Fatty acid-hydroxyethyl-quaternary ammonium compounds and preparation thereof

United States Patent Office _D 3,223,71s

Patented Dec. 14, 1965 this stage, the internal pressure was 23 pounds per square inch. The reaction was then continued for another 80 minutes at the end of which time, a test of the percentage of free fatty acid showed only .74%. The reaction was continued for an additional 50 minutes, at a pressure of 18 pounds per square inch and a temperature of 77° C.

To remove any traces of unreacted ethylene oxide, the vacuum was turned on for 25 minutes reaching a maximum of 24 inches of mercury. The batch was then steam sparged until the vacuum dropped to 10 inches of mercury and then the vacuum was reduced to zero with nitrogen gas.

The resulting product, stearyl dimethyl hydroxyethyl ammonium stearate, was a cream colored solid flake with a melting point of 64° C. The yield was 2293 grams, which was 98.3% of the theoretical yield of 2333 grams.

The final pH of the product at a concentration of 3% by weight in 50% isopropanol solution was 8.6.

Example II

The same general procedure of Example I was used ^{t lat instead of} stearyl dimethyl amine, 2254 grams (7.38) moles of dimethyl hydrogenated tallow amine was the starting material and along with 1978 grams (7.38 moles) of stearic acid were loaded into the autoclave of Example I. 330 grams (7.50 moles) of ethylene oxide were reacted m the same manner as in Example I with the mixture of dimethyl tallow amine and stearic acid. The resulting product, dimethyl (hydrogenated tallow) hydroxyethyl ammonium stearate, was a white solid flakp. melting at 59° C. and a yield of 99% of the theoretical was obtained.

Example III

Again, the same general procedure was used as in Example I except that .1767 grams (5.81 moles) of dimethyl palmityl amine and 1557 grams (5.81 moles) of stearic acid were loaded in the autoclave of Example I This mixture was reacted with 259 grams (5.88 moles) of ΡΙΠνίΑΠΑ ηνι ΤΊ-, — -..14?_ _ t .... ,- ------pxwiuvt, uimciuyi paimitvl hydroxyethyl ammonium stearate, was a white solid flake having properties similar to those in Examples I and II and with a melting point of 57° C.

Example IV th 3^hn so^{me proc}®^du_f^{re as in} Example I was used, except hat 11-60 grams (2.00 moles) of methyl dihydrogenated tallow amine and 21-8.3 grams (2.02 moles) of 70% by ⁵⁰ ^Fimni^dr?^XyTT^{tiC aC}'^{d Were l0aded in the} autoclave n so 1 ' T^hls,^{mlxture w}as reacted with 1.27 grams (2.89 moles) of ethylene oxide and with 98 grams of isopropanol for a solvent. The excess ethylene oxide was removed when the reaction was completed by pur»!

^{55 h ΠΙίΓ0}^^{η gaS}· ^{The result}ing product, methyl droxv^d^^Sw^{ated taU}°^{W) hydroxyeth}yl ammonium hyxy acetate, was an amber paste containing 92.8% of h+,'M_r^IVe ^^aterna7 ammonium compound which exS nth” ^ar ,^eX‘^{lIe SOftening} P^{roperties as} ‘he prod60 ucts of the preceding example.

Example V

The same general procedure was used as in Example I except that 1030 grams (1.776 moles) of methyf di65 hydrogenated tallow amine and 120 grams (2.00 moles) ExamrieV^Th· ^l0aded “ ^the autoclave of

Exampie I. This mixture was reacted with 144 grams (3.27 moles) of ethylene oxide. After the reaction was completed excess ethylene oxide was removed by sparg⁷⁰ mth^Wzi* ^nitl?^S.^en ,^gas· ^{The result}ing product, methyl dilhydrogeniiteci tallow) hydroxyethyl ammonium acetate, was an amber solid having a melting point of „ 3,223,718

FATTY ACID-HYDROXYETHYL-QUATERNARY AMMONIUM COMPOUNDS AND PREPARATION THEREOF

Oscar L. Scherr and Samuel F. Moses, La Mirada, Califassignors, by mesne assignments, to Emery Industries, Inc., Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed June 21, 1962, Ser. No. 204,052 7 Claims. (Cl. 260—404)

This invention relates to improvements in textile softeners used in the final rinse of laundering cycles, and to methods of preparation of such textile softeners.

