US3043706A

US3043706A - Mixtures of esters of sulfosuccinic acid

Info

Publication number: US3043706A
Authority: US
Inventors: Fair William Simeon; Kenneth D Ballou
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1959-09-29
Filing date: 1959-09-29
Publication date: 1962-07-10
Anticipated expiration: 1979-07-10

Description

United States Patent 3,043,706 MIXTURES F ESTERS 0F SULFOSUCCINIC ACID William Simeon Fair and Kenneth D. Rallou, Charlotte, N .C., assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed Sept. 29, 1959, Ser. No. 843,075 6 Claims. (Cl. 106287) This invention relates to new compounds suitable as softeners for textile materials and more particularly to new compounds which may be characterized as being suitable for use as rewettable softeners for textile materials. It further relates to the methods of preparing such compounds, their use on textile material and the textile materials finished therewith.

' In the course of their manufacture and finishing, cotton and rayon textiles are usually subjected to various heat treatments. Often the textile materials are coated or impregnated with fillers such as starch, gum tragacanth, gum ghatti, dextrines and the like, in order to impart body to the cloth. I

Frequently, however, these treatments result in the production of a relatively stitf'fabric which is harsh to the feel and less desirable commercially than fabrics possessing a soft hand. As a result the industry has resorted to the use of several types of compounds for the softening of finished fabrics and in the case of rayon textile materials for imparting thereto increased lubricity.

Among the compounds hitherto employed by the art have been sulfonated hydrocarbons, waxes, stearates, and sulfated oils such as cottonseed oil, peanut oil, coconut oil and similar oil products. Additionally, in view of the competitive economics involved in textile manufacture,-some of the most widely employed softening agents have been sulfated and/or sulfonated tallow, and sulfated, and/or sulfonated monoand diglycerides of tallow, cottonseed oil, coconut oil, peanut oil and other compounds containing the relatively longcarbon chain of the higher fatty acids. The presence of these materials even in small amounts in cotton and rayon textiles have resulted in an undesirable yellowing of the fabric subsequent to the heating thereof.

This problem which has long plagued the textile finishing industry was to a substantial measure overcome by the relatively non-yellowing products which are described in U.S. Patent No. 2,734,833, the subject matter of which is incorporated herein by reference. Softeners prepared in accordance with thedescription contained within the above referred to patent, result in the impartation of excellent softness, and relatively little yellowing, compared to that normally produced by the presence of sulfated or sulfonated vegetable oils found in a majority of textile softeners.

While such softeners are for the most part highly desirable, these and many others currently employed in the finishing of textile materials today are characterized by lack of absorbency and rewetting properties which make them less than wholly desirable. This comparative inability to absorb moisture-and to be rewetted is a serious deficiency in textile materials particularly where the end useccntemplated is in towelling such as is found in terry cloth towels and the like.

While most softeners may be characterized. as nondurable (i.e. upon washing or ordinary laundering are removed) with the vast majority of such merchandise being prepared and packaged today, so as to be ready for immediate consumer use, this inability to absorb moisture and to be rewetted has been a constant source of complaint and aggravation in the textile industry.

Accordingly, it is an object of the present invention to provide a composition suitable for use as a softener which is characterized by imparting a soft relatively nonyellowing finish to textile materials having good absorbency and rewetting properties.

It is a further object of the present invention to provide a process for preparing such a composition.

Still further objects of the present invention are to provide a method for treating textile material with such a composition, and textile materials characterized by a ready rewettability, softness and absorbency.

These and other objects and advantages of this invention will become more apparent from the detailed description thereof set forth hereinbelow.

The present invention constitutes an improvement over that disclosed and claimed in US. Patent No. 2,734,833.

We have found that by modifying members of the class of compounds described and claimed therein by a comparatively simple procedure, that a softener characterized by as much as about 30% improvement in absorbency and rewetting may be prepared.

In accordance with the present invention, a mixture comprised of:

(l) A bis-ester of sulfosuccinic acids with a. bi-molec-, ular quantity of a member selected from a group consisting of higher fatty acid glycerides, glycols, alcohols and mixtures thereof, and

(2) A mixed di-ester of sulfosuccinic acid, the mixed ester of sulfosuccinic acid being one with a substantial monomolecular quantity of saturated aliphatic alcohols having from 4 to 10 carbon atoms inclusive, a substantial monomolecular quantity of a member selected from the group of higher fatty. glycerides, glycols, alcohols and mixtures thereof.

