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Publication numberUS2596093 A
Publication typeGrant
Publication dateMay 13, 1952
Filing dateMar 28, 1950
Priority dateMar 28, 1950
Publication numberUS 2596093 A, US 2596093A, US-A-2596093, US2596093 A, US2596093A
InventorsBenneville Peter L De
Original AssigneeRohm & Haas
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface-active polyglycol ethers
US 2596093 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented May 13, 1952 assumes SURFACE-ACTIVE POLYGLYCOL ETHERS Peter L. de Benneville, Philadelphia, Pa,, assignor to Rohm & Haas Company, Philadelphia, Pa., a

corporation of Delaware No Drawing. Application March 28, 1950,

erial No. 152,520

'7 Claims. (Cl. 260-611) This invention relates to non-ionic capillary active compounds which are useful wetting, dispersing, emulsifying, and cleaning agents. It also relates to a process by which these compounds are prepared.

They are represented by the formula wherein R is an alkyl group of at least six carbon atoms, R and R are hydrogen or the methyl group, Ar is a hydrocarbon group of the benzene or naphthalene series, and n is a number of at least six. The process by which these compounds are prepared comprises reacting a halomethylated alkylated aromatic hydrocarbon with about an equimolar amount of a polyethylene glycol in the presence of an alkali metal hydroxide.

Although long-chained alcohols, phenols, carboxylic acids, non-tertiary amines and other compounds having a reactive hydrogen atom have been reacted with ethylene oxide to yield polyether alcohols, there has heretofore been no practical method for the preparation of polyether alcohols having as a terminal other group a longchained -benzyl naphthylmethyl group. The method by which such compounds are now prepared rests on a novel reaction which permits use of different types of starting material than have hitherto been utilized to provide non-ionic surface-active agents. It also allows some latitude in the choice of the starting materials which provide the hydrophobic portion of the surface-active compounds synthesized therefrom. These compounds differ from previously known phenolic derivatives in avoiding an ether linkage directly to a phenyl ring.

Alkylbenzyl and alkylnaphthylmethyl halides are available from the simple aromatic hydrocarbons, benzene, toluene, xylene, naphthalene, and methylnaphthalene through alkylation followed by haloalkylation. The alkyl group may be obtained from olefins of six or more carbon atoms, alcohols, or alkyl halides. Another method of obtaining an alkyl substituent is through introduction of an acyl group by the Friedel-Crafts reaction followed by reduction. The methods based on use of olefine, alcohol, or alkyl halide are well known. There may, however, be mentioned the method in which hydrocarbon groups can be obtained from petroleum hydrocarbons. For example, kerosene can be chlorinated and the alkyl chlorides obtained condensed with benzene, toluene, xylene, naphthalene, or a methylated naphthalene under the influence of aluminum chloride or the like.

The alkylated aromatic hydrocarbons of particular interest are those having an alkyl group of six to eighteen carbon atoms, and preferably eight to twelve carbon atoms, attached to a hen zene or naphthalene nucleus. The presence of one or two methyl groups on the ring does not interfere With the reactions. In fact, the presence of such groups in many instances seems to improve the relative ease of the reactions hereinvolved. The exact form of the alkyl group is not of importance. It may be straight or branched, primary, secondary, or tertiary. The relative position of alkyl group and methyl group is not critical. Typical alkylated compounds are hexylbenzene, hexyltoluene, hexylnaphthalene, hexyhnethylnaphthalene, (l methylhexyDbenzene, (l-ethylpentyl) benzene, (1,3-dimethyl-1- propylbutyl) benzene, (l. methylhexyl) toluene, (l-ethylpentyl) toluene, (1 methylhexyl) xylene, (l -ethylpentyl) xylene, (l-rnethylhexyl) naphthalene, (l-methylhexyl) -dimethylnaphthalene, (1- methylheptyl) benzene, (1 methylheptyDxylene, (l-methylheptyl) naphthalene, (2 ethylhexyl) toluene, (Z-ethyl-l-methylpentyl)toluene, (3,5,5- trimethylhexyl) benzene, (l,2,4,4-tetramethy1pentyl) toluene octylrnethylnaphthalenes, '(l-methylnonyl) -benzene, l-methylisononyl) naphthalene, decylbenzene, dodecylbenzene, dodecyltoluene, dodecylnaphthalene, tert-dodecylbenzene, tetradecylbenzenes, tetradecyltoluenes, tetradecylxylenes, tetradecylnaphthalenes, hexadecylbenzenes, hexadecylnaphthalenes, octadecylbenzenes, octadecyltoluenes, etc. The alkylated hydrocarbon may be'a single compound or a mixture of isomers or homologues may be used.

