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Home , Ether

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 . 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 - 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- sul rivatives thereof in the presence of a suitable fonic 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. 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, , Such as, for The process in accordance with the present in example, , 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, , monium hydroxide, , 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, 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 -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 , 1,4 terpin, 1,3 terpin, alternative procedure in accordance with this in terpin hydrate, sobrerol, pinol glycol, terpine Ol, vention, I may first 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 , 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, , 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 , such as, for example, acid, , trioxide, oleum, etc. 55 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. drying this reaction product. 240 grams of 100.9% sulfuric acid were then added dropwise over a period of one hour, the Eacample III 5 mixture being agitated throughout the addition. 200 parts of a mixture containing 115 parts of The temperature of the reaction mixture was kept pinene, 83 parts of methylphenyl ether and 2 between 15 and 25° C. The resulting mixture parts of p-toluene Sulfonic acid was treated with was then neutralized with 195 grams of sodium 170 parts of 100.9% sulfuric acid at 15° C. to hydroxide dissolved in 220 grams of water. The 20 C., naintaining the mixture at Such tempera material was then Vacuum dried to give a yield ture for One hour. The reaction product was of 385 grams of dry sulfonated condensate. Half then neutralized with sodium hydroxide, sepa of the product was washed with 40 grams of pe rated from inorganic salts by extraction with alco troleum ether to remove ariy unsuifonated con hol and dried, the final product being substantially densate. The washed product was then dried. A free from inorganic salts. yield of 185 grams of this product was obtained. Eacample IY The product was completely soluble in water. A mixture of 85 parts of diphenyl ether and 150 Eacample VIII parts of pinene was reacted with 150 parts of 10.1% 113 grams of pine oil and 57 grams of diphenyl sulfuric acid at 25 C. to 30° C. The sulfuric acid ether were mixed and cooled to 15° C. 135 grams Was added dropwise over a period of about One of 100.9% sulfuric acid were then added drop hour, mechanically stirring the reaction mixture Wise over a period of 1% hours with agitation. throughout this time. The so formed sulfonated The temperature of the reaction, mixture was kept pinene-phenyl ether condensate was then recoy 75 at 15-25 C. during this addition. A solution of 2,245,643 3 97 grams of sodium hydroxide dissolved in 120 2. The process of preparing sulfonic acids of grams of water was then slowly added until the high wetting, cleansing and emulsifying proper mixture cessame slightly alkaline to litmus. The ties which consists in sulfonating a compound product was vacuum dried at 85° C. and then from the group consisting of diaryl and alky-aryl y:ácted with absolute ethyl alcohol to extract 5 ethers and then condensing with an oxygenated the sulfonated condensate from inorganic salts terpene. present. The alcohol was then evaporated from 3. The process of preparing sulfonic acids of the alcohol extract leaving 24 grams of sulfonated high wetting, cleansing and emulsifying proper pine oil-diphenyl ether condensate free of inor ties which consists in condensing an Ogygenated 10 terpene with a compound from the group consist ganic salts, and completely soluble in water. ing of diaryl ethers and alkyl-aryl ethers and Eacample IX Sulfonating the product. 50 grams of terpineol, 65 grams of methyl 4. The process of preparing sulfonic acids of phenyl ether and 2 grams of para-toluene Sull high Wetting, cleansing and emulsifying proper fonic acid were heated together at 210° C. for 5 15 tles which consists in simultaneously condensing hours in an autoclave. The product thus obtained and sulfonating a mixture of an oxygenated ter was steam distillated to remove unreacted volatile pene and a compound from the group consisting materials. The resulting condensate was then of diaryl ethers and alkyl-aryl ethers. water washed upon which a yield of 32 grams of 5. A product from the group consisting of the Condensate Was Obtained. 20 product obtained by the process of claim 1 and The condensate was dissolved with 115 grams the product obtained by neutralizing with a suit of carbon tetrachloride and cooled to 15° C. Then able base the product obtained by the process of 13 grams of chlorosulfonic acid was added drop claim 1 said product being soluble in Water and Wise and with agitation. The mixture was then forming clear solutions therein having high Wet neutralized with 9.5 grams of NaOH in 15 grams 25 ting, emulsifying, and cleansing properties. of Water. The product thus obtained WaS vacuum 6. The process of preparing sulfonic acids of dried, extracted with anhydrous alcohol and the high wetting, cleansing and emulsifying proper alcohol evaporated from the extracted product. ties which consists in condensing an Oxygenated 21 grams of Water Soluble product were obtained, terpene with diphenyl ether and sulfonating the product. Eacample X 30 7. A product from the group consisting of the A mixture of 85 grams of pine oil, 94 grams of product obtained by the process of claim 6 and diphenyl ether, and 5 grams of para-toluene sul the product obtained by neutralizing with a suit fonic acid was heated to 220 C. for 6 hours in able base the product obtained by the process of an autoclave. The resulting liquid was steam. 