Preferably the mixture of 1 and 2 as identified above is one in which the components are present in a molecular ratio of between 1:3 to 3:1 (preferably 1:1) and still more preferably where the mixture is to be employed as a rewettable softener, the components are sulfonated in accordance with a procedure well-known in the art and (1) is a his (tallow acid glyceride monosodium sul: fosuccinate) and (2) is a mixed 2-ethyl hexyl, tallow acid glyceride diester of monosodium sulfosuccinic acid) in which 1 and 2 are present in monomolecular ratios of 1:1.

In general the individual essential component of the mixture above described may be characterized by the following general formulas:

R0% i l-OR GET-C OaMe where R is a member selected from the group consisting of higher fatty acid glycerides (monoand diglycerides) higher fatty acid glycols, higher fatty alcohols and mixtures thereof, and preferably where R is the mixed monoand di-glycerol ester of fatty acids derived from beef tallow and where Me is a salt from cation in a group consisting of alkali metals and ammonium; and

RO--% i-01y am-o,

SO Me where R and Me are as set forth above and R is a saturated aliphatic alcohol containing from 4 to 10 carbon atoms inclusive and preferably is Z-ethyl hexanol.

The term higher fatty as employed herein with respect to glycerides, glycols and alcohols, refers to materials in pure 'mono'glycerides.

'which the fatty component is characterized by a carbon chain length of from C to C inclusive and preferably from C to C inclusive. In general the higher fatty materials are preferably saturated and in the case of and to the extent that they are derivable from animal and/or vegetable oils, these materials should not have a polyunsaturated content of greater than 15 By polyunsaturation it is meant the presence of more than one unsaturated double bond per fatty unit.

As suitable source of animal and vegetable oils and fats for the higher fatty acid glycerides and glycols contemplated for this invention or for higher fatty acids- .'Il1ese. oleaginous materials do not possess any substantial amount'of hydroxy acids and they contain less than about 15% by weight of polyunsaturated acids, havingrelatively low iodine values (the quantity of iodine in mg. absorbed by 1 gm. of oil under normal conditions); and basically possess a non-drying nature.

Hydrogenated oils which do not contain any interferinghydroxy groups (such as in castor oil) may be used, provided the polyunsaturation of the fatty acids therein isreduced to below the above-mentioned 15% value and to correspondingly low iodine values. Such oils would include: hydrogenated cottonseed oil; hydrogenated corn oil; hydrogenated peanut oil; hydrogenated soya bean oil; hydrogenated sunflower seed oil; hydrogenated sesame oil;- hydrogenated kapok oil; hydrogenated rapeseed oil; hydrogenated tung oil; etc.

Although these oils and fats contain fatty acids having various carbon chain lengths, the chain length of particular use within the concepts of the present invention from the system and thereafter a mole of fumaric acid is added. Under suitable reaction conditions the fumaric acid combines the two excess moles of the monoglycerides of the tallow fatty acids and a mixed ester of maleic and fumaric acid results. This condensation product is then sulfonated by use of a bisulfite or metabisulfite containing a cationic salt-forming substituent, such as any of the alkali metals or ammonium. Preferably, the sulfonation is carried out by heating the bis-ester with an aqueous solution of alkali metal or ammonium bisulfite or metabisulfite whereby the corresponding salt is obtained directly.

l-i'e's inthe range of aboutflZ to about 20 carbon atoms,

with16-l8 being the preferred range.

It is, of course, to be understood that selected fatty acids, such as stearic acid, lying in the preferred range of carbon-chain length, and possessing. the properties characteristics noted above, may also be used.

It is not essential that the sulfosu'ccinic acid bis-ester be the reaction product resulting from the use of 100% A mixture of monoglycerides and diglycerides 'is normally commercially available and it has been found that a molar ratio of I-these two constituents within the range of about 5095% 0f monoglyceride and about 505% of diglyceride is well adapted for application to the principles of the present invention. The presence of diglycerides in greater proportions than about 50%, however, undesirably decreases the water solubility characteristics of the compound and is to be avoided.

As an -example of higher fatty acid glycols the following are illustrative: diethylene glycol monostearate, diethylene' glycol monolaurate, polyethylene glycol 200 monooleate, and the like.

