JPS6171830A - Cationic surfactant - Google Patents

Abstract

PURPOSE:To enhance the compatibility with other ionic surfactant, by preparing a cationic surfactant having either one of a urea bonding group, a thiourea bonding group and a carbonamide group in the branched chain thereof. CONSTITUTION:Epichlorhydrin is reacted with a fluorine-containing compound represented by formula I to form a fluorine-containing compound represented by formula II. An amine compound represented by formula III is reacted with the formed compound II to obtain a compound represented by formula IV. A compound represented by formula V is reacted with this compound IV to obtain a cationic surfactant having either one of a urea bonding group, a thiourea bonding group and a carbonamide group in the branched chain thereof and a cationic group in the main chain and excellent in the compatibility with an anionic surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a combination of ionic surfactants with other ionic surfactants characterized by having one of a urea-binding group, a thiourea-binding group, or a carbonamide group in the branch chain. This invention relates to a novel cationic surfactant with excellent compatibility.

Conventionally, cationic surfactants have been used as antistatic agents for textiles, dyeing aids, flotation agents, metal anticorrosive agents, bactericides, emulsifiers, etc.
It has been used in various applications that take advantage of the characteristics of cationic groups, and in general, a hydrophobic chain CEL) and a cationic hydrophilic group (zo) are connected via a divalent linking group CB), and an anionic group (X ”) bound as a counterion n-B-?
It has a structure represented by x''.

However, these conventional cationic surfactants
For example, Surfactant Handbook (published by Sangyo Tosho Co., Ltd., 1939)
As described on page 9 (1st edition), it is known that when mixed with an anionic surfactant in a solution, a precipitate will occur, making it impossible to use both together. It is widely recognized that poor compatibility is a serious drawback of cationic surfactants.

Anionic surfactants are known as cleaning agents, wetting agents,
They are used in a wide variety of applications, including foaming agents and emulsifiers.For this reason, when using cationic surfactants, it is necessary to sufficiently remove the effects of anionic surfactants; When using an active agent, it is necessary to sufficiently remove the cationic surfactant before using it. This kind of removal operation is not a complicated process, but it is possible that the effect of the surfactant remaining without being sufficiently removed may reduce the effectiveness of the different ionic surfactant used in the subsequent process.
The reality is that there are frequent cases where the ability to perform effectively is not achieved.

In view of these circumstances, the present inventors conducted intensive research on the development of cationic surfactants with high compatibility with anionic surfactants. A cationic surfactant having either a group or a carbonamide group is soluble in hard water containing a large amount of inorganic salts, such as seawater, and in a wide range of water, and anionic surfactants. The present inventors have discovered that even when used in combination with a polyester, they have excellent compatibility and do not reduce their surfactant properties, leading to the completion of the present invention.

That is, the novel cationic surfactant according to the present invention is represented by the following general formula (I).

R" However, in the formula, R is a hydrocarbon group having 4 to 20 carbon atoms or a
70-roalkyl group or #-70-roalkenyl group, A represents a linking group of 3 (i), Ql is +CH2, so CH2 is 0,
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

), R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group.

Y represents an oxygen atom or a sulfur atom. Turtle is ot or l
shows. R2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents an alkenyl group or an alkyl group containing one or two ether oxygen atoms. R5+ R4, R
5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, or an alkyl group containing one ether oxygen, and these may be the same or different, and R3 and R4 are bonded together. The nitrogen atom may be included to form a ring such as a morpholino group (-N O). ? is an inorganic or organic anion.

In the cationic surfactant (I) according to the present invention, the hydrophobic group R is a hydrocarbon group having 4 to 20 carbon atoms (particularly preferably an alkyl group or an alkenyl group) or a /70roalkyl group 4L<ldI. -170-roalkenyl group, di,
It may have a linear, branched, or cyclic structure.

+CH2CHz+rSOz- (where, i is an integer from 1 to 5, p is an inorganic or organic anion, and p is a specific VC
u cte%Bre, Ie, CH35040,01
(e1CtO?

No? , CH3CO0e or a phosphoric acid group. Examples of the cationic surfactants of the present invention include the following.

