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Publication numberUS2346454 A
Publication typeGrant
Publication dateApr 11, 1944
Filing dateAug 14, 1942
Priority dateAug 14, 1942
Publication numberUS 2346454 A, US 2346454A, US-A-2346454, US2346454 A, US2346454A
InventorsJr Hillary Robinette
Original AssigneeCommercial Solvents Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface active agent
US 2346454 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

ate-ante Apr. 11',

, 2,346,454. SURFACE ACTIVE AGENT Hillary Robinette, Jr., Arlington, Masa, assignor to Commercial Solvents Corporation, Terre Haute, llnd., a corporation of Maryland No Drawing. Application August 14, 1942,

Serial No. 454,780

9 Claims. (CI. 2.52-8.75)

, My invention relates to new and useful surface active substances. More particularly, it is concemed 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 charin which R represents an alkyl group, and X may be either cycloalkylidene, alkylidene, substituted cycloalkylidene, or the disubstituted methylene group R: R' wherein R and 1K. may be either alkyl, aryl,'or aralkyl.

Specific examples of compounds belonging to the class represented by the above generic formula are 5-amino-2,5-diethyl-Z-methyl-l,3-di-- I oxane, 5-amino-2-isobutyl-5eethyl-2-methy1-l,3-

dioxane,- 5-amino-5-methyl-2,2-diphenyl-1,3-di oxane, 5-aminoe5-methyl-2,2-pentamethylene- 1,3-dioxane, 5-amino-5-meth.yl-2,2-tetra-methyleI'ie-1,3-dioxane, 5-amino-5-methyl-2-benzyh 2-methyl-l,3-dioxane, and the like.

'In numerous industries there exists a need for certain types of chemical compounds ordinarily employed in small quantities to secure an effect which is principally the result of a wetting action, such as the effect obtained by the presence of a surface-active agent at a water-oil interface. For example, in the textile and leather treating industries there are manysituations where wetting or detergent action is highlyzdesirable. As a result, many different agents. have been proposed to reduce surface, tension and promote wetting. The materials previously employed,-

however, although satisfactory in some respects,

.. have not met with unqualified success in all instances.

The ordinary soaps, although their surface active properties have long been recognized, are deficient in many respects when employed in the field of detergent'and wetting agents. For example, although soaps act efliciently as detergents in weakly alkaline solutions, they are of no value for this purpose in acid solutions, since under such circumstances the free fatty acid whichis insoluble in water,,is liberated. In strongly alkaline solutions, on the other hand, ordinary soaps becom 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 attempt to furnish materials to such industries, free from the undesirable properties of ordinary soaps, there have been developed as detergent and wetting agents, products obtained by the sulfonation of certain fatty acids occurring in oils and fats. Such fatty acids are char acterized by containing unsaturated linkages and/or hydroxyl groups inthe molecule. In sulfonating'such acids, productsare obtained which contain sulfuric ester groups in the molecule,

and, of course, oarboxylic acid groups are attached to the terminal carbon atom. The products, however, in general possess weaker wetting and detergent properties than soaps. Such products are also relatively unstable, and are capable of being decomposed by hydrolysis;

Other proposed wetting agents comprise the semi and completely esterified products resulting from the esterification of a higher alcohol with an unsaturated polybasic acid. After the unsaturated esterified 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 aconsiderable degree of success in various industries where the need for surface active materials exists, they are not without defects. Natually, surface active agents of this type are not stable to the continued action of alkali, and in somefinstances, especially in the textile fields, much difficulty has been experienced with the tendency of the textile treating baths, containing such materials, to foam.

I have now discovered that the aminodioxanes represented by the above generic formula, when 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 agents of the present invention are not decomposed either by hard water or solutions con-.

taining appreciable quantities of alkali. These new wetting agents possess a further advantage in 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 have found that the aminodioxanes are most advantageously employed in amounts of fromabout .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 of the substance to be treated. Generally, I have found it desirable to employ the solubilizing agents in amounts varying from approximately to 35 per cent based upon the weight of the'aminodioxane used. As examples of suitable solubiliz- 1 t-i o .L o or the characteristic sulfuric acid grouping.

o t o io I l o The wetting and penetrating powers of certain of the wetting agents covered by the present inventionhave 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 .Chemlsts Year Book, vol. 17, pp. 216-222 (1940)) which determines the sinking or wetting-out of the resulting solution was then measured at time required for a 5-gram skein of unboiled 2- ply yarn in varying concentrations of aqueous solutions of "wetting agents. These tests were performed at a temperature of approximately 30 C.