The alkylated aromatic hydrocarbon is halomethylated. A CH2 Cl or -CHB rz group is introduced by reacting the hydrocarbon with for,- maldehyde and hydrogen chloride or hydrogen bromide in the presence of a catalyst formed from zinc chloride and a lower monocarboxyliic acid, which permits halomethylation under mild conditions such that fairly complete halomethylation is accomplished without production of resins. While the bromomethyl group i satisface torily introduced and ,it gives the same reaction as the chloromethyl group, the latter is economi cally advantageous.

When a benzene hydrocarbon has an alkyl substituent as large as hexyl, conditions of halomethylation mus-the adopted whichwill ensure monohalomethylation approaching completion. The difficulty of doing so increases somewhat with increasing size of alkyl group present. M groups of six to eight carbon atoms af air amount with of halomethylation is obtained by use of zinc chloride as catalyst. Yet a considerable proportion of hydrocarbon remains in the mixture. The addition of a lower aliphatic monocarboxylic acid, such as formic, acetic, chloroacetic, or propionic, brings about a remarkable improvement in the action of the zinc chloride. Acid anhydride can be used in place or of in admixture with the acid. This improvement is probably due to the formation of a complex.

A mixture of one mole of zinc chloride with 1.5 to '8 moles of an aliphatic monocarboxylic acid of not over three carbon atoms is most effective. Under preferred conditions when the alkyl group contains at least ten to twelve carbon atoms a mole ratio of 0.75 to 2.5 parts of zinc chloride per mole part of alkylated aromatic hydrocarbon is used. This ratio may be reduced as the size of the alkyl group diminishes. V

For one mole of alkylbenzene, alkyltoluene, 'alkylxylene, or alkylated naphthalene, one to 2.5 moles of formaldehyde are used. The formaldehyde may be supplied from a revertible polymer. Anhydrous hydrogen chloride or bromide is passed into the reaction mixture. At reaction temperatures of 50 to 100 C. under conditions described, a halcmethyl group is introduced without formation of resinous material. In place of formaldehyde polymer and hydrogen halide there may be used a, halomethyl ether with good results.

Further details of the preparation of halomethylated alkylated aromatic compounds are given in the following illustrative examples.

Example 1 Hexylbenzene, prepared by the alkylation of benzene with propylene dimer, was mixed in an amount of 60 parts byweight with 25 parts of zinc chloride and 25 parts of acetic acid and heated to 50 C. Thereto over a period of an hour 40 parts of dichloromethyl ether was added with stirring. The reaction mixture was stirred and held at 55 C. to 60 C. for an hour. It was then Example 2 i Commercial 3-heptanol was dehydrated at 400 C. on an alumina catalyst and the heptene therefrom redistilled. A mixture was made with 125 parts by weight of this olefine, 198 parts of benzene, and 196 parts of sulfuric acid cooled to 5 C. The mixture was stirred for three hours, allowed to form layers, and separated. The or- 'ganic layer was washed with water and a small amount of a soda ash solution, dried, and distilled under reduced pressure to yield 167 parts of heptylbenzene.

A mixture was made from 160 parts of this product, 90 parts of anhydrous zinc chloride, and 138 parts of glacial acetic acid. 'Thereto 106 parts of dichloromethyl ether were added with stirring while the temperature of the reaction mixture was kept at 60 C. The reaction mixture was stirred for five hours while this temperature was maintained. The mixture was cooled, allowed to form layers, and separated. The product layer was washed, dried, and fractionally distilled. Pure heptylbenzyl chloride was collected at 127-132 C./0.2 mm. a

Example 3 A mixture of 95 parts by weight of octylbenzene (chiefly 2-octylbenzene with some 3-octylbenzene), parts of paraformaldehyde, 54 parts of anhydrous zinc chloride, and 120 parts of glacial acetic acid was stirred at C. while hydrogen chloride was passed in for two hours at a fairly rapid rate. The reaction mixture was allowed to stratify and the upper layer was taken, washed with hot water, with a 10% sodium bicarbonate solution, and with hot water, dried over sodium sulfate and distilled. The forerun of 30 parts consisted of octylbenzene. There Was then obtained at 119-121 C./1 mm. '71 parts of octyl- V benzyl chloride.