H CH2CH20H CH5 CH5 ■C■2ca2oH OHcn3 OH OH5 The novel cationic surfactant (I) according to the present invention is produced in high yield and at low cost by the following production method.

That is, the general formula [where B e A e Q1* R1y Y * &
a R2 is as above). ] is reacted with shrimp chlorohydrin or shrimp bromohydrin to form a fluorine-containing compound represented by the general formula [wherein, RI A I Ql # R1+ Y a a
# R2 is as described above. A fluorine-containing compound represented by the above formula is obtained, and the compound is converted to the general formula [wherein R5 and R4 are as described above]. ] by reacting the amine compound represented by the general formula [wherein, R* A + Ql # R1a Y a a
s R2e R3eR4 are as described above. A compound represented by the formula % is obtained, and the compound has the general formula % ( ) [wherein R5 is as described above], and X' is a chlorine atom, a bromine atom, or an iodine atom. ] The cationic surfactant (I) according to the present invention is produced by reacting the compound represented by:

In the above production method, the compound (from ID to compound (to)
The reaction to obtain consists of the following two-stage mechanism.

(I stage) (To) (Second stage) Alkaline catalyst (v) aID The same reaction solvent can be used in the first and second stages, such as acetone, methyl ether ketone, methyl ing tyl ketone, etc. Ketone solvents, alcohol solvents such as methanol, ethanol, and isoglobil alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, dimethoxyethane, and tetrahydrofuran are preferred. As a catalyst for the first stage reaction, NaOH, 2C
O3r Li0HsCa(OH)z r CH30NI
L r NaI r LiCL, N & C2y (C2H5
)4NI, etc. and their analogous compounds, among which NaI + LiCL, (C2H5)4NI
is particularly preferred. The amount of the catalyst added is 0.01 to 2 molar equivalents, particularly preferably 0.1 to 1 molar equivalents, relative to compound Q[). The reaction temperature is 30-160°C,
Particularly preferred is 0 to 120°C. The catalyst for the second stage reaction is selected from a wide range of alkali compounds, including CI(3
Examples include tertiary amines such as ONa, NaOH, KOH, and triethylamine, and the amount added is preferably 0.8 to 162 molar equivalents relative to compound (II).

In addition, the solvent for the reaction between the fluorine-containing compound (2) and the amine compound ω and the reaction between the compound (g) and the compound (h) may be selected from a wide range of solvents, such as water, alcohol-based solvents such as methanol, and ethanol. Solvents, ketone solvents such as acetone and methyl ingtyl keto y, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as diethyl ether, inglobil ether, and tetrahydrofuran. Can be mentioned.

The temperature of the reaction between the fluorine-containing compound (g) and the amine compound surface is -10 to 100°C, preferably 0 to 80°C. The amount of amine compound (goods) to be charged is 1 for compound (g).
~10 molar equivalents, preferably 1.5 to 5 molar equivalents.

The temperature of the reaction between compound (g) and compound (to) is 0 to 12
0C, preferably 40 to 100C. Compound (b)
The charging amount is 1 to 10 molar equivalents, preferably 1.5 to 5 molar equivalents, relative to compound (g).

The fluorine-containing compound represented by the general formula (II) was prepared according to the known manufacturing method (Japanese Patent Application Laid-Open No. 57-209259) as described above. ] and the compound represented by the general formula R2-N
It is produced in good yield by reacting with an incyanato or thioisocyanate compound represented by =c-ey and an acid anhydride represented by the general formula.

The cationic surfactant according to the present invention is sweetfish. Although the mechanism of action that provides excellent compatibility with cationic surfactants is unknown, it is compatible with ordinary cationic surfactants that do not contain urea-binding groups, thiourea-binding groups, or carcinamide groups as branched chains. In terms of compatibility, there is no doubt that the functional groups in these branched chains make a decisive contribution to improving compatibility.

Next, the surfactant properties of the cationic surfactant according to the present invention will be shown.