Hitherto, commercially available textile softeners, when used on white fabrics repeatedly caused yellowing of the fabrics. Further, such available textile softeners frequently darken the cloth during ironing.

It is, therefore, the object of this invention to provide textile softeners for laundering purposes which do not cause yellowing of fabrics upon repeated washings

Another object of this invention is to provide new compositions of matter useful as textile softeners for laundering purposes which do not cause darkening of fabrics during ironing.

A further object of this invention is to provide new 25 compositions of matter useful as textile softeners for laundering which produce a soft and pleasant feel of the fabric to the touch after being treated with such new compositions of matter.

A still further object of this invention is to provide 30 compositions of matter suitable as textile softeners in laundering which are easy to handle in powder form.

A still further object of this invention is to provide compositions of matter suitable as textile softeners in aundenng which can be prepared from readily available 35 and relatively inexpensive raw materials.

These and other objects will be more readily understood by the following discussion.

These new compositions of matter are generally pre- .......— _{wnn sram}, ₍s .«_x acid Inches ^rtt^{nS W}‘^th f ^{fatty tertiary amiM Salt of a fatty 40} ®^{thylene oxide}· ^The resulting product, dimethyl palmityl acid such as stearic, palmitic or hydrogenated tallow fatty hvdrnxwthvi ---------. .. ^y P^a mityl acid and treating the fatty tertiary amine salt with ethylene oxide to produce a quaternary ammonium compound tnZ^{lng chains}- The products resulting from these methods of preparation have unusual properties as textile softeners m laundering. The following are illus^tra l^Ve ,^eXE™P^{lcs of} ihese new compositions of matter and methods of preparation:

Example I

J^F™⁸ +^{91 m01es) of stearyI} dimethyl amine and 1042 grams (3.-9-1 moles) of stearic acid were loaded mto a 2 gallon stainless steel autoclave. The autoclave was heated with steam and nitrogen gas was introduced nside the autoclave. When the temperature reached 60° C., heating was discontinued. After 50 minutes the stearic acid was melted and the agitator turned on. ’ The outlet valve was closed of the autoclave and nitrogen sparging was discontinued. The internal pressure at this stage was 2 pounds per square inch. The pH of a sample taken from the batch and tested at a concentration of 3 % by weight in 50% isopropanol showed 6.85. 177 grams (4.023 moles) ethylene oxide was added from a small ?+^e_^tardc· At this stage the initial temperature was 63 ° C. The internal pressure rose to 45 pounds per square meh.

After the reaction proceeded for 1 hour and 9 minutes the temperature rose to 75° C. and the internal pressure dropped to 27 pounds per square inch. The temperature was maintained at 72-78° C. for another 54 minutes by running steam through the jacket of the autoclave. At

3,223,718

CHa

C1SH37N—CH2CH2—OH

C—C17H35

59° C. and exhibiting textile softening properties similar to the products of the preceding examples.

The textile softening properties of the product of Example I were tested by making up a formulation of the product by first dissolving 5.50% of the product of Example I by weight in a dispersion, containing 0.30% by weight of hydroxyethyl cellulose, available commercially under the designation of Natrosol 250 HR, in 93.15% soft water at 75° C., to which was added 0.85% by weight of a nonionic emulsifier of the polyoxypropylenepolyoxyethylene type available commercially under the designation of Pluronic L-64.