Example 4 V heated at 70 C. for four hours in all. Layers I acid and distilled.

were allowed to form and were separated. The upper layer was washed with hot water, with 10% sodium bicarbonate solution, and with water. It was dried over sodium sulfate and distilled. At l55-174 C./ 2 mm. there was obtained a fraction corresponding in composition to octylbenzyl bromide. It contained by analysis 28.8% of bromine. Theory for this product is 28.3%.

Example 5 To a mixture of 184 parts of toluene and 103 parts of sulfuric acid there was added 112 parts of octene while the mixture was stirred and held at 5-13 C. The octene had been prepared by dehydration of capryl alcohol on an alumina catalyst. (Cf. Komarewsky, Ulick, and Murray, J. Am. Chem. Soc. 67, 557 (1945).) The reaction mixture was stirred for three hours at room temperature, and the product layer was separate'd. It was washed twice with concentrated sulfuric The fraction -.taken at 93-95 C./0.3 mm. corresponded in composition to sec.octylmethylbenzene.

To a mixture of 81 parts of this product, 47.5 parts of anhydrous zinc chloride, and 65 parts of glacial acetic acid there was added 46 parts of dichloromethyl ether while the mixture was stirred and held at 50-60 C. for an hour. It was stirred at 70-75 C. for four hours and allowed to form layers. The upper layer was separated, washed with water and sodium bicar bonate solution, and distilled. The fraction taken at 130150 C./0.3 mm. amounted to 43.8 parts and corresponded in composition to methyloctylbenzyl chloride.

= Example 6 To a mixture of 70 parts of 2-ethylhexylbenzene (prepared according to the method of Sulzbacher and Bergmann, J. Org. Chem. 13, 303 (1948)), 50.3 parts of anhydrous zinc chloride, and 60 parts of glacial acetic acid there was added with stirring 42.5 parts of dichloromethyl ether over the course of an hour, while, the reaction mixture was maintained at 60 C. Stirring was continued for another two hours with the temperature held at 60 C. Layers were then allowed to form and separated. The product layer was washed with sodium bicarbonate solution and distilled at -125 C.'/0.0'7 mm. The

hexylbenzyl chloride.

5 Example To: a mixture of." 138. parts by weight of. toluene and 902 parts: of." anhydrous. hydrogen fluoride,

cqnsistedg essentially of octyltoluenesz A. mixture; was; made in the reactionv vessel equippedwith-ai stirrerrof; 32 parts; of octyltolu-- one. 2.5,.parts; of. anhydrous zinc chloride, and.60 partsiof. lacial, acetic. acid. With the temperature kept at.50' to. 60 C. there, was added thereto parts of dichloromethyl ether. The temperature. of; the mixture; was. then raised to 90 C. for three hours. then separated into layers. The product layer was washed with water, with a 5% sodium bicarbonate solution, and' again with water. Upon disillation. a. fraction was obtained at 133- 148 C./0.3 mm. which corresponded, in composition to. 2 Zmethyl-5"-octylbenzyl chloride.

Example; 8.

(a-l Commercial diisobutyl" carbinol The vapors were taken offand condensed; Therefrom nonene was separated and distilled at 72-75 C./100 mm. The product, containing. by analysis 85.7% of carbon and 14.3% of hydrogen, was 2,6-dimethyl-3-heptene, for

which. the, theoretical content of carbon is. 85.8%,

To a mixture.- of 80 parts of nonylbenzene,

40. parts. of zinc chloride, and 59 parts of glacial acetic: acid there: was added at room temperature parts of dichloromethyl ether. The mixture was stirred and heated at 70 C. for three hours. It was then allowed to stand and form layers. The upper layer was separated, washedwith hot water, and with sodium bicar- Donate" solution, dried over sodium sulfate, and distilled. The fraction distilling at 141--142 6.72 mm; wasnonylbenzyl' chloride.

(b) A portion of 3l5 ,5-trimethylhexyl alcohol wasdehydrated as in Example strand 1-25-parts of'the-nonenes therefrom reacted with 200 parts of'xy-lene and 125 parts of sulfuric acid at about 0 C. for' four hours. The reaction mixture was allowed to stand. Layersformed and were separated; The organic layer was washed, dried, and distilled at low pressure. One hundred parts of the main fraction was mixed with parts of" zinc chloride and 7'0- parts of glacial acetic acid;

The reaction mixture. was

was. dripped slowly'oyer, a bed of alumina at. 400 C.

