US 2320707 A
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Patented June 1, 1943 UNITED STATES PATENT OFFICE SURFACE ACTIVE AGENT AND THE PROCESS OF TREATING FIBROUS MATERIALS THEREWITH mu Robinette, Terre Haute, Ind., assignor to Commercial Solvents Corporation, 'I'erreHaute,
' Ind., a corporation of Maryland No Drawing.
My invention relates to new and useful sur-' face active substances, and more particularly 'it is concerned with a series of compounds, the general type of which has never been, to my knowledge, recognized as possessing wetting and penetrating properties,.as well as other surface active characteristics. These compounds may be represented by the following structural formula:
c c on, A
wherein R represents an alkyl group contain vng at least flve carbon atoms, and R is an alkyl group. I
Specific examples of the substituted 13-611- Application November 15, 1941, Serial No. 419,318
7 cams. (01. 252-255) which is insoluble in water, is liberated. In strongly alkaline solutions, on the other hand, ordinary soaps become insoluble and are salted out of solution. In addition, in the presence of solutions containing calcium or magnesium salts such as ordinary hard water, the fatty acid present in the soap is precipitated as a calcium or magnesium soap, such soaps being insoluble sticky materials which, rather than having any detergent action, are regarded as undesirable impurities in solutions employed in the textile and related industries.
In an effort to furnish materials to such ind'ustries free from the undesirable properties of ordinary soaps, there have beendeveloped as detergent and wetting agents products obtained by the sulfonation of certain fatty acids ooixanes which belong to the class represented by .ction, such as the effect obtained by the presace of a surface active agent at a water-oil nterface. For example, in the textile and eather-treating industries there are many sitcurring in 011s and fats. Such fatty acids are characterized by containing unsaturated linkages and/or hydroxyl groups in the molecule.
On sulfonating such acids, products, are obtained which contain sulfuric acid ester groups in the molecule, and of course carboxylic acid groups are attached to the terminal carbon atom. The products, however, in general possess weaker wetting and detergent, properties than soaps.
lRtiOlilS where wetting or detergent action is lighly desirable. As a result, many different gents have been proposed to reduce surface ension and promote wetting. The materials reviously employed, however, although satisfacary in some respects, have not met with unqualied success in all cases.
The ordinary soaps, although their surface ctive properties have long been recognized, are
eficient in many respects when employed in the eld of detergent and wetting agents. 'For exmple, although soaps act efficiently as deterents in weakly alkaline solutions, they are of 0 value for this purpose in acid solutions, since nder such circumstances the free fatty acid,
Such products are also relatively unstable, and are capable of being decomposed by hydrolysis.
Other proposed wetting agents comprise the semiand completely-esterified products resulting from the esterification of a higher alcohol with an unsaturated pclybasic acid. After the unsaturated esterifled acid is produced, it is converted into a, more soluble form, ordinarily by treatment with sodium bisulfite to yield the corresponding sulfo derivative of the esterified polybasic acid. While such materials have met with a considerable degree of success in various industries where the need for surface-active materials exists, they are not without defects. 0bviouslv, surface-active agents of this type are not stable to alkali, and in some instances,
especially in the textile field, much difficulty has been experienced with the tendency of the textile-treating baths containing such materials, to foam.
I have now discoveredthat the aminodioxanes included by the above generic formula, when employed with a suitable solubilizing agent,.impart valuable surface-active properties to solutions thereof. Such wetting agents have been found to be particularly useful under conditions where previous wetting and penetrating agents. especially of the'type mentioned above, are of little or no value. For example, the wetting percent aqueous sulfonated parts of the aminodioxane.
i agents of the present invention are not decomposed either by hard water, or solutions containing appreciable quantities of alkali. These new wetting agents possess the further advantagein that aqueous solutions thereof do not foam.
In general. the quantity of aminodioxanes that may be employed, will be found to vary with the type of wetting operation under consideration, as well as with the material to be wetted. For the greater majority of uses, however, I
power of the resulting solution was then measured at 30 C. by the method of Draves and Clarkson, the following data being obtained:
have found that the aminodioxanes are most advantageously employed in amounts of from about .09 to 2.0 per cent by weight of the treating bath. The quantity of solubilizing material to be utilized in preparing the wetting agents of the present invention, will also be found to differ, depending of course upon the type of solubilizing agent employed and the character oi the substance which is to be treated. Generally, I have found it suitable to employ the solubilizing agent in amounts varying from approximately 10 to 35 per cent, based upon the weight of the aminodioxane used. As examples of suitable solubilizing materials which may be employed in preparing the wetting agents of the present invention, there may be mentioned sulfonated castor oil, sulfonated petroleum oils, sulionat'ed aliryl aromatic compounds, sulfated esters. sulfated ether alcohols, sulfonated alkyl diphenyls, and the like.
