US2219050A - Wetting agent and detergent aid - Google Patents

Wetting agent and detergent aid Download PDF

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US2219050A
US2219050A US248900A US24890038A US2219050A US 2219050 A US2219050 A US 2219050A US 248900 A US248900 A US 248900A US 24890038 A US24890038 A US 24890038A US 2219050 A US2219050 A US 2219050A
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wetting
alkyl
phosphoric acid
carbon atoms
ester
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US248900A
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Louis A Mikeska
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Standard Oil Development Co
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Standard Oil Development Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • This invention relates to improved detergent aids and wetting agents. More particularly, it relates to high wetting power salts of phosphoric acid partially esterifled by hydroxy aromatic compounds containing suitable hydrocarbon substituent groups.
  • wetting agent substances which improve spreading of surface coatings, increase spreading and penetrating power of liquids, such as aqueous solutions and oils, and which may act as detergent aids, emulsifying agents, and dispersing agents, all of these actions dependingsomewhat upon changes of interfacial and surface tension.
  • the wetting power of these agents can be evaluated by simple and rapid methods which measure the relative time taken for an aqueous solution of an agent to thoroughly penetrate, under prescribed conditions, a fabric or skein of flbres having a prescribed composition, form, and size. Although these methods more particularly compare the penetrating and detergent aiding action of the agents, they indicate, in general, the capacities of the agents to perform other wetting functions.
  • wetting agents and detergent aids have been prepared by neutralizing acid esters formed by reacting gaseous olefins with phenol in the presence of sulfuric acid, it has been found that salts of phosphoric acid partially esterifled by phenolic compounds are properly constltuted for high wetting power when the phenolic compounds contain suitable hydrocarbon constituents prior to esteriflcation with phosphoric acid or its condensible derivatives. While the salts of sulfuric acid partially esterifled. by alkylated phenols can be prepared by having the alkylation step occur during the esteriflcation, there are applications in which such salts are less desirable due to corrosiveness tendencies of their hydrolysis products.
  • An object of this invention is'to producefrom phenolic compounds and phosphoric acid or its condensible derivatives, wetting agents and detergent aids which have high wetting and -deter-- gent effectiveness with restricted hydrolysis.
  • Another object of this invention is to prepare acid esters of phosphoric acid which on neutralization produce stable salts having wetting pow- 5 ers comparable to the most effective ester salt derivatives of sulfuric acid, and in some applications, even greater wetting powers, yet without corrosive tendencies of the sulfuric acid ester salts.
  • a further object of this invention is to pro- Application December 31, 1938, Serial'No. 248,900
  • Suitable alkyl phenols to be used as starting materials may, be obtained by alleviation of lower phenols present in coal tar. fractions or tar acids. Petroleum 1! phenols, per se, are very suitable. But, the phenolic compounds are preferably selected when they have alkyl side chains, either simple straight chain or cyclic, containing sufficient saturated carbon atoms to make'a total of about 0 5 to carbon atoms per molecule of acid ester formed in the esterification.
  • the wetting power decreases, while the detergent powerincreases, with increase in the size of the hydrocarbon substituent.
  • 5 the phenolic compounds having hydrocarbon side groups containing about 3 to 10 saturated carbon atoms per molecule are preferred for producing'di-ester salts.
  • the diester salt should contain 5 to 20 alkyl or cycloalkyl carbon atoms per molecule, that is, it is formed from the reaction of allgyl phenols having an average-of 2.5 to 10 alkyl carbon atoms per molecule. In forming the mono-ester, it is best to esterify a phenol having at least 5 carbon atoms in the hydrocarbon side chain.