Aminodioxanes of the type mentioned above were solubilized by bending 120 parts of 14.5 per cent aqueous sulionated castor oil with parts of the aminodioxane. The sinking times or aqueous solutions containing 3 grams per liter of the blend of certain of the aminodioxanes are shbwn in the following table:

I Table Wetting-out Wcttingsgents A time I mine-2,5-diethyl-2-methyl-L3-dioxane. v 5 5- ino-5-ethyl-2,2-(l-methylpentamethylene)-1,&

5-amino-5-methyl-2,2-dipheny!-l,3-dioxane I: 35 5-amino-5.-n 1ethyl-2,2-tetmmethylene-l,3 dioxane -Bkein sinks instantly. w

Thfexamples ,which follow illustrate ypical wettings agents containing aminodioxanes of the above type, and also demonstrate the ability of said aminodioxanes to improve the Wetting characteristics of solutions containing commercially available wetting sgents.

- Example 1' A solution consisting of 50 parts of 5-amino- 2,5-diethy1-2-methyl-1,3-dioxane in 35 parts of 50 per cent sulfonated castor oil and parts of distilled water was prepared. The wetting power 30, 0., by the method of Dunes and Clarkson, the following data being obtained:

Wetting-out time, seconds Example 11 A solution consisting of 20 parts of Triton W-30 (a sulfated ether alcohol) and 10 parts of 5-amino-5-ethyl-2,2-(l-methylpentamethylene) -1,3-dioxane was found to have a wetting time of 25 seconds in concentration of 1.5 grams per liter at 25 C. according to the Braves tests.

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 35 seconds at a concentration of 1.5 grams per liter, and 25 seconds at-3 ams per liter.

Triton W-30 alone possessed a wetting time of 87 seconds at 1.5 grams per liter, and 37 seconds at a concentration of 3 grams per liter.

I Example In,

The wetting power of a solution consisting of 10 parts of Santomerse No. 1 (a sulfonated alkyl diphenyl), 10 parts of 5-amino-5-methyl-2,2-

'tetramethylene-LS-dioxane, 40 parts of per cent alcohol, and 80 parts of water, was measured in accordance with the method of Draves and Clarkson. The followingv results were obtained:

Grams of wet- Wottingout tm solution gamer time, seconds a n 5 15 4 B s 60 When Santomerse lie. 1 alone was added to water, in varyingconcentrations, the resulting solutions were found to have the following wettingout activities as determined by the method of Draves and Clarkson:

Wetting-out, time, seconds u Ovarsmin.

It will'be'evident'from the data given above,

that the addition of 5-amino-5-'-methyl-2,2-tetramethylene-1,3-dioxane to a formula using Santomerse No. 1, gives a muchfaster wetting time than aqueous solutionscontaining only Santomerse No. 1 and, as a result, such mixtures may be advantageously employed where the desired wetting power must be greater than that conven-' the application of dyestufi's.

aeeasse ing mixture. The nitrodioxane thus obtained is then reduced to the corresponding aminodioxane by reduction with hydrogen in the liquid phase under high pressure, in the presence of a suitable nickel hydrogenation catalyst and a solvent, such as methanol. Reduction of these nitrodioxanes may be efiectively carried out at temperatures of from to 35 0.

Suitable ketones which may be employed in the reaction are acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl benzyl ketone, methyl phenyl ketone, cyclohexanone, Z-methylcyclohexanone, cyclopentanone, benzophenone, and the like. As examples of polyhydroxy nitro compounds which may be utilized, there may be mentioned 2-nitro-2-propyl-1,3-propanediol, 2-nitro- 2-ethyl-1,3-propanediol, 2 methyl-2-nitro-1,3- propanediol, and the like.

