JPS58203959A - Trianion type ampholytic compound containing fluorine and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [Rf is 3-20C fluorinated aliphatic group; Z is bivalent linking group; Q is -(CH2)l- (l is an integer 1-6), -(CH2)n-O- (CH2)n- (m and n are integers 2-6), etc.; Q1-Q3 are 1-8C bifunctional aliphatic hydrocarbon, etc.; A1-A3 are anionic atomic group; M1-M3 are H or cation; X<-> is anion]. USE:An ampholotic surfactant, containing fluorine, having improved foaming property and foam stability in seawater, improved ability to reduce the surface tension and further hard water resistance and stability to pH, etc., and suitable for application to bubble extinguishers, foaming agents, detergents, leveling agents, etc. PROCESS:A compound containing fluorine of formula II is reacted with one or two of a compound of the formula X-(CH2)a1-COOM (X is Cl or Br; a1 is an integer 1-3), a compound of the formula X-Q3SO3M3, acrylic acid or a 3C or 4C alkanolactone to give the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel compound with excellent surfactant properties, characterized by having an essential content of fluorinated aliphatic groups in the molecule, such as sulfonate residues or sulfate residues. This invention relates to a fluorine trianion type amphoteric compound and a method for producing the same.

Amphoteric compounds generally have excellent hard water resistance and are highly compatible with other types of surfactants with different ionic properties.

It has recently attracted attention as a versatile surfactant.

This is because fluorine-containing amphoteric surfactants having fluorinated aliphatic groups such as K, half-0-roalkyl groups also have surfactant properties such as remarkable surface tension lowering ability and foaming ability in addition to the above-mentioned characteristics.

Its high value-added properties are being utilized in a variety of applications, such as fire extinguishing foam, wetting agents, oil repellents, and penetrating agents.

However, conventional fluorine-containing amphoteric compounds, such as C,
F,, So, N(CH,)sN(CH,), Cooe The in-type amphoteric surfactant has a strong ability to absorb water in the vicinity of its isoelectric point (pH 5 to 8) and in the strongly acidic region. It has five drawbacks, such as a decrease in solubility in the water, resulting in a significant deterioration of various surfactant properties such as surface tension lowering ability and foaming ability.

As a result of intensive research from the above viewpoint, the present inventors have found that
The following general formulas [G1], [G1] (However, Rf* zm Q+i X* Qls in the formula
Qt * Qs s Al mAm, dove, dove, dove have the same meaning as the general formula [[]] described below. ) A bulky trianionic amphoteric compound containing a sulfonate residue or a sulfate residue in one molecule has various surfactant properties such as surface tension lowering ability and foaming property.

We have discovered that it is superior to known fluorine-containing betaine type amphoteric compounds in terms of hard water resistance, water bath disintegration in the currently strongly acidic region, etc. 1. Completed the present invention 2. That is, the present invention has been completed. The present invention provides a novel fluorine-containing trianionic amphoteric compound and a method for producing the same. More details.

The present invention provides a fluorine-containing trianionic amphoteric compound characterized by containing a sulfonate residue or a sulfate residue in one molecule represented by the general formula (I), and a method for producing the same.

In the general formula [[], Rf is a fluorinated aliphatic group having 3 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, preferably a perfluoroalkyl group or a perfluoroalkenyl group, linear, It may be branched, cyclic (for example, a group such as a cyclohexyl group), or a combination thereof, and may also have an oxygen atom interposed in the main chain, such as (CFs) *CFOCFt, CFt-, etc. ()2 is a divalent linking group, specifically 10Ht
CHC Peng-1H -CZC Tsuru-14-oczcz, or -cii,
CH, 80% CH, eo-, R1 is a hydrogen atom,
-czc Chicken Tsukuda.

+cut+, o(-e for cz (however, a is 2 to 10
b is an integer of 1 to 9) or an alkyl group having 1 to 12 carbon atoms. ], preferably Y is -S He, C0,4CHeCHr\so, +C
Htcz-1co- (however, the amount!!1-5011[''al), O-C)-8Ot, OGOO- is preferable.

