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Publication numberUS2856434 A
Publication typeGrant
Publication date14 Oct 1958
Filing date22 Mar 1954
Publication numberUS 2856434 A, US 2856434A, US-A-2856434, US2856434 A, US2856434A
InventorsWarren D. Niederhauser
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
US 2856434 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 0 BENZYL ETHERS 0F ALKYLPHENUXYPOLY- ETHOXYETHANOL Warren D. Niederhauser, Hunting-don Valley, and Edwin J. Smialkowski, Philadelphia, Pa., assignors to Robin & Haas Company, Philadelphia, Pa, a corporation of Delaware No Drawing. Application March 22, 1954 Serial No. 417,939

13 Claims. (Cl. 260-613) This invention relates to low-foaming non-ionic surface-active compositions. It also relates to a process by which these compositions are prepared.

The compounds of the present invention are represented by the formula nw CH2OH2),.O ontotm wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty. The process by which these compounds are prepared comprises reacting a compound of the formula in which R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, with benzyl chloride or bromidein the presence of a strongly basic inorganic neutralizing agent. The use of benzyl chloride is somewhat preferable to the use of benzyl nwomornnon wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, are.

known and available, and usually exhibit surface activity in varying degrees of practical utility. A unit or two of propylene oxide may be "substituted for a similar amount of ethylene oxide without substantially altering the identifying characteristics of the compound. Propylene oxide and ethylene oxide are equivalent to this extent. The formation of a benzyl ether from the abovetype compound results in a product having low-foam detergent properties superior to those of the parent compound.

Although the compounds prepared by the use of benzyl chloride or bromide are considered of the greatest practical importance, satisfactorily-useful compounds may be prepared from substituted benzyl chloride or bromide. The substituents on the benzene ring should be relatively inert to the reaction components of the present invention and may include the chloro, bromo, nitro, or lower alkyl groups. Compounds that have been found to be suitable include a number having alkyl groups, chlorine or bromine atoms, nitro groups, or combinations thereof,

More- 2,856,434 Patented Oct. 14, 1958 attached to a benzene ring as, for example, methylbenzyl chloride, dimethylbenzyl chloride, trimethylbenzyl chloride, ethylbenzyl chloride, ethylmethylbenzyl chloride, chlorobenzyl chloride, bromobenzyl chloride, chloromethylbenzyl chloride, nitrobenzyl chloride, and the like. The corresponding bromides are likewise suitable.

In the formula R 0 ornom)..on

R has been defined as an alkyl group of eight to fifteen carbon atoms. Actually, there may be more than one alkyl substituent on the benzene ring. It is only important that the total number of carbon atoms in all of the alkyl substituents range between eight and fifteen. Suitable for this use are the octyl, nonyl, decyl, dodecyl or pentadecyl groups as single substituents for R. Two

groups may also be substituted for R, as, for example, an octyl and an amyl, a nonyl and an amyl, a decyl and a propyl, a decyl and an amyl, or a dodecyl and a propyl. Even three groups may be substituted for R, as, for example, three amyl substituents. The positions or the alkyl groups on the benzene rings are not indicated because they are not critical. t

The number of ethoxy units employed may be varied,

as desired, within the range of twelve to forty. The

presence of twelve ethoxy units gives the compound a hydrophilic trait sufficient to assure water solubility when the alkyl substituent is an octyl group. The presence of additional ethoxy units tends to increase the water solubility of the present compounds which is particularly desirable as the alkyl substituent approaches the limit of fifteen carbon atoms. Compounds of the subject type exhibit the property of inverse solubility. That is, for

instance, as the temperature of an aqueous 1% solution is increased a point is reached where a turbidity appears. I

This is called the cloud point. As the number of ethoxy units is increased the cloud point gradually rises. instance, the cloud point of the octyl compound having the lowest number of ethoxy units contemplated within this invention, that is, twelve, is less than 2 C. With fifteen ethoxy units the cloud point has risen to 15 C.; with sixteen ethoxy units the cloud point is 18 C.; with seventeen ethoxy units the cloud point is 23 C.;

with twenty ethoxy units the cloud point has increased. -to 39 C.; and with the greatest number of ethoxy units,

forty, the cloud point has reached 52 C.

Of course, in some respects, there is a gradation of chemical and physical properties in considering the gamut of ethoxy units in the compounds. Generally, for instance, the lower members are excellent detergents, while the higher members are, in addition, good emulsifiers. While all of the compounds, regardless of the number of ethoxy units, are excellent detergents with good foam 1 characteristics, the lower members give the best foam results.