  • Synthetic alkyl phenols' may be prepared by any of the known methods of alkylation. Suitable methods for their preparation are disclosed in U. S. Patent 1,948,287-of'February 20, 1934, o to Hyym E. Buc and Ruben Schuler, and U. S. Patent 1,954,985 of April 17, 1934, to Hyym E. Buc. These patents describe methods for alkylating phenolic compounds such as phenol, cresols, etc., with olefinic hydrocarbons having 5 more than 2 carbon atoms'per molecule and similar reactants. They indicate reactions of alkylating compounds with the phenolic compounds in the presence of strong sulfuric acid at controlled temperatures. The allnvl substltuents formed may be normal, iso, secondary, or tertiary.
  • the phenolic compounds may contain more than one alkyl substituent and other aliphatic or cycloaliphatic hydrocarbon substituents which supply the proper number of saturated carbon atoms which may be designated as paraflinic carbon atoms.
  • Petroleum phenols which to some extent simulate phenolic compounds containing a polymethylene or cycloalkyl side group, according to their hydrogen and carbon analyses, have been found to be as satisfactory as alkyl phenols of corresponding or even higher molecular weights.
  • Polyalkyl phenols may be obtained by alkylating lower phenols with suitable alkylating agents such as alcohols, olefins, alkyl sulfates, and alkyl halides, and these alkylating agents may be obtained from cracked petroleum hydrocarbon products.
  • suitable alkylating agents such as alcohols, olefins, alkyl sulfates, and alkyl halides, and these alkylating agents may be obtained from cracked petroleum hydrocarbon products.
  • R represents 1 or several alkyl substituents containing an average total of 5 to 20 saturated carbon atoms
  • Ar represents an aromatic nucleus
  • M stands for a basic metal atom.
  • the salts may be formed from a monoor di-ester of phosphoric acid, orthophosphoric acid being the esterifying acid in obtaining either the dior mono-basic salt, metaand pyrophosphoric acids being adapted for forming the di-basic salt, and halogen derivatives of the acid, e. g., POCla or PCls being used in some reactions to advantage in place of orthophosphoric acid.
  • the aqueous solution was extracted with ether and the ether extract was neutralized by pouring gradually into a sodium carbonate solution. The entire neutralized solution was then transferred into a separatory funnel, and upon standing, two layers separated, the top layer containing ether and salt; the lower layer, water and salt. The layers were separated and each was evaporated to dryness. 33 grams of a white powder were obtained from the evaporated water layer. The evaporated ether layer was leached twice with 54 A. P. I. naphtha, leaving 95 grams of white powder which was naphtha-insoluble. The characteristics of the thus separated products as wetting agents and detergent aids were determined by the method of Draves and Clarkson as published in the Proc. Am. Assoc. Textile Chem. Colorists 1931, 109. The naphthainsoluble ether extract product had the following wetting out characteristics:
  • the naphtha-insoluble salt formed a clear neutral solution with water and showed a high wetting power.
  • hard water solution containing 300 parts per million of calcium the salt tended to precipitate.
  • acidified solution the salt caused some turbidity.
  • the high'petroleum phenols having more than 10' carbon atoms per molecule show an even greater deficiency of hydrogen in this respect and also show the presence of non-phenolic oxygen. Though these higher petroleum phenols tend to darken readily in color, which may preclude their use in forming wetting agents for some purposes, they have marked resistance to alkalies and high organic solvent solubility which is a valuable property in many respects.
  • paints water, inks, dye baths,- metal plating baths, spraying compositions, ore flotation mixtures, and lead treating baths. They may be used to improve cosmetics, the wetting of glue, the mixing of cement, the finishing of pastes, the removal of grease from steel, the spreading and a penetrating power of oils, the breaking of petroleum and water emulsions of the type found in oil fields, the emulsification in lacquer forma- Other normally liquid aliphatic alco-- tion, the absorption qualities of paper in paper manufacturing, etc.
  • a naphtha insoluble di-basic alkali metal salt of phosphoric acid partially esterified by alkyl phenol molecules containing an average total of 5 to 10 alkyl carbon atoms per molecule.
