US2905681A

US2905681A - Surface-active formals

Info

Publication number: US2905681A
Application number: US685797A
Authority: US
Inventors: Benneville Peter L De; Homer J Sims
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1957-09-24
Filing date: 1957-09-24
Publication date: 1959-09-22
Anticipated expiration: 1976-09-22

Description

United States Patent SURFACE-ACTIVE FORMALS Peter de Bonneville and Homer J. Sims, Philadelphia, Pa, assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application September 24, 1957 Serial No. 685,797

9 Claims. (Cl. 260-4106) The present invention concerns specific surface-active formals. It is further concerned with specific surfaceactive formals that are stable under alkaline or neutral conditions but which may be altered by acidic conditions. This alteration may take the form of changing an oilsoluble, surface-active compound toa water-soluble, surface-active compound, or a water-soluble, surface-active compound to one of lessened or substantially no surface activity. This invention also concerns a method for the preparation of the specific surface-active formals.

The acid-sensitive, non-ionic, surface-active formals of this invention may be represented by the formula in which R represents an alkyl group of 8 to 21 carbon atoms, n is an integer from 6 to 50, and Z is an alkyl group of 8 to 18 carbon atoms, an alkenyl group of 8 to 18 carbon atoms, or an alkylphenyl group in which the alkyl portion has from 8 to 24 carbon atoms.

R may typically be octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, heptadeeyl, octadecyl, nonodecyl, heneicosyl, or the like, in any of the known spatial configurations, such as normal, iso, or tertiary.

The integer It varies from 6 to about 50. When n ranges from about 6 to 12, the product is oil soluble, and when n ranges from 13 to about 50, the product is substantially water soluble.

Z may represent an alkyl group of 8 to 18 carbon atoms, such as octyl, nonyl, decyl, dodecyl, pentadecyl, and octadecyl. Z may also represent an alkenyl group of 8 to 18 carbon atoms, such as octenyl, nonenyl, decenyl, dodecenyl, hexadecenyl, and octadecenyl. Z further may represent an alkylphenyl group in which the alkyl portion contains 8 to 24 carbon atoms and may be in the form of one or more alkyl groups as long as the restriction, as to range of carbon atoms, is ad hered to; Typical alkylphenyl representations of Z include octylphenyl, nonylphenyl, dodecylphenyl, octadecylphenyl, dioctylphenyl, dinonylphenyl, didodecylphenyl, and tetracosylphenyl. The alkyl and alkenyl representations of Z as well as the alkyl portion of the alkylphenyl representation of Z may exhibit any of the known spatial configurations, such as normal, iso, or tertiary. The alkenyl groups may have the double bond in any of the possible locations. The alkyl group or groups, as the case may be, in the alkylphenyl representation of Z, may be positioned at any of the possible loca tions on the benzene ring. Particularly useful are those representations of Z that include octyl, nonyl, dodecyl, octadeeyl, oc'tenyl, decenyl, dodecenyl, octadecenyl, octyl phenyl, nonylphenyl, dodecylphenyl, dioctylphenyl, and dinenylph y A wide variety of non-ionicsurface-active agents is known in the art, and usually these are stable in acid, basic, and neutral media In many applications, it is necessary or at least highly desirable to remove or change the surface activity of an agent at some critical point in the operation. For example, if an ordinary, non-ionic, surface-active agent is used to remove oils and waxes from raw wool by emulsification, there is obtained an emulsion in water which is not easily broken, either for the recovery of the oils and waxes or purposes of disposal. Also, the effluent from commercial laundries sium carbonate; and the like.

using non-ionic detergents remains highly surface active, causing many troublesome problems of foaming and disposal. Further, when non-ionic, surface-active agents are used for the recovery of petroleum, there is obtained an emulsion which is not easily broken without the use of certain complex and expensive demulsifying agents. The present compounds can be used in all of the above situations by employing a step in which the objectionable emulsions are treated with dilute acids which, since there is an alteration in the surface-active properties of the present compounds, permits the ready and effective conclusion of the operations described heretofore. The subject compounds may also be used in the preparation of emulsion polymers which can Well be coagulated, if desired, in fiber form by treatment with dilute acids. The present compounds are useful general-purpose detergents that exhibit low foam, good detergency, and highcloud points.