However, the fluorine-containing trianionic amphoteric compound (abbreviated as amphoteric compound) according to the present invention is characterized by containing a sulfonate residue or a sulfate residue in the molecule, and is characterized by containing a number of divalent linkages. Among the groups, the above two
It goes without saying that the present invention is not limited by the valent linking group.

The duck, pigeon, and pigeon are specifically hydrogen atoms, Li", Na", x
e, Ca2e, m2e, [N(a), (it)h]”
(However, t, R1 is an alkyl group having 1 to 4 carbon atoms or a droxyethyl group, g and h are integers of 0 to 4, and g+ =
4. ).

Q is +CH*j (however, I is an integer from 1 to 6),
(-CH, 醐0-(-CH, ￥o(-ca, +q) (however, p, q is 2 or Q3, Qm, Qm is an integer from 1 to 2 carbon atoms)
8 divalent aliphatic hydrocarbon groups, and divalent fats having 1 to 8 carbon atoms substituted with hydroxyl groups.

AIs Al s Al is an anion atomic group, and AI
is -8 to 9 or -8O8, and A, and A are -8OP-1-oso, "'-1θ -coo0mano-op(on)oo. Carp is an inorganic or organic 7-ion However, preferably O, e,
C, e, Bre■θ, Cj04e, 5O42e, CH
, 504e, NO,e, CHsCooel, phosphoric acid group, etc. are preferred.

Specific examples of the fluorine-containing trianionic amphoteric compound of the present invention include the following.

xe (CFm)t CF (CFl)* CH40HC
Ht N+ 0% CHl 80aNa ) sH Bre The fluorine-containing amphoteric compound according to the present invention can be produced in high yield and economically by the following two production methods.

As for <Manufacturing method 1>.

General formula [II): 1.Rf-Z-Q-N-QtAtMl(II)
[In the formula, Rf, Z, Q, Qt, AI, M
T,'! Same meaning as Ue. ] to the fluorine-containing compound represented by X-(-C19; C00M, [111]
In the formula, X is a chlorine atom, a bromine atom, or an iodine atom.

& is an integer from 1 to 3, and 1M has the same meaning as above. ] compound.

General formula [IVl X-Q, =SO, pigeon (IV) L formula, X
, Qs, and M have the same meanings as above. ] A compound that is reduced by
This is a method of producing by reacting acrylic resin and one or two of the following alkanocarbons having 3 or 4 carbon atoms.

In this method, the compound of general formula (II) is added to the compound of general formula Cu
When reacting the compound of 1l) or the compound of the general formula av], the reaction bath medium usually includes methanol, ethanol, inpropyl alcohol, methyl cellosolve, ethyl cellosolve, phthyl cellosolve, butyl calpitol, dimethyl sulfoxide, dimethyl formamide, acetonitrile, etc. Examples include a mixed system of water, a t+J bathing organic solvent, and water, and a mixed system of isonorobyl alcohol or butylcarpitol and water is particularly suitable. The reaction temperature and reaction time are 60 to 140°C, 5 to
16 hours is appropriate.

When reacting the compound of general formula [II) with acrylic acid or an alkanolactone having 3 or 4 carbon atoms, the reaction heating medium is dioxane, tetrahydrofuran, or acetone.

Methyl ethyl ketone, chloroform, dichloroethane,
Aprotic heating media such as acetonitrile, ethyl acetate, methyl acetate, dimethylformamide, dimethyl sulfoxide are suitable, the reaction temperature is 0 to 140°C, preferably 10 to 80°C, and the reaction time is 5 to 20 hours. preferable.

By the above method, when producing a compound of the general formula [General Zhao I] where Q*=Qm and A, =A, The molar ratio of alkanolactone charged is 2.0~
It is 2.4 times the mole, preferably 20 to 22 times the mole.

In addition, in the case of Qm + Qm or A, ~A, and in the case of K or Q, ~Q, and As''?A, 10 to 12 times the mole of the compound [■], preferably 1 .0
~11 times the molar amount of the compound of general formula (lit) and [1v], acrylic acid, and 111m in the group of alkanolactones, and then reacted with 111m in the group of alkanolactones (also in this case 1.0 ~12 times the mole, preferably 4.0 to 1.1 times the mole).

