US2409671A

US2409671A - Substantially oil soluble polyalkyl aromatic sulfonates

Info

Publication number: US2409671A
Application number: US513469A
Authority: US
Inventors: Faust Jacob
Original assignee: SONNEBORN SONS Inc L
Current assignee: L SONNEBORN SONS Inc; SONNEBORN SONS Inc L
Priority date: 1943-12-08
Filing date: 1943-12-08
Publication date: 1946-10-22
Anticipated expiration: 1963-10-22

Description

Patented Oct. 22, 1946 UNITED STATES PATENT OFFICE.

SUBSTANTIALLY' 01L SOLUBLE POLYALKYL AROMA-TIG SULFONATES Jacob Faust, Bellevillc, N. .L, assignor to L. Son

neborn Sons, Inc., a corporationoi Delaware.-

NDrawing;v Application December- 8, 1943; SerialNo. 513,469-

3 Claims. 1.

This; invention relates to new and useful improvements in substantially oil soluble polyalkyl aromatic sulfonates.

One object of the invention comprises, inter alia,. novel substantially oil. soluble polyalkyl aromatic sulfonates. possessing valuable. properties.

cordance with they invention essentially comprises.

from to 50% and preferably from m by Weight of a hydrocarbon material comprising at least one member selected. from the group con.- sisting of petroleum hydrocarbons and polyamyl naphthal'enes with at least three amyl radicals,v and from to and preferably from 60.to-

70% by weight of a substantially oil soluble.

metaland preferably alkali metalpo1yamyl naphthalene sulfonate having one MeSOa radical carried, by an unalkylated position of its. aromatioring.

Within the preferred, embodiment of: my, in-- vention by way of the novel oleophilic hydrocarbon. composition I find it advisable to use a polyamyl naphthylene sulfonate carrying branched chain amyl groups. .Although. individual poly.- amyl naphthalene sulfonates as for instance tritetra-or penta-amyl naphthalene sulfonates may be used, their mixture is ordinarily more easilyavailable since it can be conveniently produced from commercial polyamyl naphthalene which. normally occurs as a mixture of the, tri-, tetraand pentaproducts...

The petroleum hydrocarbon inaccordancewith the. invention may be. any suitable petroleum, hy-. drocarbon or petroleum hydrocarbon. out. As is conventionally understood in the art, when ref; erence is made to the term.petroleum hydrocar-. bon, such term includes not only individualhydrocarbons: but. also mixtures. thereof,

Where the metal polyamyl naphthalene sulfonate in accordance with. the invention. is. designated as being substantially oil soluble, I mean thereby that such product, as: is. well understood 2 in the art, is substantially soluble in. petroleum spirits and oils, coal tar. solvents, chlorinated hydrocarbons and terpene hydrocarbons. Where use is made of the term oleophilic or such similar expression in designation of a hydrocarbon composition in accordance with the invention, I mean. to convey thereby the compatibility of my novel; hydrocarbon composition. as such with the sol,-

vents or group ofv solvents just recited in sub-- stantially all proportions.

A suitable polyamyl naphthalene that maybe used for the preparation of the products in ac.- cordance with the invention, whether ashydrocarbon material or as source for my novel polyamyl naphthalene sulfonates, is, for instance, the

commercial product constituting a light straw- I colored Viscous liquid essentially of the following 7 physical characteristics.

Specific gravity (24 C.) 0.922 Weight'per gallon 7.717 lbs. Viscosity Saybolt at 100 F 4.73 secs. Viscosity Saybolt at 21.0" F 50 secs.

Viscosity index Minus 30 Flash point 350 F.

Fire point 410 F.

Pour point Below minus 10 F. Color (Lovibond /2'ce1l) 5Y1.5R Iodine value 28.2

Refractive index at 20 C 1.545

This commercial polyamyl naphthalene compound is ordinarily a mixture of tri-tetraand penta-amyl naphthalene in substantially the proportion, of -5-5. The amyl groups are in branched chain, that is they are attached. to methyl, propyl, and carbonyl configurations.

The polyamyl naphthalene sulfonates in accordance with the invention are obtained by subjecting a suitable polyamyl naphthalene of the requisite type and characteristics or a mixture of such polyamyl naphthalenes to the action of a sulfonating agent under sulfonating conditions.

