Patented June 17, 1941 2,245,643 UNITED STATES PATENT OFFICE 2,245,643 WETTING AGENT AND METHOD OF PRODUCING THE SAME Joseph N. Borglin, Wilmington, Del, assignor to Hercules Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application March 15, 1940, Serial No. 324,118 9 Claims. (C. 260-512) This invention relates to substituted diaryl and In proceeding in accordance with one of the arylalkyl ether sulfonic acids. More particularly, procedures of this invention I take a terpene it relates to condensation products of diaryl or such as, for example, pinene, or an Oxygenated aryl-alkyl ether sulfonic acids and terpenes or terpene compound such as, for example, terpineol, Oxygenated terpene compounds. It also relates 5 and condense this, with a diaryl ether or with an to a process for making these materials. alkyl-aryl ether in the presence of a condensing I have found that aromatic compounds substi agent such as mentioned before. I have found tuted in the nucleus by a terpene radical or the that the condensation takes place at temperatures radical of an oxygenated terpene compound may ranging from about 100° C. to about 300° C. de be obtained by condensing a diaryl Or an alkyl 10 pending upon the condensing agent being used. ary ether with terpenes or with Oxygenated re When operating, for example, with p-toluene sul rivatives thereof in the presence of a suitable fonic acid as the condensing agent, I have found acid condensing agent. I have also found that that the preferred temperature range is from . the resulting condensate may be converted into about 200° C. to about 220 C. sulfonic acid derivatives by treatment with. Ordi 5 The resultant condensate is then treated with nary sulfonating agents. Alternatively, the proc a sulfonating agent selected from the group above ess of condensation and sulfonation may be con mentioned. The sulfonation reaction may be car ducted simultaneously or the process may also be ried out at temperatures ranging from about carried out by reacting a sulfonic acid derivative -20° C. to --50° C., but I prefer using a tem of a diary or an alkyl-ary ether with a terpene 20 perature from about -5° C. to about --35 C. or with an oxygenated derivative thereof in the If desired the sulfonated condensate so formed ... presence of a suitable acid condensing agent. may then be neutralized with 8, base, Such as, for The process in accordance with the present in example, sodium hydroxide, potassium hydroxide, vention is applicable to suitable diaryl or alkyl triethanolamine, tetramethyl-annonium hydrox aryl ethers which have found to be sulfonatable, ide, trimethylbenzyl-ammonium hydroxide, am among which are, for example, diphenyl ether, monium hydroxide, pyridine, amylamine, mor methylphenylether, ethylphenylether, stylphenyl pholine, ethanolamine, diethanolamine, etc. After ether and amylphenyl ether, phenylglycery ether, drying, a product results having good emulsify cresylmethyl ether, cresyathyl ether, cresylpropyl ing and wetting out properties. ether, monomethyl ether of resorcinol, dimethyl 30 As an alternative procedure in accordance with ether of resorcinol, dimethyl ether of catechol, this invention, may also simultaneously conduct trimethyl ether of pyrogallo. the condensation and Sulfonation of a terpene Or Among the terpenes which I have found suit an oxygenated terpene compound and a diary able for the hereinabove described condensation are pinene, dipentene, terpinene, terpinolene, etc. ether or an alkyl-aryl ether. In this case the Among the oxygenated terpene compounds which reaction temperatures will desirably, although may be considered as oxygen-bearing derivatives not necessarily, be in the range mentioned above of the terpenes are such as, for example, terpineol, for the sulfonation reaction alone. As a further borneol, fenchy alcohol, 1,4 terpin, 1,3 terpin, alternative procedure in accordance with this in terpin hydrate, sobrerol, pinol glycol, terpine Ol, vention, I may first sulfonate the diary ether or i4 cineole, 1,8 cineole, beta-pinene glycol, S0 the alkyl-aryl ether and then condense the re brorerythritol, etc. Commercial cuts rich in suitant product with a terpene or an oxygenated terpenes such as gum turpentine, WOOd turpen terpene compound. tine, and crude cuts rich in oxygenated tergene Furthermore, I have found that the above con compounds such as pine oil, for example, may be 45 densation products may, if desired, be further utilized. modified by condensation with an aldehyde, pref Among the substances which are suitable con erably, although not necessarily, an alkyl alde densing agents in the method in accordance with hyde, such as, for example, formaldehyde, acetal this invention are: p-toluene sulfonic acid, Sul dehyde, paraformaldehyde, propylaldehyde, bu furic acid, chlorsulfonic acid, phosphoric acid, tyraldehyde, etc., prior