As for manufacturing method 2.

The fluorine-containing amine represented by the general formula [■'] ''[ll') Rf-Z-Q-N~□ [In the formula, Rf, Z, and Q have the same meanings as above], the general formula [■' [In the formula, X is a chlorine atom, a bromine atom, or an iodine atom,
bl is 2 or 3. ] is reacted with a halogenated alcohol represented by the general formula (lv') [wherein Rf, Z, Q, and - have the same meanings as above. ] is synthesized, and this compound is reacted with a sulfating agent of at least 18I to form a compound of the general formula (1
) is a method for producing a hydrous compound.

When compound [IV'] is synthesized by this method, methanol, ethanol, isoprobyalcohol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, and dimethyl sulfoxide are suitable as reaction solvents, and the reaction temperature is 30°C. -150°C, preferably 50-120°C.

- As a nalphating agent, a concentrated sulfuric acid solution of sulfur trioxide is used.

Sulfonic acid and sulfur trioxide are suitable. The reaction temperature for sulfation is 0 to 200°C, preferably 10 to 1
The temperature is 50°C, and the reaction solvent is preferably carbon tetrachloride, chloroform, menalen chloride, 1.1.2-)rifluoro1.2.2-trichloroethane, acetonitrile, or liquefied sulfur dioxide.

1&, -1 summarizes the l1tIl properties and surface tension of the fluorine-containing amphoteric compound water bath solution according to the present invention.

Table 1 shows the fluorine-containing amphoteric compounds of the present invention.

It is stably dissolved in pure water and seawater in a wide pH range, and does not reduce the interfacial viscosity properties in any of the acidic, medium Ft, and salt pH ranges. That would be extremely useful.

It was found that the amphoteric compound of the present invention has good calcium ion stability and has excellent seawater resistance.

Calcium ion stability was examined by the modified Hardt method.

The fluorine-containing amphoteric surfactant of the present invention has a hardness at pH 7.5, and completely dissolves at pH 7.5 and 10 ppm or more (in terms of CaCO). On the other hand, the known Betai/a! ! One example of surfactant: C, ・F, , SO, N
(CHI)IN(CH,)ICH2C'00''' is
At 1,500 ppm, t0 separation begins and surface activity %* is lost.

Below 1. As is clear from the above, the fluorine-containing amphoteric compound of the present invention has excellent foaming properties in seawater, foam stability, surface tension lowering ability, and hard water resistance. ,
Due to its surface-active properties such as excellent stability against pH, it is especially suitable for use in foam fire extinguishing agents, water film-forming oil fire extinguishing agents, foaming agents, detergents, and wetting agents. Are suitable.

It is also suitable for use in leveling agents, paint additives, antifouling agents, oil repellents, plastic additives, mold release agents, and the like.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In a 60ON fourth round bottom flask equipped with a cooling condenser and a stirrer, 2-hydroxy-N-(N'-barfluorohexylsulfonyl-r-aminopropyl)-6
-Amituprovir sulfone relative soda 10&((1016
2 moles).

5.2 g (0,0162 mol) of 2-hydroxy-6-chloropropanesulfone-related soda, 30 I of isopropyl alcohol.

Then, 40 g of water was weighed out and dissolved by heating. 20aj of an aqueous solution in which sodium hydroxide u, 68II (α0162 mol) was dissolved was added dropwise over 2 hours while stirring at 85 to 90°C. After dropping FM-j', reflux at 90°C for 8 hours?
4. Add sodium monochloroacetate (1.9100162 mol) to the reaction system without taking out the product in the flask, and add 68 g (0.0162 mol) of sodium hydroxide.
was added dropwise over 2 hours while stirring at 65 to 90°C. After further refluxing at 90°C for 7 hours, isopropyl alcohol and water were distilled off under reduced pressure, and the oil residue was heated to 70°C. 2. Dry with hot air. ethanol/
It was purified by recrystallization from water and yielded 1101 g of bean paste.