Th'ereto. was added 50 parts of dichlbrm= methyl. ether. The. reaction mixture. wa'sfgradiuallyr warmed to. about; C... and stirred, for

fourhours. The mixturewas allowed to stand. It; formed; layers; which were separated. The

organic layer' was washedwith water, sodium. bi.--

carbonate solution and again with water, and: dried over calciumsulfate. The product. obtained'. gave an. analysis which corresponded closely to that for nonyldimethylbenzyl. chloride.

Example-.9.

(a) The procedur of Example 81) was applied to naphthalene in place of xylene. There; was obtained nonylnaphthylmethyl. chloride; of good purity.

(ibl) A mixturewas made from 100 partsor propylene dimer, 150 parts of; dimcthylnaphthalene, and 150 parts of sulfuric acid, which had been chilled to about. 0 C. The mixture was stirred at 0-5 C. for two hours and then for two hours withoutcooling. The-reaction mixture: was left standing until layers formedi They were separated. The organic layer was 7 Washed with water, with soda ash solution; and l with water again, was dried over calcium sulfate, and heated'under low pressure to remove: unreacted starting material. The product re maining' had the. correct composition for hexyls dimethylnaphthalenei A mixture was made from 120" parts of this:

product, 50 parts. of zinc chloride, 75 parts: of acetic. acid, 15 parts of acetic anhydride, and 25: parts: of paraformaldehyd'e. Hydrogen chloride.

was. passed into the mixturewhile-lt was: stirred.

' Reaction beganand carried the temperaturev to about C., where it was controlled by rate of addition of hydrogen chloride and by cooling. After. three hours the mixture was left: standing. Layers formed and were separated. The upper layer was washed with water, with 10% sodiunr bicarbonate solution, and with water; Itwas. dried over calcium sulfate and heated under-low= pressure. The product was: essentially hexyldimethylnaphthylmethyl chloride.

(c) There were mixed 156 parts of a-crude methylnaphthalene and 156 parts of sulfuric acid; both of, which had been chilled to 0" C; The mixture Was stirred and 212 parts of propylene tetramer was slowly added, maintaining the temperature below ZOFC; The reaction mix-'- ture was stirred for three hours at roomtemperature and the organic layer, was then separated and distilled. There was thus obtained 122 parts. of dodeoylmethylnaphthalene boiling over' the A mixturezof' 155, parts, of this: product; 75*. parts of zinc chloride, and parts of acetic acid was stirred and theretowasjadded partsof' chloromethyl etherover a period; of an hour. with the temperature at" 70 C. The temperature was maintained at" this level and stirring was continued for three hours. The layers were separated as inprevious examples and dodecyle methylnaphthylmethyl chloride obtained as a residue.

(dl Toa mixture of 96' partsof naphthalene and 60 parts" of 96% sulfuric acld cooled below 10 C. there was addedover a periodo'fiomim' utes 101 parts of propylene polymer which averaged-four propylene units. The reaction mix ture was stirred for three hours. Layers were allowed to form and were separated. The or ganiclayer' was treated with alittlelime and distilled; After aforerun of naphthalene, there was obtained a darlt =coloredoil distilling at 263 C./ mm. and amounting to 108 parts by weight. This oil was redistilled, a fraction of 83 parts being taken at 185-225 C./3 'mm. which corresponded closely in composition to dodecylnaphthalene. The molecular weight determined ebullioscopically was 305 (theory, 296).

There were mixed 65 parts of this product, 13.5 parts of paraformaldehyde, 30 parts of anhydrous zinc chloride, and 100 parts of glacial acetic acid. Into this mixture at 5070 C. hydrogen chloride was passed for five hours. Layers were formed and separated. The upper layer was washed with water'and with dilute sodium bicarbonate solution. It was stripped under low pressure to yield 63 parts of a light brown, viscous oil which was essentially dodecylnaphthylmethyl chloride. It contained by analysis 108% of chlorine (theory, 10.4%).

Example 1 0 To a mixture of 312 parts of benzene and 180 parts of sulfuric acid was added dropwise at 10-20 C. 281 parts of decene, which was freshly prepared by dehydration of n-decanol on alumina. vThe mixture was stirred for five hours at room temperature. It was then allowed to form layers. The upper layer was separated, washed with concentrated sulfuric acid twice, and distilled. The fraction distilling at 115-127 C./ 1.3 mm. was identified as sec.-decylbenzene.