The wetting and penetrating powers of certain of, the wetting agents covered by the present invention have been compared with some of the commercially-available agents, the results of the tests performed appearing in the table below. The wetting properties of the various agents tested were measured by the method of Draves and Clarkson (Am. Assoc. Textile Colorists and Chemists Year Book, vol. 17, pp. 216-222 (1940)) which determines the sinking or wetting-out time required for a five-gram skein of unboiied two-ply yarn in varying concentrations of aqueous solutions of wetting agents. These tests were performed at a temperature of approximate- Aminodioxanes of the type mentioned above were solubilized by blending 120 parts of 14.5 castor oil with 50 The sinking times of aqueous solutions containing three grams per liter of the blend of certainof the aminodioxanes, are shown in the following table:
Grams per liter Instantaneous.
Example H 5 5-amino 5 ethylda-heptyl)-1,3-dioxane was found to have a wetting time of 2,1 seconds in concentrations of 1.5 grams per liter at 25 0..
according to the Braves test. The wetting time is instantaneous at a concentration of 3 grams per liter in distilled water. In water of 18 grains hardness, the solution exhibited a wetting time of 32 seconds at a concentration of 1.5 grams per liter, and 23, seconds at 3 grams perliter. Triton W-30 alone possessed a wetting time of 8'? seconds at 1.5 grams per liter, and 37 seconds at a concentration of 3 grams per liter.
Ewample H2 7 Grams per liter Wettlngout time 6 12 seconds. 5 15 seconds. 2 SOscconds. 0' ..1 seconds.
Under similar conditions the wetting power of solutions containing only Santomerse No. 1, in varyingconcentrations, were found to have the following wetting-out activity when measured according to the method of Draves and Clarlrson:
Wettingout time 6.2 seconds. 12.0 seconds.
Table I Wetting agent Wetting-out time 5-amino-5-methyl-2-(3-hcptyl)-l,3-dioxane.. Skcin sinks instantly. G-aaIjiino'Ii-cthyI-Z-(l-cthyl-l-pentenyl)-1,3- 36 seconds. 60
oxane. 6-amino-6-cthyl-2-(3heptyl)-l,s4lioxane.... Skein sinks instantly. ii-amino-5-ethyl-2-hendecyi-i,3-dioxane. 60 seconds.
acteristics of solutions containing commercially-available wetting agents.
\ Example I 34 seconds.
It will be apparent fromthe above data that that addition of 5-amino-5-ethyl-2-(3-heptyl) 1,3-dioxane to a formula using Santomerse No. 1
gives a much faster wetting time than aqueoussolutions containing only Santomerse No. 1. For example. 6 grams per liter of the wetting agent containing both 5-amino-5-ethyl-2-(3-heptyl)- 1,3-dioxane and Saritomerse No. 1 is equivalent to .84 gram per liter of Santomerse No. 1. The
former wetting agent, in concentrations of 6 grams per liter, gives a .solution possessing a wettingtime of 12 seconds, whereas a solution containing. gram per liter oi Santomerse No. 1
possesses a wetting time which is appreciably excess of 34 seconds.
The aminodioxanes of the present invention may be prepared in accordance with any ofsev- Over Bminutes.
eral suitable procedures. I prefer, however, to produce such materials by means-of the process described in U. S. Patent No. 2,247,256 granted June 24, 19.41, to Murray Senkus. According to this procedure, the corresponding nitrodioxane is subjected to high-pressure hydrogenation in the presence of a nickel catalyst and a suitable solvent, such as methanol, at a temperature in the neighborhood of 25-30 C. The startingmaterials in this process are conveniently prepared by condensing a suitable poly-hydroxy nitro compound with an aliphatic aldehyde, such as hexanal, heptanal, heptaldehyde, 2-ethyl-hexanal, dodecanai, and the like. This condensation reaction is carried out by heating the polyhydroxy nitro compound in the presence of the desired aldehyde and a small quantity of an acid catalyst, and if desired, in the presence of an organic liquid, such as benzene or toluene, which is capable of removing the water produced during the reaction in the form of a constant boiling mixture.