Elemental analysis CHN F Na Analysis value (%) 24.0 2.5 3.3 2B
, 6 6.4 Calculated value (%) 23.7 2.5
5.5 2ay aa NMR spectrum (D, 0 solvent, D8B standard) 184 ppm (m, 2H), i20p
pm (m, fiH) 551 ppm (d, 4) 1),
4.15 ppm (8,2H) 4.22 ppm (
m, 2H) IR spectrum 12105II-' (SO, Na J/as) 15
70aa″″l (80, N yas ) 16503
1" (COONm) in a 300 d four-day round bottom flask equipped with a cooling condenser and a stirrer.
Hydroxy-N-(β-hydroxy-N'-n -7'
-ropyru N'-perfluorooctylsulfonyl-r-
Aminopropyl)-2-hydroxy-3-amitube sodium bilsulfonate 10 JI (10129 mol), monoiodoacetic acid sodium 5-319 (0,0283 mol), isopropyl alcohol 50 g, and water 40.9 were weighed out and heated. Dissolution I, ta. Woodblock sodium 129 (102
83 mol) was dissolved in 20 ml of a water bath solution at 85 to 90° C. while stirring for 2 hours and 1 hour. After finishing the pottery, the mixture was refluxed at 90°C for 8 hours.

Isopropyl alcohol and water were distilled off, and the paste residue was recrystallized from ethanol. The yield was 8.8I.

C'HNF Onibunze [Value (%) 25.1 2.2 2.6
315 t7NMR7H vector (D, 0 solvent,
D88 standard) 195 ppm (d, 3H), 163
ppm (m, 2H) N3~'6ppm (m, 10
H), xsoppm (m, IH) 4.14 ppm (m
, IH), 4.22 ppm (S, 4H) IR spectrum 1210 cm-' (80, Naj'am) 1 3
70 (It-' (80, N yas ) 11
60cx-' (COONm) Example 3 N-(β-hydroxy-N'-per70roheptylcarbonyl-r-aminopropyl) was placed in a 300-4 day round bottom flask equipped with a cooling condenser and a stirrer. -6
-Aminoprobylsulfonic acid soda 10j (α0158
mol), potassium hydroxide t8!1 (10316 mol),
Then, 100 g of acetotrile was weighed out, and while stirring at 30° C., a bath liquid 3011 of acetonitrile in which 2.511 (α0316 mol) of acrylic acid was dissolved was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was stirred at 40° C. for 3 hours. Acetonitrile was distilled off under reduced pressure, and the residue was recrystallized from ethanol. The yield was 9.51.

Nine analysis CIN F K Analysis value (%) 27.7 2.8 N5
32.1 62M1)! Hani (%) 27.6
2.5 N2 52.8 9. ONMR spectrum (D, 0 solvent, DAB standard) 2, 20 ppm ('m
, 6H), S, 05ppm (t, 2H), 5.29
ppm (m, 6H), 555ppm (m, 4H).

5.88 pp+n(m, IH) IR spectrum 1210m-' (80, Mayas) 164
05IK-' (CON) Example 4 N-(6-aminohexyl)-p-
Par709 nonenyloxybenzenesulfonamide 5 (
['(0,043 mol), ethylene chlorohydrin I
Aa & (α172 mol), methanol 1001 were weighed out, and while stirring at 75°C, potassium hydroxide 4.81JF was added.
(1086 mol) methanol solution 50II
It took two hours to put it under the rope. After the completion of the reaction, the mixture was stirred at 80° C. for an additional 5 hours, methanol was removed, and the residue was recrystallized from chloroform. The yield was 3[16N.

e41rm (%) 57.1 1 3,1
36.9 IR spectrum 1370cIL-' (80,N νam) Fluorine-containing compound 101 (0,0
115 mol) and 40 g of acetonide 1 lyl in 20011
7d) It was weighed into a 6-neck round resistance flask, and while stirring vigorously at 60 to 40°C, 4.211 (10357 mol) of chlorosulfonic acid was added dropwise over 40 minutes to remove the precipitate. The sample was taken, washed with acetonitrile, and then dried under reduced pressure at 40°C. The obtained dry solid 6I was dissolved in ethanol 4[
', neutralized with 1ON aqueous sodium hydroxide solution,
Ethanol and water were distilled off. The obtained solid residue was recrystallized from isopropyl alcohol and purified. Yield is 5,5I and nine element analysis CHN F Na Analysis value (%) 29.7 2.8 2.5 29.0
4.3 NMR spectrum (D, O solvent, DSS standard)
t 53 ppna (m, 8 H), 3.1~A3
ppm (m, 10H).