A mixture of 54.5 parts of this sec.-decylbenzene, 27.3 parts of zinc chloride, and 60 parts of glacial acetic acid was stirred and heated to 70-75 C. while 28.8 parts of dichloromethyl ether was slowly added. Stirring was continued at '70-80 C. for live hours. Layers were allowed to form. The upper layer was separated, washed with water and sodium bicarbonate solution, dried, and distilled. At 155-1'75 C./1.8 mm. there was obtained a fraction of 30 parts which corresponded in composition to sec.-decylbenzyl chloride.

Example 11 Dodecyltoluene was prepared by mixing 344 parts of toluene and 294 parts of concentrated sulfuric acid and, while the mixture was stirred and the temperature maintained below 10 0., dodecylene was slowly added. The dodecylene used was a propylene tetramer. After 506 parts of dodecylene were added, the mixture was allowed to come to room temperature and stirring was continued for 24 hours. After separation from the acid layer, the product was washed with concentrated sulfuric acid and distilled in vacuo. Five hundred fifty-five parts of a colorless liquid boiling at 110-160 C. at 1.2-2.2 mm. of mercury was obtained.

A mixture of 450 parts of dodecyltoluene with 105 parts of formaldehyde, 1'75 parts of anhydrous zinc chloride, and 250 parts of glacial acetic acid was stirred at 60-70 C. while hydrogen chloride was passed in rapidly for two hours. Absorption was rapid and the reaction was accompanied by a rise of temperature. The lower catalyst layer was drained off and the product washed with water, 10% sodium carbonate solution, and again with water, then dried in vacuo on asteam-bath. Four hundred ninety parts of a yellow liquid having a chlorine content of 11.2% was obtained. The theoretical chlorine content of dodecylmethylbenzyl chloride is 11.5%. This material distills almost completely at 145-185 C. at 0.5-1 mm. of mercury. It may, however, be usedwithout further purification.

Example 12 To a mixture of 156 parts of benzene and parts of anhydrous hydrofluoric acid at 0-5 C. was added 252 parts of octadecylene at such a rate that the temperature did not exceed 10 .C. The mixture was then stirred for three and onehalf hours at 5-10 C. and after it had stood overnight at room temperature the mixture was poured on ice, washed with water, then with 10% sodium bicarbonate and water, dried, and distilled. The product was collected between 195 and 210 C. at 1.5-2 mm. mercury, amounting to 225 parts. 7 7

To a mixture of 30 parts of octadecylbenzene, 35 parts of anhydrous zinc chloride and 80 parts of glacial acetic acid was added 16 parts of bischloromethyl ether dropwise at 55 C. The mixture was then stirred for two and one-half hours, allowed to stand overnight and the upper product layer separated, dissolved in benzene and washed with water, 10% sodium bicarbonate and water, and dried over anhydrous calcium chloride. The benzene was stripped to yield 32 parts of a straw-colored liquid containing 9.02% chlorine (theory, 9.37%). This was essentially octadecylbenzyl chloride.

Example 13 Hydrogen chloride was passed into a mixture of 104 parts of dodecyltoluene, 24 parts of paraformaldehyde, 53.3 parts of zinc chloride and 59.2 parts of propionic acid for two hours at 70 C. The reaction product was worked up as in the preceding example. One hundred eighteen parts of methyldodecylbenzyl chloride was obtained.

Example 14 To a mixture of 138 parts of toluene and parts of sulfuric acid at about 0 C. there was slowly added with stirring 196 parts of an olefine fraction which contained olefines from C12 to C15 and averaged C14. The mixture was stirred at 0-10 C. for three hours and then separated. After the organic layer had been washed with water and soda ash solution, it was dried and distilled. A fraction obtained between 120 and C. at 2 to 0.5 mmrconsisted of alkylated For the preparation of alkylbenzenes from relatively inexpensive materials kerosene .or close-cut naphthas may be taken. For instance, an aliphatic type distillate having a distillation range of to 250 C. and having an average molecular weight of. about 190 was chlorinated until one equivalent of chlorine was taken up per average molecular unit. The alkylchlorides thus formed were reacted with toluene in the presence of 10% of its weight of aluminum chlo.- ride. 1 The resulting alkyltoluenes were stripped free of reactants and distilled'at low pressures fro'm'100-l60 C./2-0.5 mm.

