid residue 7rf from ethanol.

IR spectrum 1570 Cr1-' (S o2N(Va
m)1240crn-' (-0803yas)
NMR spectrum (1), O/CD, 0D=1/1 solvent, DSS standard) 2, 10 ppm (m, 2H), 5.20 ppm (
s, 611) 550 ppm (m, 6H), 58
0 ppm (t, 2H) [Contamination 1 Example 6] 300 g of pyridine was charged into the same reactor as in Example 1, and dissolved by heating to 70°C.

Using a dropping funnel, 1 g of m-sulfuric acid was slowly added dropwise while being careful not to generate heat, and the mixture was allowed to react at 70° C. for 7 hours. The mixture was cooled to room temperature (7), the precipitate was taken out by filtration (17), and V11 crystals were separated from ethanol to obtain the desired substance.

nl calculated value (ql)) 25.4 2.4
4,0 45.6 IR and NMR spectra were completely identical to those of Example 1.

[Contaminants 1 Examples 4 to 10] The same procedure as in Example 1 was carried out, except that the starting materials in Table 1 were changed and the amounts listed were used.
The product materials listed in the table were obtained in the amounts listed in each column.

The obtained product was analyzed by elemental analysis, IR, and NMR, and the results are also shown in Table 1, and it was confirmed that the target substance was obtained.

[Reference Examples 1 to 10] Surface active property values (surface tension and foaming properties of aqueous solutions) of the compounds of the present invention synthesized in Examples 1 to 10 are summarized in Table 2.

In addition, the surface tension was measured at 25°C using the Wilhelmy method.
The foaming property was measured by the Ross-Miles method at 25° C. by measuring the foam height immediately after foaming and after 5 minutes.

However, distilled water and synthetic seawater were used as solvents, and the composition of the synthetic seawater was NaC62, 50% MgC/I2.6u, o 1.10% Na, So
, 0.40% CaCA! 2 ・2II20 0.16%, and the rest is distilled water Table 2 However, in the table, the upper row represents the distilled aqueous solution, and the lower row represents the synthetic seawater solution, and the concentrations are 0.1% by weight in both cases.

Moreover, since Example 6 was made of the same substance as Example 1, it was omitted.

Two major patent applicants: Nippon Ink and Chemical Industry Co., Ltd. Kawamura Physical and Chemical Research Institute

Claims (1)

[Claims] 1. Represents the general formula [I] WASU). Fluorine-containing sulfatopetaine represented by 1. The fluorine-containing sulfatopetaine according to claim 1, wherein 'l, R, is a covered fluoroalkyl group or a perfluoroalganyl group. 8. A sulfating agent is applied to the compound represented by general formula [II) to neutralize it as necessary to form the compound represented by general formula [1] [However, in the formula, R2, Z, R,, Y, R14R, and Q are Same as above] A method for producing fluorine-containing sulfatopetaine, which is characterized by producing a compound represented by the following. The manufacturing method according to claim 6, wherein chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, or sulfur trioxide is used as the sulfating agent. 5. A compound represented by the general formula [■[] in which R7, Z, Y, R, , R1 and Q+ are the same as above] is reacted with a sulfating agent to form the compound of the general formula [I] [where R, , A method for producing fluorine-containing sulfatobetaine, which produces a compound represented by the following: Z, Y, R1, R8, and Q are the same as above. 6 iFJγ using chlorosulfonic acid, fA sulfuric acid, fuming sulfuric acid, or sulfur trioxide as a sulfating agent [Production method according to claim 6πj of box jM.