In the formation of the alkylphenoxypolyethoxyethan- 01s in the range of twelve to forty ethoxy units, there is sometimes obtained a mixture of compounds having different numbers of ethoxy units. This is known 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.

the suitable agents that may be used are the alkali metals,

such as sodium and potassiums, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide,

For I The choice of a specificpotassium ethoxide; sodium butoxide, sodium carbonate, lithiumhydroxide;-the'alkaliearth--metal-hydroxides;-such as barium hydroxide, calcium hydroxide and strontium hydroxide, and the like. The alkali agent should be present in an amountsomewhat; greaterthanthe molar amount of the alkylphenoxypolyethoxyethauol. "This is desirable to assure the complete --'neutralization of the hydrochloric tor hydrobromic acid formed in thereaction. The exeess agent causes no interference-with the desired result and may-easily be removed at =a-eonvenient later stage.

The reaction will satisfactorily occur in the range of temperatures from about 50 "to 200 C. The preferred range is about 100 to 150, C. "The temperature. of the reaction is t not extremely -critical I and temperatures may be-usrdother-than those mentioned. Howeverfithe best results are obtained -using-thetemperature ranges set forth above.

*The *reactionqis essentially i-cornpleted at the end .of about-"one hour althougha somewha't longer reaction time is usually provided -to *assure maximumresults. *The yieldsconsistently-average 93--to -97'% of the benzylether product-based on-=the weight ofthe alcohol used.

1f desired; the-reactio11 *may -be conducted in the; presence ofa'volatileyinert'organic solvent. Suitableffor1'this use-are benzene,-xylene, toluen e -and the; like. The use of sueh solve'nts isa matter of'choice' because thereaction proceeds satisfactorily without a solvent.

:At the conclusion =of the reaction 'the excess unused reactantsare removedfrom 'the productby'standardprocedures. The-reaction mixture is--washed with-water land -the. wash'water discarded. If*desired, an inert volatile-hydrocarbon solvent such asf-benzene. toluene, or the like, may be used-to' aidintheseparation of the water layer from the product layer. 'This is-not usually necessary and, if--not-'necessary, -would -not beused because su'cha step would add the -problem of removal of the hydrocarbon solvent-from the'product' layer. Unreacted benzyl-chloride or bromide and-formed benzyl alcohol are-preferably removed by vacuum steam distillation. The-product-is finally dried, preferably under-vacuum at any convenient temperature, and filtered.

The-method offorma'tion of'the products of this inven tion is set'forth in the following illustrative examples. Parts by wei'ght are used 'throughout.

.lExample l glntovi'a. fiaslercquipped -with a stirrer aud -azthcrmometer 82tpartssof 0.10 H210 B913 H layer wasisteamastripped to'remove toluene, :benzylzchloride, and benzylyalcohol. The-:productwas dried,'by heatingto;100-C.-at5-20 pressure-and filtered. The yield f thebenzyl ether .of

immtoetumt0it was' 860 pa-rts which= represents 95% aof-thattheoretically possible. The color: of '-the-;.product= was equiv'alent -to ahoute4 .on'ithe Gardner-color: scale (Standards *of 1-933). Therproduct-ahadua. cloudapoint of. 1 5 C.

"analogous manner.

Example 2 There was added to 747 parts of in a flask 50 parts of sodium hydroxide. The temperature was-raised to to-.80 C- to-acceleratedhendissolution-'ofzsodium hydroxide. To the rtiixturefwas added llSzpartsof benzyl chloride "over-a peritaiddfBO-minutes and the temperature of the system was increasedtolIO to C. The mixture wasstirred for. three; hours at which time 200 parts of "water was'added and the temperature raised to the boiling point of thecontents of the flask. The mixture'wasallowed to-settle'and form layers. The aqueous lower layer was discarded and the product upper layer :wassteam stripped to remove benzyl alcohol and benzyl chloride. The product was dried; by heating to 100 C. at 20 mm. pressure; and "filtered. 'Theproduct hadga Gardner'teolor value of about 3 and a :cloud point of about 2 C. The yield was 811 parts (97% 'o'f theoretical) Benzyl bromide "functions in a manner similar to benzyl chloride in this reaction. Metallic sodium or potassium or calcium hydroxide-maybe used as the alkali agent to producesimilan results.