The two high molecular weight hydrophobic groups in the compounds of this invention contribute to the oilsolubility of the molecule up to-quite high molecular weights as represented by the number of oxyethylene units. For this reason, it is possible to prepare compounds which are initially oil-solubl e and water-insoluble, with sufiicient surface activity to function as emulsifying and suspending agents. Solutions of these compounds may be altered by acidic conditions in water to convert them to water-soluble, surface-active compounds. Thus, the surface activity can be transferred from the oil phase to the water phase. Another advantage of these compounds is the small amount of foam which is generated in water solutions.

The present compounds are preferably prepared byreacting a compound having the formula II RCOCH X with one having the formula ZO CH CH O) ,,H

ducted in the presence of a strongly basic inorganic neutrallzmg agent. Among the basic agents that may be employed are the. alkali metals, such as sodium and I potassium; the alkali metal hydroxides, such as sodium hydrox1de, potassium hydroxide, or lithium hydroxide;

alkaline earth metal hydroxides, such as barium hydroxide, calcium hydroxide, and strontium hydroxide; aI-' kali metal carbonates, such as sodium carbonate, potas- The basic agent should be present in an amount somewhat greater than an equivalent amount of the reactants in order'to'assure the complete neutralization of the hydrochloric or hydrobromic acid formed in the reaction.

The compounds of this invention are prepared by conducting the reaction in the temperature range of about l0 to 40 C., preferably 0 to 20 C. The reaction is exothermic in nature. It is preferred to mix the alcohol and the halogenated compound in a solvent and then add the basic agent gradually in small amounts. Suitable as a solvent in this respect are benzene, toluene, xylene,'ancl the like. Reaction time is not critical but generallyiwill vary from about 30 minutes to 10 hours or more, depending largely on the individual reactants employed.

While a solvent is not required in this reaction, one is effects of the exodesirable in order to minimize the thermic nature of the reaction as previously indicated and also in order to aid in the separation of the inorganic salt by-product formed.

Typical reactants that may be employed include:

ll CsHn 0 OHQO].

ll Q mCOCHzCI ll in aGOGH Br ll 01 E3 0 0 OHQOI 018E210 OCHaCl ll oumgooomoi or any mixtures thereof,

The reactants of this invention are known compounds or readily prepared by known methods. In a preparation of the ethoxy alcohol reactants having 6 to 50 ethoxy units, there is frequently obtained a mixture of compounds having different members of ethoxy units. This is known in the art and is no deterrent to the present reaction since satisfactory and useful compounds are formed from the mixture of compounds in the same way as the individual compounds. it is to be understood, therefore, that the integer n stands for either the number of ethoxy units in a single compound or an average value in a mixture of compounds. Likewise the reactants n i Joornx are derived from fatty acids which are obtained frequently in commercial practice as mixtures. These mixtures also lead to satisfactory and useful compounds.

At the conclusion of the reaction, the halide salt formed as a reaction by-product is removed by filtration. The product is obtained as the filtrate. If a solvent has been employed, as indicated previously, it may be removed by stripping in a conventional manner. Even if a solvent has not been employed during the course of the reaction, the use of one is often advantageous in the isolation of the product in order to facilitate the removal of the inorganic halide salt formed.

The products of this invention, having the utilities previously stated, possess the hydrophobic-hydrophilic balance required for a substance to exhibit surface activity. As has been presented previously, it is frequently desirable to employ a surface active material at one stage of a process and not have such material interfere at a later stage of the process as has been outlined heretofore. The present compounds may be used as valuable surfaceactive agents at one stage of a process and then chemically altered to change its surface-active characteristics at a later stage of the process as will be apparent hereinafter. The present compounds are quite stable in alkaline or neutral media but may be chemically altered in an acidic media, particularly at temperatures approaching about C. Hydrochloric acid or the like is particularly convenient and effective for use in this respect, and the change is effected usually in a matter of minutes, such as 5 or 10, depending largely on the temperatures and compounds involved. The present compound is split into three fragments: one, an oily, water-insoluble compound of no surface activity; two, formaldehyde; and the third, a water-soluble, surface-active compound.