Synthesis Example 1 N-(3-methylaminopropyl) was added to a 500-mm three-necked round bottom flask equipped with a dry silica glue tube and a stirrer.
Par70 octylsulfonamide 57 N (0,1
mol) and 250 moles of sufficiently dehydrated tetrahydrofuran were weighed out under a nitrogen atmosphere, and dissolved with stirring at room temperature. Methyl incyanate 5.99,! 20 d of a tetrahydrofuran solution in which i' (0,105 mol) was dissolved was added dropwise at room temperature with vigorous stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and tetrahydrofuran was distilled off under reduced pressure to obtain 52.9% of a slightly yellow solid. Usually, one or more operations can obtain a product of sufficient purity for use in the next reaction.

If necessary, recrystallize from chloroform/n-hexane.

mp -64.5~65.5℃ Elemental analysis HNF Analysis value (%) 26.5 λ1 6.7 51
．． 4 Calculated value (%) 26.8 λ2 6.7 5
1.5IRs 1370I2-1 (-8O□N8νas)16-4
5cm-' (N-C0-NH-)NMR, X
(CD3COCD, solvent, TMS standard) 1
．． 80ppm (m, 2H), Z90ppm (s, 3H)
3.09 ppm (d, 3H), 3.21 Ppm (m
, 4H) Synthesis Example 2 H3 N-(3-Methylaminopropyl) 70-neck hexylsulfonamide 90 F (0,1
91 mol) and pyridine 134I were weighed out, and while stirring vigorously at room temperature, acetic anhydride 29.3, p (0,28
7 mol) was gradually added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 3 hours, and pyrinone was distilled off under reduced pressure. 150 ml of distilled water was added to the obtained viscous solid residue to ripen the crystals. Collect the white crystals by filtration, wash with water, and heat at 70°C.
It was dried under reduced pressure. Yield 100.9゜mp-77,0~78.5℃ Analysis value) 28.0 2.4 5.7 Calculated value (%) 28.1 2.5 5.5IR spectrum 1370cm-'(-8o3N< νas )16
40crn-'(-CON<) source spectrum 1.83ppm (m, 2H), ZO4pprn (s
,3H)3,O5ppm (s,3H), 3.27
ppm (t, 2H) 3.48 ppm (t, 2H) Synthesis Example 3 Fluorine-containing compound 6 obtained in Synthesis Example 1 was placed in a 500-day round bottom flask equipped with a cooling condenser and a stirrer.
2.7.9 (0.1 mol), methyl ethyl ketone 60.
9, ttczo, +2.9 (o, o1 mol).

The epichlorohydrin level is 18.5! i (0,2 mol)
was weighed out and stirred at 70°C for 1.5 hours. Then CH3O
28 Thimethanol solution of Na 19.2. ! 7 (0,09
95 mol) was added dropwise. After cooling the inside of the system to room temperature, 500 frl of ethyl acetate was added, and the organic layer was washed twice with liquid-liquid using 200 ml of distilled water each time. Organic layer is treated with anhydrous N&2
After drying with S04, the solvent was distilled off under reduced pressure.

A pale yellow paste of 64.2# was obtained as a residue. This Pace I was identified as infrared absorption spectrum and 1H-NMR slippage.

The above pale yellow yeast 60I, 33 g of a 40% aqueous solution of dimethylamine, gg (0.3 mol), and methanol 60
Weigh Ii into a 300-round bottom flask.

The mixture was stirred at 10°C for 48 hours. Excess dimethylamine and solvent were distilled off under reduced pressure, leaving a light brown paste 63.
4.9 was obtained. Infrared absorption spectrum and 'I(-11G
The image shows that the epoxy ring has completely disappeared.

was identified.

Light brown base above) 601! , iohihimethyl4λ6p
(0.3 mol), and inpropyl alcohol 200
! Weigh out the i into a 50 oi round bottom flask and heat it at 70°C.
The mixture was stirred for 4 hours. Too much! By distilling off methyl iodine and impropyl alcohol of No. 3 under reduced pressure, a pale brown homologue was obtained as a residue. This solid was recrystallized from inpropyl alcohol/n-hexane and dried to obtain 58.6 g of a pale yellow solid. Through elemental analysis,
It was confirmed that this was the desired compound. mp=78
．． 0℃HNFI Analysis Direct (I) 27.3 3.3 6.7
37.6 13.9 Calculated value (%) 27.6 3
．． 2 6.4 37.1 14.6 Synthesis Example 4 Fluorine-containing compound 51.21 obtained by synthesis f112 according to the same method as Synthesis Example 3! (0.1 mol) , NaI
1.5/i (0.01 mol), Ebibromohuman 9 phosphorus 27.411 (0.2 mol v), 2 of CHONa
8 timemethanol solution 19, 21 (0,0995 mol)
, and using 28 g (0,46 mol) of 28% aqueous ammonia? H3 (light yellow paste) 49II was obtained.