  • Patent dated Oct. 22,1940 Disclaimer filed Sept. 18, 1946, by the assignee, Standard Oil Development Company. Hereby enters this disclaimer to claim 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented Oct. 22, 1940 2,219,050 WETTING AGENT AND DETERGENT AID Louis A. Mikeska, Roselle, N. J assignor to Standard Oil Development Company, a corporation of Delaware No Drawing.
12 Claims.
This invention relates to improved detergent aids and wetting agents. More particularly, it relates to high wetting power salts of phosphoric acid partially esterifled by hydroxy aromatic compounds containing suitable hydrocarbon substituent groups.
By wetting agent is meant substances which improve spreading of surface coatings, increase spreading and penetrating power of liquids, such as aqueous solutions and oils, and which may act as detergent aids, emulsifying agents, and dispersing agents, all of these actions dependingsomewhat upon changes of interfacial and surface tension.
The wetting power of these agents can be evaluated by simple and rapid methods which measure the relative time taken for an aqueous solution of an agent to thoroughly penetrate, under prescribed conditions, a fabric or skein of flbres having a prescribed composition, form, and size. Although these methods more particularly compare the penetrating and detergent aiding action of the agents, they indicate, in general, the capacities of the agents to perform other wetting functions.
Although wetting agents and detergent aids have been prepared by neutralizing acid esters formed by reacting gaseous olefins with phenol in the presence of sulfuric acid, it has been found that salts of phosphoric acid partially esterifled by phenolic compounds are properly constltuted for high wetting power when the phenolic compounds contain suitable hydrocarbon constituents prior to esteriflcation with phosphoric acid or its condensible derivatives. While the salts of sulfuric acid partially esterifled. by alkylated phenols can be prepared by having the alkylation step occur during the esteriflcation, there are applications in which such salts are less desirable due to corrosiveness tendencies of their hydrolysis products.
, An object of this invention is'to producefrom phenolic compounds and phosphoric acid or its condensible derivatives, wetting agents and detergent aids which have high wetting and -deter-- gent effectiveness with restricted hydrolysis.
Another object of this invention is to prepare acid esters of phosphoric acid which on neutralization produce stable salts having wetting pow- 5 ers comparable to the most effective ester salt derivatives of sulfuric acid, and in some applications, even greater wetting powers, yet without corrosive tendencies of the sulfuric acid ester salts.
A further object of this invention is to pro- Application December 31, 1938, Serial'No. 248,900
(Cl. 260-461) I vide monoand di-esters of alkyl phenols and phosphoric acid and to provide such esters which can be reacted with alkali metal bases, to form naphtha-insoluble'and ether-insoluble salts having high wetting numbers in aqueous solutions. 5 Other specific objects will appear from the description which follows. I
These objects are achieved by partially esterifylng phosphoric acid, or a halogen derivative thereof, with selected phenolic compounds to ob- 1o tain acid esters which are subsequently neutralized to form the desired salts. Suitable alkyl phenols to be used as starting materials may, be obtained by alleviation of lower phenols present in coal tar. fractions or tar acids. Petroleum 1! phenols, per se, are very suitable. But, the phenolic compounds are preferably selected when they have alkyl side chains, either simple straight chain or cyclic, containing sufficient saturated carbon atoms to make'a total of about 0 5 to carbon atoms per molecule of acid ester formed in the esterification. As a rule, the wetting power decreases, while the detergent powerincreases, with increase in the size of the hydrocarbon substituent. For optimum results, 5 the phenolic compounds having hydrocarbon side groups containing about 3 to 10 saturated carbon atoms per molecule, are preferred for producing'di-ester salts. More exactly, the diester salt should contain 5 to 20 alkyl or cycloalkyl carbon atoms per molecule, that is, it is formed from the reaction of allgyl phenols having an average-of 2.5 to 10 alkyl carbon atoms per molecule. In forming the mono-ester, it is best to esterify a phenol having at least 5 carbon atoms in the hydrocarbon side chain.