As examples of fatty alcohols the following are illustrative: stearyl' alcoholcommercial grade, myristyl alcohol-commercial grade, lauryl alcohol-+c0mmercial grade, and the like. I

The composition of this invention may be prepared by separately preparing the essential components, those materialscorresponding to the general formulas set forth hereinabove and blending and by preparing the essential Alternatively, maleic anhydride may be reacted with an equal or substantially equal molecular quantity of, for example, tallow acid monoglyceride and the resulting maleate reacted with a suitable saturated aliphatic alcohol such as 2-ethy1 hexanol. The resulting product is thereafter reacted with sodium sulfite and sodium bi sulfite to prepare a mixed ester of monosodium sulfosuccinate. This material is then blended or mixed with a material such as is contemplated by general formula 1 above.

The mixture forming the composition of this invention may be applied to textile material by employing conventional textile processing equipment (pad mangle, dye-beck and package machine) from aqueous solutions in concentrations suflicient to deposit from between 0.25 to about 2.0% solids on the weight of the material after drying. Cellulosic fabrics so treated exhibit excellent handling and draping qualities and are readily rewetted by. water or aqueous solutions as required in compressive shrinkage processes for dimensional stabilization or in finishes for towellings and other absorbent fabrics.

In order to illustrate the present invention, the following examples are given primarily by way of illustration. No details or enumerations contained therein should be construed as limitations on the present invention except insofar as pertaining to the present claims. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 g. (1 mole) of 2-ethyl hex-anol were reacted with 98 g. (1 mole) of maleic anhydride at 85-90 C. in a closed vessel equipped with water-cooled reflux condenser and agitator, until the acid value reached .239 (5 hours). Yield was 228 g.1(1 mole) of mono-Z-ethyl hexyl maleate. To this quantity, in the same vessel, was added 1,034 g. (3 moles) of the monoglyceride of tallow fatty acids and .226 g. of xylene. 18 g. :(1 mole)v of water was removed from the. system by azeotropic distillation at 170? C. (3 /2 hours). 116 g. (1 mole), of fumaric acid was added slowly and azeotropic distillation continued forlO hours at 170 C. until an additional 36 g. 2 moles) of water were removed, (Acid value: 14.)

Xylene was removed by distillation under vacuum C. at 10 mm. Hg). Yield was 1300 g. of mixed 2-ethy1' hexyl and tallow acid monoglyceride esters of maleic and fumaric acids.

To 1250 g. of the above mixed esters were added 309 g. water, 51 g. sodium sulfite, 121 g. sodium bisulfite I and g. isopropanol. This mixture was reacted at 86 C. under reflux for 6 hours. Yield was 1875 g. of a water dispersible material containing 76.5% real mixed 2-ethy1 hexyl and tallow acid monoglyceride sodium sulfosuccina-tes.

, 1 EXAMPLE 2 400 g. (1.16 mole) of tallow acid monoglyceride was mole) of water was removed (acid value=14). Xylene was removed by distillation under vacuum (150 C. at mm. of Hg). Yield was 630 g. of 2-ethy1 hexyl, tallow acid monoglycen'de maleate.

600 g. (1.08 mole) of above ester were refluxed with 36 g. of sodium sulfite, 68 g. of sodium bisulfite, 78 g. isopropanol and 156 g. of water at 8688 C. for 5 hours. Yield was 930 g. of a water dispersible paste containing 76% of real 2 ethyl hexyl, tallow acid monoglyceride mono sodium sulfosuccinate.

50 g. of the product above was blended with 38 g. of his (tallow acid monoglyceride) sodium sulfosuccinate and 12 g. of water to form a water dispersible paste useful as a rewettable softener for cellulosic fabrics.

EXAMPLE 3 v This procedure is the reverse of that employed in Example 2. Mono-2-ethyl hexyl maleate was prepared, re-

acted with tallow and monoglyceride to form the mixed ester. This ester was sulfonated and blended with an equal weight (real basis) of bis (tallow acid monoglyceride) sodium sulfosuccinate.

In order to demonstrate the superiority of the rewettable softener of this invention over those commercially available and typical of the prior art, the below comparative 'data has been assembled.