- A portion of the distillate in an amount of 75 parts was mixed with 12 parts of paraformaldehycle, 30 parts of zinc chloride, .30 parts of acetic acid, and 30 parts of acetic anhydride. The mixture was heated to about 60 C. and hydrogen chloride was passed in. The temperature increased to about 85 C. After three hours the mixture was cooled. Layers formed and were separated. The organic layer was washed with water, with sodium bicarbonate solution and again with water. The product was dried over calcium sulfate.

Polyethylene glycols, the second type of reactant needed in the process of this invention, are well known. They can be prepared from ethylene oxide over a wide range of molecular sizes. While it may happen that a polyglycol preparation which has an apparent molecular weight of 550, 600, 800, 1200, 1500, 1800, or the like may in fact be a mixture of glycols, this does not alter the reaction or yield compounds which are any less useful because of utilization of a mixture. The polyethylene glycol should supply a chain of at least six --OC2H4- units and enough such units to give to the final product dispersibility or solubility in water. There is no fixed upper limit to the number of such units which may be present in polyethyleneglycol or final product. The properties gradually change as more and more such units are used, but a practical upper limit is about forty.

A polyethylene glycol, HcoomcHn nOII, where n has a value of about six to forty, is reacted with an alkylated benzyl or naphthylmethyl halide in about an equal molar amount in the presence of about an equal molar amount of an alkali metal hydroxide. Theoretically, the polyethylene glycol, halide, and hydroxide react in equimolecular proportions, but strict adherence to this proportion is not absolutely essential as the presence of a little of the bisalkylbenzyl polyether derivative, formed when an excess of halide is used, does not lessen the utility of the product.

Excess of the hydroxide gives no difiiculty.

The reaction is carried out by heating the mixture of polyethylene glycol, hydoxide, and halide between 80 and 150 C. The reaction is usually complete in one to five hours. The reaction mixture can then be cooled and diluted with a volatile organic solvent such as toluene, petroleum ether, isopropanol, or the like. Salt formed in the reaction can then be removed by filtering. It is usually preferred to effect the separation of salt, although it is not essential. Free halomethylated alkyl aromatic hydrocarbon may be removed by dissolving the reaction mixture in an aqueous medium and extracting th solution with a waterimmiscible organic solvent.

There follow examples of typical preparations of compounds of this invention.

Example 16 There were mixed 4.4 parts by weight of sodium hydroxide and 30 parts of a polyethylene glycol having an average molecular weight of about 300 and containing, therefor, about six -OC2H4- units. The mixture was heated to 80 C. and 21 parts of hexylbenzyl chloride was slowly added. The mixture was stirred and heated for four hours with the temperature carried up to 140 0., cooled, :andextended with toluene. The solution was filtered and the filtrate was evaporated to leave a straw-colored oil. This has the composition CeH13CsH4CI-I2(OCH2CH2)nOH where n has a value of six or a little more on average. The product is-water-soluble and surface-active. Its

10 solutions have low surface and interfacial tensions.

Example 17 A mixture of 4.4 parts of sodium hydroxide and 36 parts of polyethylene glycol having an appar ent molecular weight of 300 was heated at C. and 26 parts of hexylnaphthylmethyl chloride slowly added thereto. Stirring was continued at temperatures gradually increased to C. for a period of four hours. The reaction mixture was cooled, diluted with toluene, and filtered. The filtrate was evaporated to leave a yellow oil. This product Was water-soluble and gave solutions of low surface tension. It dispersed carbon black and other fine particled solids.

Emample18 A mixture of 40 parts of polyethylene glycol having a molecular weight of about 400 and 6.4 parts of potassium hydroxide was heated to 90 C. and thereto was slowly added with good stirring 28 parts of octylmethylbenzyl chloride. After addition was complete, the reaction mixture was stirred and heated to C. over the course of three hours. The reaction mixture was cooled, diluted with toluene, and filtered. The solvent was evaporated to leave an amber oil, which was water-soluble and surface-active, having wetting, emulsifying, and dispersing actions.