The pH of the emulsion was adjusted to 5.0 with 0 20% hydroxyacetic acid. This emulsion had a viscosity, using a Brookfield Viscometer, of 420 centipoises at 25° C. Samples of the emulsion were stored in a refrigerator, then kept overnight in an oven heated to 110° F. The samples were then rotated for 12 hour periods alternately for one week, first in the refrigerator, then kept at room temperature and then placed in a 110° oven. No separation was noted in any of the samples.

This resulting formulation was tested for textile sottening properties by adding 50 cc. to the final rinse in a Kenmore home washing machine containing a normal load of 8-9 pounds of clothes. These clothes had been previously laundered with a commercial anionic household laundry detergent advertised under the trademark Tide. After the final rinse and drying of the clothes, the clothes were examined for feel and softness. The clothes had an exceptional smoothness and softness as compared to other available textile softeners on the market. This washing and softening procedure was repeated 20 times without any noticeable yellowing or darkening upon ironing of the clothes.

Another formulation was made up in a similar manner as before, containing 3.00% by weight of the product of Example III dissolved in a dispersion of 0.20% by weight of hydroxyethyl cellulose, available commercially under the designation of Natrosol 250 HR, in 96.15% soft water 40 at 70° C. A nonionic emulsifier, the same one as in the preceding formulation, was added in the amount of .50% by weight to the resulting mixture, and the pH was adjusted to 5.0 with .15% hydroxyacetic acid. _ A viscosity of 270 centipoises at 25° C. was obtained with a Brook- 45 field Viscometer on the finished product. Subjecting samples of the emulsion for 12 hour periods for one week in succession to the refrigerator, the 110° F. oven and at room temperature did not cause any separation of the samples. .

ounces of this formulation was added in a test to the final rinse as before in a home washing machine under the same conditions. Clothes laundered and treated with this formulation repeatedly for 20 times exhibited no yellowing or darkening upon ironing. The treated 55 clothes had an unusual smoothness and softness to. the touch as compared to clothes treated with commercially available textile softeners.

The structural formula of these new compositions of _{1O LU} uaiuum awma, jlv2 *□ _r —— matter may be illustrated as follows, with reference to _{60 s}i_sting of an acyclic hydrocarbyl radical having from 16 the preparation of the product of Example I:

Stearyl dimethyl hydroxyethyl

Stearate ammonium

Any normal aliphatic carboxylic acid or hydroxylated carboxylic acid having from 2 to 22 carbon atoms may be used in place of stearic acid as shown above. Further, any normal aliphatic radical having from 16 to 22 carbon atoms could be used in place of the palmityl or stearyl radical of the amine. Also, any normal aliphatic radical having from 16 to 22 carbon atoms may be used to replace both the stearyl radical and one of the methyl groups of the tertiary amine. The term “normal aliphatic radical” as used herein means an acyclic hydrocarbyl radical.

The compositions defined above may be more conven20 iently and accurately expressed by the following formula:

R₂

[OOCR3]CHi in which Ri is an acyclic hydrocarbyl radical having from 16 to 22 carbon atoms, R₂ is selected from the group consisting of an acyclic hydrocarbyl radical having from 16 to 22 carbon atoms and a methyl radical, and R₃ is selected from the group consisting of alkyl and hydroxy alkyl radicals having from 1 to 21 carbon atoms, and two of the radicals of the R_t, R₂ and R₃ are long chain. These compositions, as illustrated above for preparation of the product of Example I, are made by reacting an aliphatic carboxylic or hydroxy carboxylic acid R₃COOH in which R₃ has the values given in the above formula with a tertiary amine having the formula Ri(R₂)N—CH₃ in which Rt and R₂ are defined as above to form a neutral amine salt of the acid. Thereafter, the amine salt is reacted with ethylene oxide in approximately equal molar quantities to alkylate the neutral amine salt and form a quaternary ammonium compound by introduction of the hydroxyethyl group as shown above.

While we have described preferred examples of this invention as to compositions of matter and methods of preparation it is understood that the scope of the invention is not to be limited thereby but numerous variations are possible without departing from the spirit of the invention as claimed hereinafter.