The sulfonation reaction may be carried out in any suitable conventional manner such as, for instance, by treatment with gaseous S03 or by the addition of fuming. sulfuric acid such as, for in-. stance, from 50 to. by Weight of a normal 20% fuming sulfuric; acid. In the latter ca the acid may be added as desired, either in a single treatment or in a multiple number of shots. In most cases and particularly with acid amounts approaching or equaling 100% the sulfonation pp oach s quanti ey e ds, Itmay e .0 .1 times. advisable, dependent. upon special. condi-. tions. and treatments, to carry out; the, Sui-0 1 5:

tion reaction in. the presence of a substantially non-sulfonatable organic solvent as, for instance, a suitable halogenated hydrocarbon, such as carbon tetrachloride, ethylene dichloride, amyl chloride, polyamyl chloride and chloroform.

Upon completion of the sulfonation reaction, the reaction mass is allowed to settle and such acid sludge as may have formed is withdrawn. The remaining layer is then suitably neutralized, preferably with the aid of an aqueous caustic solution such as aqueous caustic potash or soda solution, to, for instance, phenol-phthaleine end point neutrality. The crude polyalkyl naphthalene sulfonate obtained may then be purified after the removal of the aqueous layer, by for instance extraction with 50% aqueous alcohol. Alternatively, the sulfonation mix may be dissolved in benzol and the benzol solution may be thereupon washed with water to free the same fromsalts, thereafter distilling clf the benzol and recovering the purified product.

The polyamyl naphthalene sulfonates obtained in accordance with the invention are substantially soluble in petroleum hydrocarbons even in the cold and they are colloidally soluble in water. These novel sulfonate products, when incorporated into petroleum hydrocarbons, render the same substantially spontaneously emulsifiable in aqueous media without the use of any auxiliary linking agents or solvents and the oleophilic hydrocarbon products containing the novel sulfonates in accordance with the invention possess excellent foaming, wetting and penetrating power.

Still further the polyamyl naphthalene sul- -fonates in accordance with the invention are Valuable for textile processing and treating agents. They also constitute valuable agents as plasticizers in the preparation of synthetic rubber, conditioning agents for asphalts, dispersing aids in paint and paint pigment compositions, dispersing agents for insecticides and fungicides in agricultural sprays, assistants in leather processing and finishing, solubilizing agents for resins, dyes and other materials normally insoluble in oil and as ingredients in corrosion inhibiting and rust proofing compositions.

The following examples are furnished by way of illustration and not of limitation:

Example I 50 parts by weight of oleum having a 20% S03 content were slowly stirred into 100 parts by weight of a commercial polyamyl naphthalene of the description and properties hereinabove recited. A sulfonate mass formed which was allowed to settle at a temperature of 140 to 150 F. A small amount of acid sludge was produced and was drawn off, whereupon the upper layer was diluted with an equal volume of benzol and exactly neutralized with 20% caustic soda solution using phenol-phthaleine as indicator. The resulting aqueous layer was allowed to settle and was then drawn oif. The remaining upper layer was distilled to remove the benzol, thus obtaining a puri fied product. The percent conversion to polyamyl naphthalene sulfonate was 55.5%. The resulting product contained about 44% unreacted polyamyl naphthalene.

Example II 100 parts by weight of oleum having a 20% S03 content were slowly stirred into 100 parts by Weight of a commercial polyamyl naphthalene of the description and properties hereinabove re- 4 cited; a sulfonate mass formed which was allowed to settle at a temperature of 140 to 150 F. A small amount of acid sludge was produced and was drawn ofi, whereupon the upper layer was diluted with an equal volume of benzol and exactly neutralized with 20% caustic soda solution using phenol-phthaleine indicator. The aqueous layer was allowed to settle and drawn off. The

upper layer was distilled to remove the benzol, ob-

taining a purified product. The percent conversion to polyamyl naphthalene sulfonate was 90.4%. The resulting product was almost free from unreacted polyamyl naphthalene.

Example III To 100 parts by weight of the polyamyl naphthalene sulfonate product obtained in Example II were added 40 parts by weight of 100 viscosity (Saybolt at 210 F.) Gulf Coast pale oil and the mixture stirred cold to obtain a homogeneous composition containing approximately a polyamyl naphthalene sulfonate content of and an inert hydrocarbon carrier content of approximately 35%.