Example 19 A mixture of 50 parts of a polyethylene glycol having a molecular weightpf 500 and 8.4 parts of potassium hydroxide was heated to 90 C. and 24 parts of an octylbenzyl chloride was slowly added. The reaction mixture was stirred and heated up to 150 C. for three hours. It was cooled, diluted with toluene, and filtered. The filtrate was evaporated to yield a light brown oil, which was water-soluble. Its solutions were capillary active. A 0.5% solutionhad a surface tension of 30.5 dynes/cm, for example, and an interfacial tension against a white mineral oil of 4.5 dynes/cm. The composition of this product was C8Hl'IC6H4CH2(OCH2CH2)110E. It was found an efiective detergent.

-.ram ple 20 A mixture of 50 parts of a polyethylene glycol having a molecular weight of 500 and 8.4 parts of potassium hydroxide was heated to 90 C. Thereto was slowly added 28.5 parts of octylbenzyl bromide. Th reaction mixture was stirred and heated to 150 C. .forthree hours. It was then cooled, extended with toluene, and. liltered. The filtrate ,was evaporated to yield a light brown oil, which was soluble in water and had properties almostidentical with thoseof the product of Example A mixture of 60 partsof a polyethyleneglycol having an apparent molecular weightof 6 0,0, 80 parts of toluene, and 5.5 parts of potassium hydroxide was heated on a steam-bath and thereto over a one hour period 26 parts of nonylbenzyl chloride was added. Heating of the mixture was continued for 3.5.hours and the mixture was. filtered to remove the salt. The toluene was dis.- tilled chi and the resulting oil was dissolved in equal parts of water and methanol. This .solution was twice extracted with 80 parts of .heptane. The solution was then stripped of solvents. A yield of 69 partsof an oil was obtained. It had 11 the composition C9Hl9C6H4CH2(OC2H4) nOI-I. Its solutions were capillary active. The wetting times of canvas patches were determined as follows: At 0.5% of the product 25.9 seconds, at 0.2% '73 seconds, and at 0.1% 132 seconds. The solutions had fairly good foaming power. The.

product was a dispersing and emulsifying agent and had good cleaning power.

' Example 22 By the method of Example 21 there were mixed 60 parts of the polyethylene glycol with a moleular weight of 600, 80 parts of toluene, and 5.6 parts of potassium hydroxide. Thereto parts of monylnaphthylmethyl chloride was added and reacted therewith. Purification was accomplished in the same way. The product obtained had the composition Example 23 A mixture of parts of a polyethylene glycol having a molecular weight of 4.00 and 5.8 parts of potassium hydroxide was heated at 90-100 C. and 25.7 parts of nonylbenzyl chloride was slowly added. The reaction mixture was then heated for four hours with the temperature carried to 140 C. Purification was accomplished by solution in isopropanol followed by filtration. The filtrate was extended with water and the solution extracted with toluene. A yield was obtained of 57 parts of where n averages 8.7. The product was watersoluble and gave surface-active solutions. A 0.5% solution gave a wetting time by the canvas patch method of 16 seconds.

Example 24 A mixture of 80 parts of a polyethylene glycol having a molecular weight of about 800 and 6 parts of potassium hydroxide was heated to about 100 C. while 31 parts of dodecylmethylbenzyl chloride was slowly added. Heating was continued for four hours while the temperature was raised to 140 C. The reaction product was purified by filtration of its solution in toluene and extraction with heptane of a solution in aqueous isopropanol. The product was a viscous oil, which was water-soluble. It had the composition C12H25 (CH3) CeHsCI-Iz (OCHzCHz) OH when n had an average value of almost 18. The water solutions were capillary active as shown by low surface and interfacial. tensions. The product had emulsifying, dispersing, and cleansing properties.

Example 25 V A mixture of 125 parts of a polyethylene glycol having a molecular weight of 1250 and 6 parts of potassium hydroxide was reacted at -100 C. with 32 parts of tetradecylbenzyl chloride. The reaction mixture was heated for five hours up to 140 C. and purified as in the previous examples. The product obtained had the composition where n had a value of 28. I This product was water-soluble and had emulsifying and dispersing actions.

Example 26 A mixture of 90 parts of a polyethylene glycol of a molecular weight of about 1800 and 2 parts of sodium hydroxide was heated to about C. and 19 parts of octadecylbenzyl chloride slowly added. The reaction was continued by heating for five hours at -150 C. The reaction product was purified as in the previous example and, when it was cooled, it became waxy. It dispersed in water to give solutions having reduced surface tension. It had emulsifying and dispersing actions. The composition of this product corresponds to the formula madam. (OCH2CH2) ..on

where a has a value of about 40.