Synthetic alkyl phenols'may be prepared by any of the known methods of alkylation. Suitable methods for their preparation are disclosed in U. S. Patent 1,948,287-of'February 20, 1934, o to Hyym E. Buc and Ruben Schuler, and U. S. Patent 1,954,985 of April 17, 1934, to Hyym E. Buc. These patents describe methods for alkylating phenolic compounds such as phenol, cresols, etc., with olefinic hydrocarbons having 5 more than 2 carbon atoms'per molecule and similar reactants. They indicate reactions of alkylating compounds with the phenolic compounds in the presence of strong sulfuric acid at controlled temperatures. The allnvl substltuents formed may be normal, iso, secondary, or tertiary.
The phenolic compounds may contain more than one alkyl substituent and other aliphatic or cycloaliphatic hydrocarbon substituents which supply the proper number of saturated carbon atoms which may be designated as paraflinic carbon atoms. Petroleum phenols which to some extent simulate phenolic compounds containing a polymethylene or cycloalkyl side group, according to their hydrogen and carbon analyses, have been found to be as satisfactory as alkyl phenols of corresponding or even higher molecular weights. Polyalkyl phenols may be obtained by alkylating lower phenols with suitable alkylating agents such as alcohols, olefins, alkyl sulfates, and alkyl halides, and these alkylating agents may be obtained from cracked petroleum hydrocarbon products.
Compounds which are to be preferably produced according to the present invention may be represented as including types having the following generalized compositions and structures:
where R represents 1 or several alkyl substituents containing an average total of 5 to 20 saturated carbon atoms, Ar represents an aromatic nucleus, and M stands for a basic metal atom. It is to be noted that the salts may be formed from a monoor di-ester of phosphoric acid, orthophosphoric acid being the esterifying acid in obtaining either the dior mono-basic salt, metaand pyrophosphoric acids being adapted for forming the di-basic salt, and halogen derivatives of the acid, e. g., POCla or PCls being used in some reactions to advantage in place of orthophosphoric acid. The desired partial esters containing the tervalent radical, EP=O, are thus obtained by using pentavalent phosphorus compounds which on hydrolysis yield phosphoric acid. The following equations, wherein R represents a hydrocarbon side group, are typical of the reactions carried out:
P o a 211.0 l\ O o oa (BOO) P0Ol+2NaOH (BOO) POONa+Na0l i To prepare a sodium salt of di(tertiary amylphenyl) phosphate, 9. one liter three-way flask Tertiary amyl phe n'm 164 D=\P gms 85 Tnluene N 250 The above materials werestirred and heated to 118 C. for 20 hours. Hydrogen chloride gas was liberated copiously in the early part of the reaction and at the end of this time the evolution of hydrogen chloride gas was slight. The toluene and excess POCla was distilled off and the residue was added slowly to stirred cracked ice. The aqueous solution was extracted with ether and the ether extract was neutralized by pouring gradually into a sodium carbonate solution. The entire neutralized solution was then transferred into a separatory funnel, and upon standing, two layers separated, the top layer containing ether and salt; the lower layer, water and salt. The layers were separated and each was evaporated to dryness. 33 grams of a white powder were obtained from the evaporated water layer. The evaporated ether layer was leached twice with 54 A. P. I. naphtha, leaving 95 grams of white powder which was naphtha-insoluble. The characteristics of the thus separated products as wetting agents and detergent aids were determined by the method of Draves and Clarkson as published in the Proc. Am. Assoc. Textile Chem. Colorists 1931, 109. The naphthainsoluble ether extract product had the following wetting out characteristics:
Wetting numbers Weight cone. percent Neutral Second; 4
Accordingly, the naphtha-insoluble salt formed a clear neutral solution with water and showed a high wetting power. In hard water solution containing 300 parts per million of calcium, the salt tended to precipitate. In acidified solution, the salt caused some turbidity.