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 flax 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, in scouring and cleaning operations on textile fabrics and fibers, furs, metals, plastics, ceramics, and as an ingredient'in compositions employed as general detergents, dish-washing compounds, and the like.

A second class of uses of these new surface active agents constitutes their use as assistants in They may be employed as dye-levelling agents, due to their wetting'andz' penetrating powers in neutral or alkaline dyeing baths, and are capable of facilitating dyeing with developed dyes, the dyeing of acetate fibers and insoluble dyes, the dyeing of animal fibers with vat dyes, the dyeing of various synthetic fibers, and the dyeing'of leather.

T the scope of said invention.

My invention now having been described, what I claimis:

1. An aqueous bath for the .wet treatment of textiles comprising an added solubilizing compound of the sulfoxy type and an amino dioxane of the formula:

Nu, m

wherein R represents an alkyl group, and X is a member selected from the class consisting of cycloalkylidene, alkylidene, substituted-cycloalkylidene. and

wherein R and R are members selected from' the group consisting of alkyl, aryl, and aralkyl.

2. An aqueous bath for the wet treatment of textiles comprising an added solubilizing compound of the sulfoxy type and 5-amino-2,5-diethyl-2-methyl-1,3-dioxane.

3. An aqueous bath for the wet treatment of textiles comprising an added solubilizing compound of the sulfoxy type and 5-amino'-5-ethyl- 2,2-(1-methy1 pentamethylene) -1,3-dioxane.

4. An aqueous bath for the wet treatment of textiles comprising an added solubilizing com.- pound of the sulfoxy type and 5-amino-5-methyl- 2,2-tetramethy1ene-1,3-dioxane.

5. The method for improving the surface-active properties of aqueous solutions, which comprises adding thereto a composition consisting of a solubilizing compound of the sulfoxy type and an aminodioxane of the formula:

' NH: R1

0 CH1 \(EH: A o

in which R represents an alkyl group, X is a member selected from the group consisting of cycloalkylidene, alkylidene, substituted-cycloal- -kylidene, and

wherein R. and R are members selected from the group consisting of aryl, alkyl, and aralkyl.

6. A method {or the wet treatment of textiles,

which comprises subjecting the same to the action of an aqueous bath comprising a solubilizing compound of the sulfoxy type and an amlnodioxane of the formula:

wherein R and R are members selected from the group consisting of alkyl, aryl, and aralkyl.

7. A method for the wet treatment of textiles,

4? mmem which comprises subjecting the same to the ac" tion or an aqueous bath comprising a solubiiizing compound of the suitoxy type and 5-amino-2,5- diethyl-2-methy1-1,3-dioxane.

8. A method for thewet treatment of textiles, which comprises subjecting the same to the action of an aqueous bath comprising a solubiiizing compound or the suifom type and 5-amino-5- ethyl- 2,2 -(1 methylpentamethyiene) -1,3-di.ox-


9. A method for the wet treatment of textiles, which comprises subjecting the same to the ac-- tion of an. aqueous bath comprising a solubilizing compound or the suitoxy type and 5-amino-5- methyl-2,2-tetramethv1ene-1,3-dioxane.


Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2543473 *Oct 12, 1949Feb 27, 1951Commercial Solvents CorpAmino cyclic acetals
US5482965 *Sep 3, 1993Jan 9, 1996Rajadhyaksha; Vithal J.Compositions and method comprising aminoalcohol derivatives as membrane penetration enhancers for physiological active agents
U.S. Classification8/576, 252/8.83, 549/371, 510/499, 516/DIG.500, 516/9, 516/914, 516/203, 516/DIG.700, 8/127, 549/333
International ClassificationC07D319/06, D06L1/12, C07D319/08, D06M11/38, D06P1/645
Cooperative ClassificationY10S516/07, Y10S516/914, D06P1/645, D06M11/38, D06L1/12, C07D319/08, Y10S516/05, C07D319/06
European ClassificationC07D319/08, D06L1/12, C07D319/06, D06M11/38, D06P1/645