192 ppm (t, 6H) IR Spectrum 137 Dam-' (801 N yas) Example 5 - In a 300-' round-bottom Nolasco equipped with a ready-to-use condensate length and a stirrer, N-[2-hydroxy -N'-(
2-hydroxyethyl)-N'-half-0-octylethanesulfo-6-amituprovir]-2-aminoethanesulfonic acid nota 20,9 ((1025'5 mol), potassium hydroxide 2.8y (LL0505 mol) ,β
-Propiolactone 3.6I (0.05Ll 6 mol)
, and acetonitrile 10 (l?L, 2 at 60°C)
Stirred for 0 hours. The acetonitrile was distilled off [7], and the paste residue was recrystallized from isopropyl alcohol (-the total yield was 211%).

Elemental analysis value (%) 27.5 2.6 2.7 1.7
61NMg spectrum (He〇 solvent, Dis standard) 1.
84ppm (t, 2H), 2.19ppm (t, 4H
), 2.42ppm (t, 2H), 5QOppa+(
t, 2H)i19ppm(t, 2H), 3.30p
Pm (m, 8H) 3.57ppm (d, 2H), ! h
, 81 ppm (m, IH) IR spectrum 1210 (IN (So, Na yas) 1710 m
(80, N νam) 1650aa-' (CO
OK yas) % Pestle Applicant Two Major Nippon Ink Chemical Industries Co., Ltd. Kawamura Physical and Chemical Research Institute

Claims (1)

[Scope of Claims] t A fluorine-containing trianionic amphoteric compound represented by the general formula [[]. 2 Rf is a barflo tetraalkyl group having 3 to 20 carbon atoms, and 2 is -Y-N- [However, Y is a divalent linking group and -SO
,-11-co-14CHt CH! +180* -+CH
t CHt old co- (however, ``1'' indicates -0-()←co-, hydrogen atom. CHv CHy OH, + CHt)0 +CHt-+
bCHs (however, %a is an integer from 2 to 10, b is 1
) or an alkyl group having 1 to 12 carbon atoms. ] Claim 1 characterized in that
The fluorine-containing trianionic amphoteric compound described in . , A, and A are −SOP, and M1 is −C
OO8, Ml, Peng, Peng is Nae, and Koi is cto! J
ii. The fluorine-containing trianionic amphoteric compound according to item 1 or 2. can be,? The fluorine-containing trianionic amphoteric compound according to claim 1 or 2, wherein is Cjo. 5. General formula [“] Rf −Z Q N QrAtMt−=・(II
)■ Fluorine-containing compound K shown by. General formula Cm)
The compound represented by l, general formula (IV)
Reacting the compound represented by V) and one or two of the alkanolactones having 6 or 4 carbon atoms,
A method for producing a fluorine-containing trianionic amphoteric compound, which comprises obtaining a compound represented by the general formula [1']. & A fluorine-containing amine represented by the general formula is reacted with a halogenated alcohol represented by the general formula [m'] Expression (+
v' ] [In the formula, Rf, Z, Q, X, b have the same meanings as above. ] is synthesized, and this compound is reacted with at least one sulfating agent to form a compound with the general formula [1″] −・
A method for producing a fluorine-containing trianionic amphoteric compound, which comprises obtaining a compound represented by -.-[:['). 7. Rf is a perfluoroalkyl group having 3 to 20 carbon atoms; 2 is -Y-N (However, Y is a divalent linking group and -8O2-
1-co-. 1 4CHICH,)r802-1-(-CH,CH tongue Co
- (However, i is an integer from 1 to 3.), -〇→σ＞
SO, -, or -〇〇〇- and b ``l is a hydrogen atom, -CH, CH, OH. -(-CHt90 +cu!+bCHm (However, a is an integer from 2 to 10, is an integer of 1 to 9.) or represents an alkyl group having 1 to 12 carbon atoms. Method for producing amphoteric compounds.