The above compound was dissolved in 100 g of methanol and neutralized with hydrogen iodide. The solvent was distilled off under reduced pressure.

The target compound (pale yellow crystals) was obtained by recrystallizing from chloroform.

HNFI analysis value (ch) 25.6 2.6 5.6 34.7
17.6 Example 1 The results of the compatibility test of the cationic surfactant No. 1 according to the present invention with anionic surfactants are shown in Table IK.

That is, 0.5vt% of the cationic surfactant according to the present invention
An aqueous solution and 0.5 wt% of the following anionic surfactant were mixed in equal amounts, and the state of the aqueous solution after 10 minutes of mixing was shown in four stages. 4: Transparent, 3: Slightly cloudy. 2: Cloudy. 1
: Solid precipitates.

Anionic surfactant C,H.

03H.

07F, 5000K Sodium Hadecyl Sulfate Sodium Niolate E The above results show that the cationic surfactant according to the present invention has extremely excellent compatibility with the anionic surfactant.

Example 2 Table 2 shows the foaming properties of an equivalent mixture of a 0.1 wt% aqueous solution of a cationic surfactant according to the present invention and a 0.1 wt% aqueous solution of an anionic surfactant, and the foaming properties of each alone. . The sample numbers in Table 1 indicate those in Table-1.

From the above results, it can be seen that the cationic surfactant according to the present invention does not reduce its surfactant properties even when used in combination with an anionic surfactant.

Agent: Patent attorney Katsutoshi Takahashi Procedural amendment (spontaneous) October 1980, aJ Japan Patent Office Commissioner Manabu Shiga1, Indication of the case 1982 Patent Application No. 1925942, Name of the invention: Cationic interface Activator 3, relationship with the case of the person making the amendment Patent applicant: 35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
8) Dainippon Ink & Chemicals Co., Ltd. Representative Kawa
Shigeru Kuni Mura 4, Agent Address: Dainippon Ink and Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 (I) “+CH2CH2÷iSO” on page 7, line 6 of the specification
□-" is corrected to "+CH2CH2+, 502N-".

(2) “+CH2÷2S+CH2÷2” on page 7, line 7
CO-1 (or more)

Claims (1)

[Claims] 1. An anion characterized by having one of a urea-binding group, a thiourea-binding group, or a carbonamide group in its branched chain, and having a cationic group in its main chain. A cationic surfactant with excellent compatibility with other surfactants. 2. The cationic surfactant has the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is a hydrocarbon group having 4 to 20 carbon atoms, a perfluoroalkyl group, or -fluoroalkenyl group, A is a trivalent linking group, Q_1 is -(CH_2)-_l, -(CH_2)-_l
O-(CH_2)-_p (However, l and p represent integers from 2 to 6.) or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, R_6 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), R_1 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, Y is an oxygen atom or a sulfur atom, a is 0 or 1, R_2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms , an alkenyl group, or an alkyl group containing one or two ether oxygens, R_3, R_4, R_5 are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, hydroxyalkyl groups, or alkyl groups containing one ether oxygen These may be the same or different, and R_3 and R_4 contain the bonded nitrogen atom to form a ring like a morpholino group (▲There are numerical formulas, chemical formulas, tables, etc.▼). and X^■ is an inorganic or organic anion. ] The cationic surfactant according to claim 1. 3. A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, Z
is a divalent linking group -SO_2-, -CO-, -(CH2
_CH_2)-_iSO_2- (however, i represents an integer from 1 to 5), -(CH_2)-_2S-(CH_2
) −_2CO−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] The cationic surfactant according to claim 2.