Example 27 A mixture of 151 parts of'a polyethylene glycol having a molecular weight in excess of 1500 and 6.4 parts of potassium hydroxide was heated to 90 C. and 36 parts of dodecylmethylnaphthyl methyl chloride slowly added. The reaction was continued at IMP- C. for four hours. The product was purified by removal of salt through filtration of its toluene solution and extraction of a solution. in 50% aqueous isopropanol with the aid of heptane. The product obtained as a residue on evaporation of solvents was an un ctuous waxy material which was .dispersible in water. Its solutions were capillary active. It had dispersing and emulsifying actions. This product contained about 34 ethoxy groups.

Example 28 hours with the temperature being carried to 150"- C. The product was purified as in previous examples. A viscous oil was obtained which was water-soluble and capillary active. Its composition corresponds to the formula where n has a value of about 23. This product had good dispersing, emulsifying, and cleansing properties.

The compounds of this invention, obtained by the reaction of an alkylbenzyl or alkylnaphthylmethyl halide and polyethylene glycol in the presence of an alkali metal hydroxide, are useful surface-active materials of the non-ionic type. They supply effective dispersing and emulsifying actions and can be used in conjunction with either anionic or cationic surfaceactive agents. They may also be used in conjunction with alkaline detergents, supplying wetting, dispersing, and emulsifying actions. An example of an efiicient cleaning and sanitizing which comprises reacting at 80 to 150 C. about one mole of a polyglycol or the formula H(OCH2CH2) "OH and about one mole of a halide of the formula R R R ArCHzX in the presence of about one mole of an alkali metal hydroxide, R being an alkyl group of 6 to 18 carbon atoms, R and R being members of the class consisting of hydrogen and the methyl group, Ar being a member of the class consisting of benzene and naphthalene groups, n being a number from 6 to 40 and at least of sufficient size to ensure the dispersibility of the compound in water, and X being a halogen from the class consisting of chlorine and bromine.

2. A process for preparing a compound of the formula R CeI-I4CH2 (OCHzCHz) 11011 which comprises reacting at 80 to 150 C. about one mole of a polyglycol of the formula I-I(OCH2CH2) "OH and about one mole of a halide of the formula R C6H4CI-IzC1 in the presence of about one mole of an alkali metal hydroxide, R being an alkyl group of 8 to 12 carbon atoms and n being a number from 6 to 40 and at least of sufficient size to ensure the dispersibility of the compound in water.

3. A process of claim 2 in which R is an octyl group.

4. A process of claim 2 in which R is an nonyl group.

5. A process for preparing a compound of the formula R (CH3) CsH3CH2(OCH2CH2) "OI-I which comprises reacting at 80 to 150 C. about one mole of a polyglycol of the formula H(OCH2CH2) "OH and about one mole of a halide of the formula R (CH3) C'sHaCHzCl in the presence of about one mole of an alkali metal hydroxide, R being an alkyl group of 8 to 12 carbon atoms and n being a number from 6 to 40 and at least of suflicient size to ensure the dispersibility of the compound in water.

6. The process of claim 5 in which R is a nonyl group.

7. The process of claim 5 in which R is a dodecyl group.

PETER L. DE BENNEVILLE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1 2,209,911 Bruson et al. July 20, 1940 2,213,477 Steindorff et al. Sept. 3, 1940 2,459,526 Heckenbleikner Jan. 18, 1949 FOREIGN PATENTS Number Country Date 202,352 Germany Oct. 3, 1908 422,948 Germany Dec. 16, 1925 655,871 France Dec. 22, 1928

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2784140 *Nov 3, 1954Mar 5, 1957Rohm & HaasEmulsifier composition and insecticidal emulsions obtained therewith
US2923739 *Mar 17, 1958Feb 2, 1960Universal Oil Prod CoOxyalkylated omega-methylol-substituted alkylacetophenones
US3128314 *May 8, 1958Apr 7, 1964Petrolite CorpOxyalkylated condensates
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US3379708 *Nov 23, 1964Apr 23, 1968Phillips Petroleum CoEsters of tall oil pitch and polyoxyethylene compounds and their use as drilling fluid additives
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Classifications
U.S. Classification568/607, 585/456, 510/506, 510/535
International ClassificationC08G65/34
Cooperative ClassificationC08G65/34
European ClassificationC08G65/34