When only partially sulfonating a suitable polyamyl naphthalene, as is for instance the case when using amounts of acid materially less than the resulting product may be recovered free from unreacted polyamyl naphthalene, or such unreacted polyamyl naphthalene may be left in the resulting sulfonate product, the latter to be used as such with the unreacted polyamyl naphthalene as a diluent therein. In such case, when incorporating the polyamyl naphthalene sulfonate product in a suitable hydrocarbon oil within the scope of the invention, the unreacted polyamyl naphthalene, depending upon the amount present, may be treated as the sole hydrocarbon material or as part of the hydrocarbon material to which the sulfonate is to be added in preparing the oleophilic hydrocarbon composition in accordance with the invention.

The exceptionally high surface activity exercised by our novel oleophilic polyamyl naphthalene sulfonate hydrocarbon composition is, for example, shown by the product resulting from Example III, which in 0.25% aqueous solution shows a wetting time (standard Draves test) of about two seconds and a surface tension of about 36.4 dynes per cm.

Another exceptional and valuable property of our novel sulfonates resides in the fact that they are capable of emulsifying chlorinated hydrocar bons, such as chloroform, carbon tetrachloride, dichlor ethyl ether and the like, to yield emulsions of an exceptionally high degree of stability as is required, for example, in the use of such chlorinated hydrocarbon emulsion for dormant agricultural sprays. None of these chlorinated hydrocarbons has hitherto satisfactorily responded to such emulsification by other wetting agents.

The properties and characteristics inherent in and exercised by the novel polyamyl naphthalene sulfonates are substantially unaffected by the particular hydrocarbon material with which they are compounded in accordance with one of the embodiments of the invention and it is therefore in most cases immaterial whether the same is a petroleum hydrocarbon or unreacted polyamyl naphthalene. To this extent the product resulting, for instance, from Example I shows wetting and surface tension characteristics of substantially the same order as those hereinabove described as exhibited bythe productobtained in accordance with Example II. One of the prime advantages inherent in the presence of unreacted polyamyl naphthalene, however, whether present alone or present in conjunction with petroleum hydrocarbons, essentially resides in the ease of blendability with other components in the preparation of compositions to be compounded, for instance, for textile use, cutting oil use and compositions for such other uses to which the polyamyl naphthalene sulfonates, as an ingredient in accordance with the invention, may lend themselves. For this reason I find it often of advantage, within the scope of one preferred embodiment of my invention, to only partially sulfonate a polyamyl naphthalene in a manner yielding from to 50% and preferably from to by weight of unreacted polyamyl naphthalene, and from to 75% and preferably from to by Weight of polyamyl naphthalene sulfonate of the herein described character and nature. Such a product results, for instance, when proceeding in accordance With Example I. When desiring to obtain a product in accordance with the invention containing in the requisite amounts only unreacted polyamyl naphthalene as the hydrocarbon material, it is possible to achieve this result by using from 50 to of fuming sulfuric acid in the sulfonation treatment herein referred to.

The foregoing description is for purposes of illustration and not of limitation and it is therefore our intention that the invention be limited only by the appended claims or theirequivalents wherein I have endeavored to claim broadly all inherent novelty.

I claim:

1. A new substantially oil-soluble polyalkyl aromatic sulfonate which consists of a substantially oil soluble polyamyl naphthalene sulfonate having one metal sulfonate radical carried by an unalkylated position of the aromatic ring and having at least three amyl radicals.

2. A new substantially oil-soluble polyalkyl aromatic sulfonate in accordance with claim 1 in which said polyamyl naphthalene sulfonate carries branched chain amyl groups.

3. An oleophilic petroleum hydrocarbon composition which comprises from 25 to 50% of a hydrocarbon material comprising at least one member selected from .the group consisting of petroleum hydrocarbons and polyamyl naphthalenes with at least three amyl radicals and from 50 to 75% of a polyamyl naphthalene sulfonate having one metal sulfonate radical carried by an 1111- alkylated position of its aromatic ring and having at least three amyl radicals.

JACOB FAUST.