7 The compounds of this invention, as well as the methods for their preparation, may be more fully understood from the following examples which are offered by way of illustration and not by way of limitation. Parts by weight are used throughout.

Example 1 There are introduced into a reaction vessel 25 parts of chloromethyl laurate, 60 parts of and 100 parts of benzene. The mixture is cooled to 5 C. and to it there is added gradually over a period one hour 8 parts of powdered commercial potassium hydroxide. The temperature is maintained below 10 C. during the addition of the potassium hydroxide by application of an ice-salt bath at intervals. The mixture is stirred at 10 C. for 2 hours and then allowed to come to room temperature. The reaction mixture is then filtered and the benzene is removed from the filtrate under vacuum to yield 65 parts of a light yellow oil. This oil is identified as octylphenoxynonaethoxymethyl laurate, C11H23COOCH2O 9C6H4C3H17. This product is soluble in hydrocarbon oils, and may be used to promote their emulsification with water.

In like manner there are prepared emulsification.

By the same procedure there are also prepared 21 43 2 z z 5o e 4 12 25 a l'i z z z 34C6H3 12 25) z and C H COOCH O(CH CH O) C H C H which are water-soluble waxes useful as detergents and emulsifiers.

Example 2 There are introduced into a reaction vessel 50 parts of chloromethyl laurate, 116 parts of rz zs z Hz 9 The mixture is cooled to 20 C. and to it is added in portions 5 parts of powdered sodium hydroxide over a period of /5 hour. The mixture is held at 20 C. by use of an ice-bath. The mixture is stirred for one hour after, the end of the addition of the sodium hydroxide and then allowed to come to room temperature. It is filtered and the benzene is removed from the filtrate under vacuum to yield 130 parts of a clear, light yellow oil which is identified as dodecycloxynonaethoxymethyl laurate C H COOCH O (CH CH O C H In similar manner there are prepared C H COOCH O (CH CH O C H C H COOCH O CH CH O C H 21 43 2 2 z )o 1a :-1'7 and rs z'z z z z 20C18H35 We claim: 1. A composition of matter having the formula R OCH2(OCHZC 2)nOZ in which R is an alkyl group of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is a member of the class consisting of alkyl groups of 8 to 18 carbon atoms, alkenyl groups of 8 to 18 carbon atoms, and alkylphenyl groups in which the alkyl portion has from 8 to 24 carbon atoms.

2. A composition of matter having the formula R'OCHflOCHgCHQnOZ in which R is an alkyl grotp of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is an alkyl group of 8 to l8 carbon atoms.

3. A composition of matter having the formula II R 0 0CH2(O cnlomnoz in which R is an alkyl group of 8 to 21 carbon atoms, n is an integer of from 6 to 50, and Z is an alkenyl group of 8 to 18 carbon atoms.

4. A composition of matter having the formula II R 0 0 0112(0 C 2 2)n Z in which R is an alkyl group of 8 to 21 carbon atoms, 11 is an integer of from 6 to 50, and Z is an alkylphenyl group in which the alkyl portion has from 8 to 24 carbon atoms.

5. A composition of matter having the formula References Cited in the file of this patent UNITED STATES PATENTS 2,395,265 Gresham Feb. 19', 1946 2,596,091 De Benneville May 13, 1952 2,796,423 Cottle et al. June 18, 1957 FOREIGN PATENTS 888,688 German Sept. 3, 1953 OTHER REFERENCES McCutcheon: Synthetic Detergents, 1950, pp. 156- 157.

Claims

1. A COMPOSITION OF MATTER HAVING THE FORMULA

2. A COMPOSITION OF MATTER HAVING THE FORMULA