The corresponding dodecyl- -and pentadecyl"alcohols=react to form similar products'in a-waysimilar-tmthe octyl alcohol.


rIQQSImat-ts of 701-par-ts of potassium*-hydrox'ide'was ad'ded. 0verja period of about --3 0-minutes '180-parts of benzyl chloride was added-and the temperature of the-system was, raised to=-l25ato "C. The'mixturewasstirredfor about three hoursandthen-ZOOparts ofwater were added. The temperature of-"the system was raised' to" the-boiling point and then**th e mixture-was allowed tosettle. and formilayers. 'T-The aqueous lowerla-yer was discarded and 'the product upper layer was -steam stripped to removewoiatile components. '1' he product was -drie'd""by .hcatiugdto 100-'- to 05 ---'C. "at 22 mm. pressure anddilteretl.

. product hada Gardner colorwalue'of -"about 4 and -a"cloud point of 23 C. The yield of the benzylether was 1002 parts (96% of theoretical).

The corresponding nonyl and decyl alcohols react similarly to the octyl alcohol.


' To. a .mixtuteQf;1086 parts of discarded. "The upper layer-was steam strippedyand'then drie'dand-filtered. Ayield of "l'096 parts j(93'% o'fftheoretical) --was obtained. The color 'of'the pro'ductwas about' 5on the Gardner scale. It'had a cloudpoint'o'f 39C.

The corresponding Pdecylamyl --alcohol-- works satisfactorily in thisexample.

Example A 60-part portion of sodium methoxide was added to 1966 parts of I To this mixture, 175 parts of benzyl chloride was added over a period of 28 to 30 minutes. The temperature of the system was adjusted to 120 to 135 C. for a period of three hours. Water was added and a separation into layers efiected. The water layer was discarded and the product layer was steam stripped to remove volatile components. The product was dried by he'atingand then filtered. A yield of 1961 parts (95% oftheoreticallwas obtained. The benzyl ether product had a color of 4 to 5 on the Gardner color scale and a cloud point of 52 C.

Sodium or potassium hydroxide produces results similar to those produced by sodium methoxide.

Example 6 There were added to 1540 parts of 100 parts of potassium ethoxide and 200 parts of benzyl bromide. The temperature of the system was raised to 135 to 150 C. and maintained at that level for about two and one-half hours. Water was added to the mixture and the temperature was increased to the boiling point. The mixture was allowed to settle and separate into layers. The aqueous lower layer was discarded and the product upper layer was steam stripped to remove benzyl alcohol and benzyl bromide. The product was dried and filtered. The yield was 1549 parts (95% of theoretical).

Benzyl chloride produces the same result as benzyl bromide. Sodium methoxide and sodium ethoxide per form in the same manner as potassium ethoxide.

Example 7 There was added to a mixture of 910 parts of osnnt emanation and 50 parts of sodium hydroxide 180 parts of benzyl chloride. The benzyl chloride was added at a rate of about 6 parts per minute during which time the tempera ture of the system was raised to 135 to 150 C. The temperature was maintained at this level for about two hours and then water was added to the system. The mixture formed layers and the water layer was removed and discarded. The product layer was steam stripped, dried, and filtered. The benzyl ether product was obtained in the amount of 952 parts (95% of theoretical). The Gardner color value of the product was about 5 and the cloud point was 18 C.

Detergency and foam characteristics were determined on the products obtained from the above examples. All were excellent detergents when tested under dishwashing and laundering conditions. For instance, the octyl product containing 20 ethoxy units in the amount of 10 parts, in conjunction with 90 parts of an alkaline builder which was made up of 60% sodium tripolyphosphate, 20% sodium silicate, and 20% sodium sulfate, gave a 95% detergency rating in a standard mechanical dishwashing test which is markedly superior to known commercial detergents.

The foam characteristics of these compounds at 70 C. were determined under simulated mechanical dishwashing conditions. All were excellent. The following shows the foam results on the octyl compounds:

Foam heights in cm; Compound with 12 ethoxy units 0.0 Compound with 15 ethoxy units 0.0 Compound with 16 ethoxy units 0.0

Compound with 17 ethoxy units 0.0

These results indicated foam characteristics superior to those of known commercial compounds of the corresponding polyethoxy alcohol type which under identical conditions gave foam heights of 9.0 to 11.8 cm. The

wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty.