In regard to the siiigle compounds covered by certain of the appended claims, these products,
. i. e., -amino-5-methy1-2-( -heptyl) -1,3-dioxane and 5-amino-5-ethyl-2- (3-hepty1) -1,3 -dioxane, may be prepared by first synthesizing the corresponding nitrodioxane, which in the case of the former compound involves the condensation of 1 mole of 2-methyl-2-nitro-1,3-propanediol with 1 mole of 2-ethylhexanal, while the latter amino dioxane requires the condensation of 1 mole of 2-ethy1-2-nitro-1,3-propanediol with 1 mole of 2-ethyl-hexanal. Both condensation reactions require the presence of a small quantity of a mineral acid, such as sulfuric acid to serve as a catalyst. The respective nitro dioxanes, prepared in this manner, are then dissolved in a suitable solvent such as methanol and subjected to the action of hydrogen at a temperature of 25-30 0., and at a pressure of 2000 pounds per square inch in the presence of Raney nickel, to produce the corresponding amino dioxan'e.
It is understood that applicant does not claim the amino dioxanes per se described and referred to herein but instead claims merely the new and novel use of said compounds which is disclosed herein.
Wetting agents of the type contemplated by the present invention are especially suited for use in the preparation of printing pastes and sizing mixtures. They may also be used as penetrants in fiax-retting baths. These products serve as useful wetting, cleansing, and penetrating agents in bleaching liquors, such as those used in kier boiling of cotton goods, and may be added to the lye liquors used for mercerizing cotton goods. They can also be used to assist in twist setting of yarn and in processes of stripping colors. Such compounds also find use as assistants in processes of stripping dyes from dyed textile material.
A second class of uses of these new surfaceactive agents constitutestheir use as assistants in the application of dyestuffs. They may be employed as dye-leveling agents due to their wetting and penetrating powers in neutral or alkaline dyeing baths, and are capable of facilitating dyeing with developed dyes, the dyeing of acetate fibers with insoluble dyes, the dyeing of animal fibers with vat dyes, the dyeing of various synthetic fibers, and the dyeing of leather.
It will readily be seen from the foregoing description that by'means of the present invention, a large group of new surface-active substances has been made available, and that such agents are adapted for use in numerous industrial processes which require surface-active materials. It will also be apparent to those skilled in the art that many widely different embodiments of the present invention exist, and that such embodiments may be utilized without departing from the scope of said invention. v
My invention now having been described, what I claim is:
1. A bath for the wet treatment of organic fibrous materials to change the surface active properties thereof, comprising an added solubilizing compound of the sulfur-containing type and an aminodioxane having the formula:
in which R represents an alkyl group containing at least 5 carbon atoms, and R is an alkyl group.
3. An aqueous bath for the wet treatment of organic fibrous materialsto change the surface active properties thereof, comprising an added' solubilizing compound of the sulfur-containing type and from about 0.09 to 2 per cent by weight of the bath of an aminodioxane having the formula:
wherein R represents an alkyl group containing at least 5 carbon atoms, and R. is an allq'l group.
4. An aqueous bath for the wet treatment of organic. fibrous materials to change the surface active properties thereof, comprising an added solubilizing compound of the sulfur-containing type and 5-amino-5-ethyl-2-(3-heptyl);1,3-dioxane.
. 5. In the process for the wet treatment of organic fibrous materialsrin an aqueous bath to improve the surface active properties thereof, the improvement which comprises incorporating in the bath in an amountto change its surface active properties a composition consisting of an wherein R represents an alkyi group having at least 5 carbon atoms, and R is an alkyl group.
6. In the process for the wet treatment of organic fibrous materials in an aqueous bath to improve the surface active properties thereof, the 15 improvement which comprises incorporating in the bath in on amount to ohmic its surisce sctive properties e composition consisting of an added soiubiiisinz scent of the miiur-ccntsinins type and fi smino-i-ethyi-z-(ii-heptyi)-i.3-diossne.
7. In the process for the wet treatment 0! organic nbrous materials in an aqueous both to improve the surisce active properties thereof, the improvement which comprises incorporating in the bath in an' amount to change its surisce active properties a composition consisting of an added soiubiiizin: scent oi the sulfur-conteininz type and 5-amino-5-methyl-2-(3-heptyi) -1,3-dioxsne.