" ABSORBENCY A x 6 inch specimen of towel fabric weighted at one end, is suspended with the weighted end immersed to a depth of one inch in distilled water containing a watersoluble dyestutf. The capillary rise of the colored liquid in the fabric is observed at intervals. The height at the end of two minutes compared with that in untreated towelling similarly tested is the percent absorbency.

SEWABILITY This test is a measurement of the lubricating properties of the finish. It is made on a harsh fabric of heavy construction (sulfur-dyed twill) to simplify the determination.

A 12" seam is sewn through four layers of the fabric under test in the warp direction using a high speed sewing machine (4000 stitches per minute) equipped with a No. 19 needle at 16 stitches per inch. A 3" length of the seam is then ravelled to expose the yarns traversed by the seam and the number of broken filling ends in the third layer of fabric counted. Best sewability, expressed as average number of breaks per inch, is indicated by minimum yarn breakage.

SOETNESS RATING- The relative softness or handling characteristics of I Table I EVALUATION OF SOFTENERS FOR TOWEL FINISHING Relative softness Yellowing, Percent Ratings Reflectance Ab- Sewing,

' sorbency Rewetting Sulfur Ratio of On Terry (secs) Dyed Softener Applied Solids 0n Seorch- Accele- Towel, Denim Twill,

Applied Terry On lng, rated Percent Loom Breaks] Towel- Cotton 30 secs. Storage, of Goods Inch ing Percale at 72 Hrs. Untreated 400 F. at 95 C.

Softener A 1 1 1 94 88 mogg than 15 1 Softener B 1 2 2 94. 5 88 84 14 2 Mixture:

Softener A/bis(2ethyl hexyl) mono 1. 3 3 3 92 87. 5 84 4 29 sodium sulfosucclnate 1.2/1 solids rat 0. Untreated 0 4 4 95 90 100 H1258 than 32 In the applications, the softeners were padded onto towelling in the solids indicated in Table l and thereafter the towelling was dried for 15 minutes at 225 F. temperature.

In the comparative work reported in Tables 1 and 2 hereinbelow, the tests referred to therein are conducted as follows:

YELLOWING Searching-A specimen of the treated fabric is placed between two metallic plates maintained at 400 F. for 30 seconds (Suder scorch tester). The reflectance of blue light (470 m from the scorced area is then measured with any suitable instrument and expressed as percent of the reflectance from a magnesium carbonate standard.

Accelerated st0rage.A specimen of the treated fabric is enclosed in a tightly sealed jar containing 0.25 ml. distilled water and stored for 72 hours at 95 C. The reflectance of blue light (470 m from the fabric surface is then measured with any suitable instrument and expressed as above.

Table I hereinbefore demonstrates that Softener B the softener of this invention, is substantially superior with respect to softness compared with mixtures of Softener A andbis-(Z-et-hyl hexanol) monosodium sulfosucoinate, and was superior with respect to yellowing by either of the tests identified in Table I. Further, Table I demonstrates that Softener B is markedly superior with respect to absorbency, when compared with Softener A and is characterized by excellent sewability with respect to either Softener A or the mixture.

A further evaluation of mixtures of Softener A and bis-(Z-ethyl hexanol) monosodi-um sulfosuccinate was conducted in order to demonstrate that such mixtures are not the equivalent of such softeners as Softener B.

In this comparison, two mixtures of Softener A and the above referred to monosodium sulfosuccinate were prepared and applied at the solids indicated in Table II below. The finished towelling was then dried for 15 minutes at 225 F. temperature. The results appear in Table I I below.

Table II EVALUATIONOF SOFTENER A/BIS-(Z-ETHYL HEXYL) MONO 'SODIUM' S ULFOSUOCINATE MIXTURES FOR TOWEL FINISHING Table II demonstrates that the lower the mono sodium sulfosuccinate content, the poorer the absorbency and therefore a solids ratio of approximately 9-10 to 1, which would be typical of a 2-ethyl hexyl content in the softeners of this invention (see Example 1), would be markedly inferior in absorbency to the softeners of this invention. While the present invention and compositions described therein have been limited to softeners of the type contemplated by this invention, it should be kept in mind that such compositions may contain other materials as for example stabilizers, additional softeners'or textile modifying agents, lubricants, and the like.