35 claim 6 said product being soluble in Water and distilled to remove unreacted materials and the forming clear solutions therein having high wet condensate (residue) was water washed. 122 ting, emulsifying, and cleansing properties. grams of condensate was obtained. 8. The process of preparing sulfonic acids of 80 grams of the pine oil-diphenyl ether con high wetting, cleansing and emulsifying proper densate was mixed with 300 grams of carbon 40 ties which consists in condensing an Oxygenated tetrachloride and cooled to 15° C. Then 33 grams terpene with methylphenyl ether and sulfonating of chlorosulfonic acid was added dropWise While the product. the mixture was agitated. The mixture was neu 9. A product from the group consisting of the tralized by slowly adding a solution of 23 grains product obtained by the process of claim 8 and of NaOH in 23 grams of water. The product the product obtained by neutralizing with a Suit thus obtained was vacuum dried, washed with 60 able base the product obtained by the process of grams petroleum ether. The washed product Was claim 8 said product being soluble in water and then dried, whereby 71 grams of product was forming clear solutions therein having high wet obtained. ting, emulsifying, and cleansing properties. The products obtained in accordance with this 50 10. The process of preparing sulfonic acids of invention in the form of the free acids or of high wetting, cleansing and emulsifying proper products obtained by neutralization of the free ties which consists in condensing an oxygenated acids with a suitable base produce clear solutions terpene with a compound from the group consist in water and show excellent wetting, emulsifying ing of diaryl ethers and alkyl-aryl ethers and and cleansing properties. Furthermore, the 55 sulfonating the product. emulsifying action of these products, especially 11. A product from the group consisting of the at low concentrations of emulsifier, is superior product obtained by the process of claim 10 and to that of the prior art emulsifiers. the product obtained by neutralizing with a suit This application is a continuation-in-part of able base the product obtained by the process of my application, Serial. No. 172,859, filled Novem 60 claim 10 said product being soluble in water and ber 4, 1937, now U. S. Patent 2,202,281, disclosing forming clear Solutions therein having high wet but not claiming sulfonated oxygenated terpene ting, emulsifying, and cleansing properties. compound-aryl ether condensates. 12. The process of preparing sulfonic acids of It will be understood that the examples here high wetting, cleansing and emulsifying proper inbefore set forth are illustrative only, and that 65 ties which consists in condensing an oxygenated the invention as broadly described and claimed terpene with diphenyl ether and Sulfonating the 'is in no way limited thereby. product. What I claim and desire to protect by Letters 13. A product from the group consisting of the Patent is: product obtained by the process of claim 12 and 1. The process of preparing Sulfonic acids. Of 70 the product obtained by neutralizing with a suit high wetting, cleansing and enlulsifying proper able base the product obtained by the process of ties which includes the step of condensing an claim 12 said product being soluble in Water and oxygenated terpene with an ether containing an forming clear solutions therein having high wet aryl group and the step of sulfonating the said ting, emulsifying, and cleansing properties. 75 14. The proceSS of preparing Sulfonic acids of ary group. 4. 2,245,843 high wetting, cleansing and emulsifying proper ties which consists in condensing an Oxygenated product obtained by the process of claim 16 and terpene with methylphenyl ether and Sulfonating the product obtained by neutralizing with a suit the product. able base the product obtained by the rocess of 15. A product from the group consisting of the 5 claim 16 said product being soluble in water and product obtained by the process of claim 14 and forming clear Solutions therein having high weis the product obtained by neutralizing with a suit ting, emulsifying, and cleansing properties. able base the product obtained by the process of 18. The process of preparing sulphonic acids of claim 14 said product being soluble in Water and high Wetting, cleansing, and emulsifying proper forming clear Solutions therein having high Wet ties which includes the step of condensing ter ting, emulsifying, and cleansing properties. 0 pineol with an ether containing an aryl group 16. The process of preparing Sulfonic acids of and the step of Sulphonating the Said aryl group. high Wetting, cleansing and emulsifying proper 19. A product from the group consisting of the ties which consists in cohdensing an oxygenated product obtained by the process of claim 18 and terpene with a compound from the group consist the product obtained by neutralizing with a suit ing of diaryl ethers and alkyl-aryl ethers, sul 5 able base the product obtained by the process of fonating and condensing the reaction product claim 18, said product being soluble in Water and With an aldehyde. forming clear solutions therein having high wet 17. A product from the group consisting of the ting, emulsifying, and cleansing properties. JOSEPH. N. BORGLIN.