US3336372A - Surface biactive amphoteric agents - Google Patents

Description

United States Patent 3,336,372 SURFACE BIACTIVE AMPHOTERIC AGENTS Philip G. Abend, Cleveland Heights, Ohio, and Warner M. Linfield, Evanston, and Belen C. Brown, Chicago, Ill., assignors to Armour and Company, Chicago, Ill., a corporation of Delaware No Drawing. Filed Dec. 23, 1963, Ser. No. 332,938 Claims. (Cl. 260-501) This invention relates to surface biactive amphoteric agents, and, more particularly, to amphoteric surface active agents which possess both detergent and fabric softening properties.

While the desirability of providing a single surfactant which would provide both detergent and fabric softening properties has been recognized, yet it was thought that the specific diverse attributes of such a surfactant necessary to produce respective detergency and softening were normally not compatible in a single compound. Detergency has been usually, though not exclusively, attributed to the so-called anionic surfactants, while fabric softening has been generally attributed to the cationic surfactants. Yet it has been further generally accepted that anionic surfactants are not normally compatible with cationic materials and are frequently precipitated from solutions by cationic materials and even by certain inorganic cations such as aluminum, calcium, magnesium, etc., with which they combine to form compounds having little or no surface activity.

Therefore, one object of this invention is to provide a class of compounds in which each compound is amphoteric in the sense that it possesses both the anionic attribute of detergency and the cationic property of fabric softening, and in which the respective anionic and cationic centers are compatible and do not become ineffective as a result of precipitation in solution.

Also, it is a further object of this invention to provide surface biactive amphoteric agents which minimize the undesirable characteristics of yellowing, waterproofing, and soil redeposition on multiple application, and which may be used as the active component of a heavy-duty liquid detergent softener formulation.

The surface biactive amphoteric agents which we have obtained have in common the following structural formula:

In the foregoing formula, R is an alkyl group containing from 12 to 18 carbon atoms, R is a hydrocarbon chain which is either an alkylene containing from 2 to 6 carbon atoms or a phenyl alkylenecontaining from 2 to 4 carbon atoms in the alkylene chain, and R is an alkyl group containing from 1 to 8 carbon atoms, or, a hydroxy alkyl group containing from 2 to 8 carbon atoms in the chain with the hydroxyl group in the number two position from the nitrogen atom. It is'to be understood in the foregoing, that while R is an alkyl group containing from 12 to 18 carbon atoms, such as stearyl or palmityl, for best softening properties stearyl is to be preferred.

The surface biactive amphoteric agents having this chain structural formula possess both detergency and softening properties. As is observable from the formula, compounds 0 ia av C H S O aNa Patented Aug. 15, 1967 possessing both softening and detergency properties appear to demonstrate a ratio of the number of fatty chains to cationic centers of 1:1.

In obtaining the surface biactive amphoteric agents with which this application is concerned, we first synthesized compounds as follows:

EXAMPLE 1 Synthesis of the bis-Schic base (p,p'-xylylidinea,a'-bis-octadecylam ine) A mixture of terephthalic aldehyde (0.25 m., 35.5 g), octadecylamine (0.50 m., 134 g.) and 200 mls. of benzene was refluxed with azeotropic removal of water. After one-half hour of refluxing, 10 mls. of water had distilled over. 100 mls. of benzene were drawn off and refluxing was continued for 15 minutes more. The mixture was cooled, diluted with 800 mls. of acetone and kept in the freezer for 18 hours. The precipitate was filtered, washed with acetone and dried. Yield: 152 g. This synthesis may be expressed by the following:

EXAMPLE 2 Synthesis of the bis-amino sulfonate (p,p'-xylylene-a,o'- bis-octadecylamina-disodiumw -sulfonate) A mixture of the bis-Schiif base (P. 0835 m., 53 g.), prepared as described in Example 1, an aqueous solution of sodium bisulfite (0.167 m., 33.4 mls. of a 5 M solution) and 150 ml. of ethanol was refluxed for one hour. The mixture was cooled, diluted with 400 mls. of acetone, kept in the freezer for a few hours, filtered and dried. Yield: 70.5 g. This synthesis may be expressed by the following:

Synthesis of the amphoteric (p,p'-xylylene-'a,a'-bisdim'ethyloctadecylamm0nium-a,a-sulf0nate) A mixture of the bis-amino sulfonate (0.0818 m., 69 g.), prepared as described in Example 2, 500 mls. of isopropanol and 2 mls. of phenolphthalein indicator was heated to 70 C. Dimethyl sulfate (0.328 m., 42 g.) and a 30% aqueous solution of sodium hydroxide (0.164 m., 6.55 g.) was added dropwise simultaneously to the bisamino sulfonate so that the mixture was just slightly pink. All the sodium hydroxide solution was added when about one-half of the dimethyl sulfate was in. Addition of the dimethyl sulfate was continued, the total addition time being one hour. The mixture was then refluxed for one-half hour C.) and filtered while hot.