We claim:

1. A mixture consisting essentially of (1) a bis-este of sulfosuccinic acid with a substantially bi-molecular quantity of a member selected from the group consisting of higher fatty acid glycerides, higher fatty acid glycols,

higher fatty acid alcohols and mixtures thereof, said higher fatty radicals being characterized by a carbon chain length of from C to C inclusive and (2) a mixed di ester of sulfosuccinic acid with a substantially mono molecular quantity of saturated. aliphatic alcohols having from 4 to carbon atoms inclusive and a substantially mono molecular quantity of a member selected from the group consisting of higher fatty acid glycerides, glycols, alcohols and mixtures thereof said higher fatty radicals being characterized by a carbon chain length of from C to C inclu'sive said (1) and (2) being present in a molecular ratio of about 1:3 to about 3:1, respectively.

.2. A'mixture according to claim 1 in which (1) and (2) are presentin molecular ratio of 1:.-1. 3. A mixture according to, claim 1 in which (1) and (2) are sulfonated.

4. A mixture according toclaim 3 in which (1) is a bis (tallow acid glyceride) mono sodium sulfosuccinate and (2) is a mixed Z-ethyl hexyl, fallow acid glyceride di-ester of monosodium sulfosuccinic acid.

5.A method of treating textile materials which com succinic acid with a substantially bi-molecular quantity of a member of the group consisting of higher fatty acid glycerides, higher fatty alcohols and mixtures thereof, said higher fatty radicals being characterized by a carbonchain length of from C to C inclusive and (2) a mixed di-ester of :sulfosuccinic acid with a substantially monomolecular quantity of saturated aliphatic alcohols having from 4 to 10 carbon atoms inclusive and a substantially mono-molecular quantity of a member selected from the group consisting of higher fatty glycerides, glycols, alcohols and mixtures thereof said higher fatty radicals being characterized by a carbon chain length of from C to C inclusive said (1) and (2) of said rewettable softening agent being present in a molecular ratio of about 1:3 to about 321, respectively. I

6. A textile material characterized by a softness of hand and ready rewettability comprising a textile material having distributed thereon, (1) a bis-ester of sulfo succinic acid with a substantially bi-molecmlar quantity of a member of the group consisting of higher fatty acid glycerides, higher fatty acid glycols, higher fatty alcohols and mixtures thereof, said higher fatty radicals being characterized by a car-hon chain length of from C to C inclusive and (2) a mixed di-ester of sulfosuccinic acid with a substantially mono molecular quantity of saturated aliphatic alcohols having from 4 to 10 carbon atoms inclusive and a substantially mono molecular quantity of a member selected from the group consisting of higher fatty glycerides, glycols, alcohols and mixtures thereof said higher fatty radicals being characterized by a carbon chain length of from C to C inclusive said (1) and (2) being present in a molecular ratio of about 1:3 to about 3:1, respectively.

References Cited in the file of this patent UNITED STATES PATENTS 2,637,663 Thurston May 5, 1953 2,734,833 Thurston Feb. 14, 1956 2,761,795 Carncs Sept. 4, 1956 2,826,514

Schroeder Mar. 11, 1958

Claims

1. A MIXTURE CONSISTING ESSENTIALLY OF (1) A BIS-ESTER OF SULFOSUCCINIC ACID WITH A SUBSTANTIALLY BI-MOLECULAR QUANTITY OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF HIGHER FATTY ACID GLYCERIDES, HIGHER FATTY ACID GLYCOLS, HIGHER FATTY ACID ALCOHOLS AND MIXTURES THEREOF, SAID HIGHER FATTY RADICALS BEING CHARACTERIZED BY A CARBON CHAIN LENGTH OF FROM C12 TO C20 INCLUSIVE AND (2) A MIXED DIESTER OF SULFOSUCCINIC ACID WITH A SUBSTANTIALLY MONO MOLECULAR QUANTITY OF SATURATED ALIPHATIC ALCOHOLS HAVING FROM 4 TO 10 CARBON ATOMS INCLUSIVE AND A SUBSTANTIALLY MONO MOLECULAR QUANTITY OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF HIGHER FATTY ACID GLYCERIDES, GLYCOLS, ALCOHOLS AND MIXTURE THEREOF SAID HIGHER FATTY RADICALS BEING CHARACTERIZED BY A CARBON CHAIN LENGTH OF FROM C12 TO C20 INCLUSIVE SAID (1) AND (2) BEING PRESENT IN A MOLECULAR RATIO OF ABOUT 1:3 TO ABOUT 3:1, RESPECTIVELY.