In some cases, it was found advantageous to carry out the condensation of the phosphorus oxy chloride with the alkylated phenol in the presence of pyridine or an equivalent base. In most cases, however, the use of the base was found. unnecessary.
In a second experiment using the same type of procedure as explained in the foregoing experiment, phenolic compounds from a petroleum oil fraction were reacted with P001: to form the di-ester chlorophosphate, and the resulting chlorophosphate was neutralized with potassium hydroxide to obtain an ether-extracted naphthainsoluble salt having the following wetting properties in a neutral aqueous solution:
Concentration of salt by weight in aqueous solutionpercent 0.2 0.1 0.07"
Wetting numbers in soft water sec 4.5 30 187 From these "data it can be observed that the lower petroleum phenolic compounds, which comprise phenols containing parafflnic hydrocarbon side groups having a lower hydrogen to carbon ratio than is present in simple alkyl groups, form simple aryl ester salts of phosphoric .acid which are as effective in wetting power as s about C3.3H'1.5'C6H4OH. This deficiency of hydrogen in the saturated hydrocarbon substituent group is attributed to the presence of cycloalkyl groups, which makes the hydroxyaromatic com-' pound partly simulate a naphthenic compound. The high'petroleum phenols having more than 10' carbon atoms per molecule show an even greater deficiency of hydrogen in this respect and also show the presence of non-phenolic oxygen. Though these higher petroleum phenols tend to darken readily in color, which may preclude their use in forming wetting agents for some purposes, they have marked resistance to alkalies and high organic solvent solubility which is a valuable property in many respects.
In a third experiment, a mol of phosphoric acid was esterified with one mol of tertiary amyl under some conditions may be made.
phenol to obtain a mono-ester, which,' in turn, was neutralized with two mole of sodium hydroxide to produce the corresponding di-sodium salt of the mono-ester, which was extracted by isopropyl alcohol. The ether-insoluble portion of the isopropyl alcohol extract made a clear 2% concentration solution with distilled water and showed a wetting number of 37 seconds, and in a .2% concentration in hard water containing 300 parts per million of calcium ion gave a perfectly clear solution having a wetting number of 25 seconds. hols may be substituted for the isopropyl alcoholin the extraction.
Such experiments demonstrate that the naphtha-insoluble di-ester salts of the phosphoric acid esters were particularly effective wetting agents and detergent aids in neutral aqueous solutions, while the ether-insoluble salts of the mono-esters were more effective in hard water solutions. While certain classes of alkyl and cycloalkyl phenols have been emphasized as being of major importance for selection in'forming the improved wetting agents by esterification with, phosphoric acid or its halogen derivatives, various modifications to improve performance For example, aliphatic alcohols, naphthenic alcohols, or aralkyl alcohols may be used auxiliary to the phenols in forming the phosphoric acid esters.
, amino, sulfonate, sulfate, and halogen groups,
or other suspensoids in liqu1d vehicles, e. g.,
paints, water, inks, dye baths,- metal plating baths, spraying compositions, ore flotation mixtures, and lead treating baths. They may be used to improve cosmetics, the wetting of glue, the mixing of cement, the finishing of pastes, the removal of grease from steel, the spreading and a penetrating power of oils, the breaking of petroleum and water emulsions of the type found in oil fields, the emulsification in lacquer forma- Other normally liquid aliphatic alco-- tion, the absorption qualities of paper in paper manufacturing, etc.
This invention is not to be limited by the specific examples given nor by any theory advanced on the mechanism of operation, but only by the 5 appended claims in which it is intended to claim all novelty inherent in the invention as broadly as the prior-art permits.
l. A base metal salt of a phosphoric acid ester 10 containing at least one alkylaryl group and a total of 5 to 20 saturated carbon atoms in the alkyl radicals of said alkyl-aryl groups.
' 2. A mono basic alkali metal salt of a phosphoric acid ester in which the ester groups con-' sist in alkyl phenyl radicals containingan average total of 5 to about 20 alkylcarbon atoms per molecule-of the salt.