The filtrate (a yellow solution) was evaporated to dryness, then taken up in 200 mls. of ethyl acetate, heated to boiling and filtered. The filtrate was kept in the freezer for 16 hours. The product, a white solid, was filtered, washed well with acetone and dried. Yield: 57 g. This synthesis may be expressed by the following:

CH1: SOa

- 3 EXAMPLE 4 Synthesis of 2-butyne-L4-bis (dimethyloctadecylammonium chloride) A mixture of 1,4-dichlorobutyne-2 (12.3 g., 0.10 m.), dimethyloct-adecylamine (59.4 g., 0.20 m.), 400 ml. of n-propyl alcohol and 25 ml. of water was refluxed for 8 hours. The solvent was removed by evaporation under reduced pressure and the residue extracted with 200 ml. of hot ethyl acetate. The solution was cooled to C. for 16 hours and the resulting crystals filtered, washed with petroleum ether, then air-dried. Yield: 50 g. of a 100% active product. This synthesis may be expressed by the following:

After these compounds were prepared, they were then tried on soiled fabrics under actual washing conditions and the evaluation of the representative detergency and softening properties made. The representative compounds which resulted from the syntheses set forth in Examples 3 and 4 demonstrated both detergency and softening properties.

Additional examples of bis-amphoteric compounds can be prepared as follows:

EXAMPLE 5 Synthesis of butane-1,4-bis(diethyldodecylammonium) 2,3-disulfonate Reflux a mixture of 1,4-dichlorobutylne-2 (12.3 g., 0.10 mole), diethyldodecylamine (48.2 g., 0.20 mole), 400 ml. n-propanol and 25 ml. of water for 8 hours. Remove the solvent by evaporation under reduced pressure and extract the residue with 200-250 ml. of hot ethyl acetate. Cool the solution to 0 C. until crystallization of the intermediate bis-quaternary salt occurs. This material may be filtered, washed with petroleum ether, and used as is for the second step of the preparation. Reflux a mixture of crude 2-butyne-1,4-bis(diethyldodecylammonium chloride) (30.2 g., 0.05 mole), 200 ml. of n-propanol, sodium bisulfite (20.8 g., 0.20 mole), and 400 ml. of water for 5 hours. Remove the solvent by evaporation under reduced pressure and extract the residue with 300 ml. of isopropanol. The product may be precipitated by pouring the isopropanol solution into 1 liter of acetone. This bisamphoteric is filtered and air-dried.

EXAMPLE 6 Synthesis of butane-1,4-bis(bis (Z-hydroxyethyl) dodecylammonium 2,3-disulfonate Reflux a mixture of 1,4-dichlorobutyne-2 (12.3 g., 0.10 mole), bis(2-hydroxyethy1) dodecylamine (57 g., 0.20 mole), 400 ml. n-propanol and 25 ml. of water for 8 hours. Isolate the intermediate bis-quaternary and treat with four equivalents of sodium bisulfite as in preparation of Example 5.

EXAMPLE 7 Synthesis of butane-1,4-bis(di-n-hexyld0decylammonium) -2,4-disulfonate Reflux a mixture of 1,4-dichloro-butyne (12.3 g., 0.10 mole), di-n-hexyldodecylamine (71 g., 0.20 mole), 400- 500 ml. of n-propanol, and 25 ml. of water. Isolate the intermediate bis-quaternary and react it with four equivalents of sodium bisulfite as in the preparation of Examples 5 and 6.

While in the foregoing specification this invention has been described in relation to certain preferred embodiments and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details set forth herein can be varied considerably without departing from the basic principles of the invention.

We claim:

1. As new compositions of matter, the class of compounds represented by the structural formula wherein R is an alkyl group containing from 12 to 18 carbon atoms and R is a hydrocarbon chain selected from the class consisting of alkylene containing from 2 to 6 carbon atoms and phenyl alkylene containing from 2 to 4 carbon atoms in the alkylene chain and R is selected from a :grOup consisting of an alkyl containing 1 to 8 carbon atoms and a hydroxy alkyl having 2 to 8 carbon atoms with the hydroxyl in the number two position from the nitrogen atom.

2. The class of compounds of claim 1 wherein R is alkylene containing from 2 to 6 carbon atoms.

3. The class of compounds of claim 1 wherein R is phenyl alkylene containing from 2 to 4 carbon atoms in the alkylene chain.

4. As a new composition of matter, the compound represented by the structural formula:

5. As a new composition of matter, the compound represented by the structural formula:

6. As new compositions of matter, the class of compounds represented by the structural formula:

CH3 so. CH;

1t s1- r-N C 131 37 CH: 303 CH;

wherein R is alkylene containing from 2 to 6 carbon atoms.

7. As new compositions of matter, the class of compounds represented by the structural formula:

References Cited FOREIGN PATENTS 10/1957 Germany.

OTHER REFERENCES Schwartz et al.: Surface Active Agent and Detergents, vol II 1953 page 140.

Moilliet et al.: Surface Activity (1961), page 399.

LORRAINE A. WEINBERGER, Primary Examiner.

MARY B. WEBSTER, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,336 ,372 August 15 1967 Philip G. Abend et al It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 65 to 67, the formula should appear as shown below instead .of as in the patent:

C H NHCH CHNH-C H 4 (CH SO ZNaOH fi SO Na O Na bis column 2 line 9 for "bis-Schic", in italics read the formula,

Schiff in italics column 4 lines 43 to 46 in for "S0 each occurrence read SO Signed and sealed this 25th day of June 1968.

(SEAL) Attest:

EDWARD J. BRENNER EDWARD M.FLETCHER,JR.

Commissioner of Patents Attesting Officer

Claims (1)

1. AS NEW COMPOSITIONS OF MATTER, THE CLASS OF COMPOUNDS REPRESENTED BY THE STRUCTURAL FORMULA