to or subsequent to any hydrochloric acid, aluminum chloride, zine chlo neutralization of the sulfonated condensate. ride, etc. All of the condensations and sulfonations de Among the sulfonating agents suitable in ac Scribed above may also be carried out in the cordance with this invention are chlorsulfonic presence of an inert Solvent, such as, for example, acid, sulfuric acid, sulfur trioxide, oleum, etc. 55 ethylene dichloride, carbon, tetrachloride, trichlo 2 as: 2,245,648 roethane, tetralin, dichloroethyl ether, chloro ered by steam distilling off the excess pinene and form, etc. diphenyl ether. Lightness in color of the products obtained by To prepare a neutralized condensate of the the method in accordance with this invention may character hereinbefore described, 50 grams of the be attained (1) by using terpenes or oxygenated sulfonated pinene-diphenyl ether condensate terpene compounds which have been purified by were made slightly alkaline to methyl orange by steam distillation or by steam distillation in the adding thereto 160 cc. of a 40% aqueous Solution presence of a base such as Sodium hydroxide, of trimethylbenzyl ammonium hydroxide. The potassium hydroxide, etc. (2) by using freshly resulting product was then dried, yielding 73 distilled diaryl or alkyl-aryl ethers (3) by con O grams of a white, somewhat flaky Solid. ducting the reactions in the presence of an inert Eacample V atmosphere such as carbon dioxide or nitrogen. Having now described in a general way the A mixture of 85 parts of diphenyl ether and 150 nature of this invention, will now proceed to a parts of pinene was reacted with 150 parts of more detailed disclosure thereof with reference to 1.01% sulfuric acid at 25° C. to 30° C. The sulfuric various examples, illustrating the practical adap acid was added dropwise over a period of about tation of the invention. All parts shown are one hour, mechanically stirring the reaction mix parts by Weight. ture throughout this time. The so formed Sul Eacample I fonated pinene-phenyl ether condensate was then 350 parts of pinene, steam distilled in the pres 20 recovered by steam distilling off the excess pinene ence of sodium hydroxide, was heated for four and diphenyl ether. hours in an autoclave at 210° C. with 200 parts To prepare a neutralized condensate of the of diphenyl ether in the presence of 5 parts of character hereinbefore described, 50 grans of the p-toluene sulfonic acid. After removal of the ex sulfonated pinene-diphenyl ether condensate Were cess pinene and diphenyl ether by steam distilla made slightly alkaline to methyl orange by adding tion, and washing with water, the yield of Con thereto 55 cc. of triethanolamine. This mixture densate obtained was 399 parts. was placed in a vacuum oven for 8 hours at the 100 parts of the condensate dissolved in 300 end of which time 69 grams of a pale yellow liquid parts of carbon tetrachloride was sulfonated by were obtained. adding 27 parts of chlor-sulfonic acid at 27 C. 30 Eacample VI to 30 C., maintaining the mixture at such ten 127 grams of terpineol and 81 grams of methyl perature for one-half hour, then neutralizing phenyi ether were mixed and cooled to 15° C. To with sodium hydroxide and drying, thus obtaining this mixture 178 grams of 100.9% sulfuric acid 92 parts of the product. were added dropwise over a period of 1/2 hours 3 5 while agitating the mixture throughout the addi Eacample II tion. The temperature of the reaction mixture 350 parts of pinene, steam distilled in the pres was kept between 15 and 25 C. throughout the ence of sodium hydroxide, was heated for four reaction. At the end of the reaction, a solution hours in an autoclave at 210° C. with 200 parts of of 130 grains of Sodium hydroxide in 130 grams of diphenyl ether in the presence of 5 parts of 40 water was slowly added until the resulting mix p-toluene sulfonic acid. After removal of the ture became slightly alkaline. i excess pinene and diphenyl ether by steam distill The product was then vacuum dried at 95 C. lation, and washing with water, the yield of con The solid residue was extracted with absolute densate obtained was 399 parts. ethyl alcohol to separate the insoluble salts from 100 parts of the condensate dissolved in 300 45 the sulfonated condensate, and the alcohol then parts of carbon tetrachloride was sulfonated by evaporated from the extract. 50 grams of prod adding 50 parts of chlor-Sulfonic acid at 27 C. to uct, free from inorganic salts and completely 30° C., maintaining the mixture at such tempera water soluble, was obtained. ture for one-half hour, then neutralizing with Sodium hydroxide, further treating the product Eacample VII so formed with 35 parts of a 40% by weight solu 240 grams of terpin and 137 grams of methyl tion of formaldehyde at 20° C. to 25 C., and phenyl ether were mixed and cooled to 15° C.