3. A naphtha insoluble di-basic alkali metal salt of phosphoric acid partially esterified by alkyl phenol molecules containing an average total of 5 to 10 alkyl carbon atoms per molecule.
4. A di-basic alkali metal salt of a phosphoric acid ester in which the ester group consists in an alkyl phenyl radical containing a total of 5 25 to about 20 alkyl carbon atoms per molecule of I the salt.
5. An ether-insoluble alkali metal salt of phosphoric acid partially esterified with an alkyl phenol containing 5 to 10 alkyl carbon atoms per 30 7 molecule.
6. The preparation of improved wetting agents by a process which comprises condensing with a pentavalent phosphorus compound which hydrolyzes to phosphoric acid a limited quantity as of phenolic molecules containing hydrocarbon substituents which have an average total of 5 to 20 saturated carbon atoms per molecule of said ester salts by a normally liquid alcohol and 5 leached with ether. 0
9. The preparation of improved wetting agents and detergent aids by a process which comprises condensing phosphoric acid with alkyl phenols having an average of 2.5 to 10 alkyl carbon atoms 55 per molecule and reacted in a quantity to produce phosphoric acid di-esters, then neutralizing resulting acid esters with analkali metal base to obtain their ester salts.
10. The preparation of improved wetting 60 agents by a process which comprises condensing phosphorus oxychloride with a limited quantity 'of phenolic compounds containing paraflinic bydrocarbon substituents having an average of 2.5 to 10 carbon atoms per molecule to obtain phosphoric acid di-esters, and neutralizing said acid di-esters with an alkali metal base to, obtain their ester salts.
11. The preparation of improved wetting agents by a process which comprises condensing phosphoric acid with an alkyl phenol containing 5 to about 20- alkyl carbon atoms per molecule and reacted in a quantity to produce a phosphoric acid mono-ester, and neutralizing 5 in which R represents at least one alkyl subthe resulting acid ester with an alkali metal base to produce an ester salt.
DISCLA 2,219,050.L0uis A. Mikeska, Roselle, N. J.
which is 3.
LOUIS A. MIKESKA.
EMER
WETTING AGENT AND DETERGENT An).
Patent dated Oct. 22, 1940. Disclaimer filed Sept. 18, 1946, by the assignee,
Standard Oil Development Company. Hereby enters this disclaimer to claim 1.
[Ofiicz'al Gazette October 22, 1.946.]
DISCLAIMER 2,219,050.-L0uis A. Mikeska, Roselle, N. J. WETTING AGENT AND DETERGENT A11).
Patent dated Oct. 22,1940. Disclaimer filed Sept. 18, 1946, by the assignee, Standard Oil Development Company. Hereby enters this disclaimer to claim 1.
[Qfiicial Gazette October 22, 1946.]
US248900A 1938-12-31 1938-12-31 Wetting agent and detergent aid Expired - Lifetime US2219050A (en)

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GB28878/39A GB533327A (en) 1938-12-31 1939-10-27 An improved manufacture of detergent aids and wetting agents
FR862643D FR862643A (en) 1938-12-31 1939-12-30 Wetting agents and detergents

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2777807A (en) * 1952-11-22 1957-01-15 Du Pont Process of suppressing foam formation in distillation of acrylonitrile
US3000750A (en) * 1953-03-06 1961-09-19 Dehydag Dentsche Hydrierwerke Process of preparing dispersions of pulverulent material and preparations obtained thereby

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2777807A (en) * 1952-11-22 1957-01-15 Du Pont Process of suppressing foam formation in distillation of acrylonitrile
US3000750A (en) * 1953-03-06 1961-09-19 Dehydag Dentsche Hydrierwerke Process of preparing dispersions of pulverulent material and preparations obtained thereby

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GB533327A (en) 1941-02-11
FR862643A (en) 1941-03-11

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