2. As a composition of matter the compound having the formula C7Hi1 (O CHgCHDuO CHgCuHs 3. As a composition of matter the compound having the formula 0.1119 (0 CHzCHzhaO CHzCaHIi 4. As a composition of matter the compound having the formula ClHn (OCH:CH5)z0O CHmCsHs 5. As a composition of matter the compound having the formula 00H" (OCHgCHDWO CHrC6 5 6. As a composition of matter the compound having the formula 7. A process for the preparation of compounds having the formula wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer from twelve to forty, comprising reacting a benzyl compound from the class consisting of benzyl bromide and benzyl chloride with an alcohol having the formula R (OOH:CHz)..OH

wherein R and n have the same significance as above, in the presence of a strongly basic inorganic neutralizing agent at a temperature of about 50 to 200 C., and then separating the product. i

8. A process as defined in claim 7 wherein R is an octyl group and n is equal to 12.

9. A process as defined in claim 7 wherein R is a nonyl group and n is equal to 15.

10. A process as defined in claim 7 wherein R is an octyl group and n is equal to 20.

11. A process as defined in claim 7 wherein R is a nonyl group and n is equal to 30.

12. A process as defined in claim 7 wherein R is an octyl group and n is equal to 40.

13. A process for the preparation of compounds having the formula wherein R is an alkyl group of eight to fifteen carbon atoms and n is an integer; from: twelve to forty, comprising reacting a benzyl compound. from. the class consisting of bromide and chloride with an alcohol having the formula,

womcmnon wherein R and n have the same significance as" above,

in the presence of'anexcessof zr-,strong-1y-basic inorganic" neutralizing agent at a-temperatureof'a-bout 50 to 200 C., then Washing the reaction mixture with Water, removing the volatile components by distillation, drying by heating up to 100' C; at" about 20 mm. pressure, and obtaining the product as the residue.

References Cited. in thefile of this patent UNITED STATES PATENTS 2,178,831

OTHER REFERENCES Schwartz et al;; Surface Active Agents 1949 pp. 18,,

LUncist'ed et aL; Journal Amer. Oil Chemists Society, vol. 285 (1951), p. 295.


UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,856,434 October 14, 1958 Warren D. Niederhauser et a1.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, lines 34 to 36, Example 3, the formula should appear as shown below instead of as in the patenta nwCHaCH2h1OH column 6, lines 21 to 23, claim 2, the formula should appear as shown below instead of as in the patent CsH1 (0CEnCHg)uOCHQOQH5 lines 41 to 43, claim 6, the formula should appear-as shown below instead of as in the patentmmQwomommo 01110511,

Signed and sealed this 20th day of January 1959.

[SEAL] Attest KARL H. AXLINE, ROBERT C. WATSON, Attesting Oficer. Gammissz'oner of Patents.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2913416 *4 Mar 195517 Nov 1959Rohm & HaasLiquid detergent composition
US3072515 *9 Mar 19598 Jan 1963Diversey CorpMethod and composition for chemically polishing metals
US3082172 *5 Apr 196019 Mar 1963Economics LabDefoaming rinse composition
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US3293191 *29 Oct 196420 Dec 1966Cumberland Chemical CorpEthylene oxide adducts of tertiary acetylenic alcohols
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US3334147 *28 Feb 19621 Aug 1967Economics LabDefoaming and surface active compositions
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US3444242 *4 Mar 196813 May 1969Economics LabSurface active agents
US4518459 *17 Jan 198321 May 1985Economics Laboratory, Inc.Methods of deinking secondary fibers
US5286300 *12 Aug 199215 Feb 1994Man-Gill Chemical CompanyRinse aid and lubricant
US5417808 *1 Feb 199323 May 1995Lion CorporationDeinking composition for flotation and deinking method
US5503768 *31 May 19942 Apr 1996S.T. Chemical Co., Ltd.Halogen scavengers
US5583097 *25 May 199510 Dec 1996Ppg Industries, Inc.Deinking agent of nonionic surfactants
DE2800710A1 *9 Jan 197812 Jul 1979Kuraray CoHigh purity etherified polyoxyalkylene cpds. prepn. - by etherifying polyoxyalkylene which has been treated with hydrogen in presence of hydrogenating catalyst
U.S. Classification568/608, 510/535, 510/506, 510/218, 510/234, 510/356, 510/220
Cooperative ClassificationC10M171/007