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Publication numberUS3004057 A
Publication typeGrant
Publication dateOct 10, 1961
Filing dateDec 1, 1959
Priority dateNov 12, 1959
Also published asDE1210854B, US3004056
Publication numberUS 3004057 A, US 3004057A, US-A-3004057, US3004057 A, US3004057A
InventorsJr Leslie G Nunn
Original AssigneeGen Aniline & Film Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface active compositions
US 3004057 A
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Description  (OCR text may contain errors)

No Drawing. Filed Dec. 1, 1959,58. No. 856,367 15 Claims. (Cl. 260-461) This invention relates to the production of surface active compositions, and more particularly to an improved process for preparing surface active compositions containing mixtures of primary and secondary phosphate esters of hydroxylic organic compounds.

Hydroxylic organic compounds have been previously esterified with a number of different phosphating agents including phosphoric acid, P H11 and POCl and the like. While such processes have in some instances produced surface active compounds or compositions, they have been commonly subject to a number of procedural disadvantages and/or have failed to produce a surface active product having optimum properties for certain end uses. Thus, the use of P001 as the phosphating agent yields products containing bound chlorine atoms, and in addition requires careful manipulation to remove the HCl produced during the reaction. Further, the 'HCl raises problems of corrosion. The use of phosphoric acid or solutions of P 0 in phosphoric acid as phosphating agent generally yields inconsistent mixtures of different types of esters, including esters of pyrophosphoric acid, phosphoric acid, primary, secondary and tertiary phosphates, and the like. When P 0 has been employed, considerably greater molar ratios of the hydroxy compounds were regarded as necessary to bring the solid P 0 into solution. 1

In the copending application of Leslie G. Nunn and Stanley H. Hesse, Serial No. 852,188, filed November 12, 1959, a process is disclosed for producing phosphate esters of hydroxylic organic compounds, which process is directed towards eliminating the above mentioneddisadvantages.

Said process broadly comprises reacting one mole of P 0 with 2 to 4.5 moles of a nonionic surface active agent having the molecular configuration of a condensation product of at least one mole of ethylene oxide with one mole of a compound containing at least 6 carbon atoms and a reactive hydrogen atom under substantially anhydrous conditions and at a temperature belowabout 110 C. This process does not require the use of an excess of the hydroxylic organic compound (in this instance the defined nonionic surface active agent), in order to bring the P 0 into solution. Substantially no tertiary phosphate ester is formed by this process and little or no P 0 remains in the composition. Depending upon the particular ratio of P 0 to the nonionic surface active agent employed, and the nature of such nonionic, the product may in some instances contain some unreacted nonionic surface active agent which for certain uses is actually advantageous.

For similar reasons, the proportions of secondary phosphate esterzprimary phosphate esterzfree nonionic in the products of this invention will in general fall within the range of about 20 to 45% secondary esterz30 to 80% primary ester:0 to 40% nonionic, byweight.

While the process disclosed in said application is highly effective, it has been found that the products thus pro-, duced are somewhat colored and that such products tend to become discolored or to darken on storage. Uncolored or light colored products are required in many uses for surface active agents and many formulators of such compositions, particularly liquid detergent compositions, have rigid color specification for the components of such foratent' 3,094,051 vPatented Oct. 10, 1961 ice mulations which require substantially colorless raw materials.

It is an object ofthis invention to provide a process for producing phosphate esters of nonionic surface active agents which will result in lighter colored or substantially colorless products. Another object of this invention is to improve the process disclosed in said copending application whereby lighter colored or substantially colorless products are formed. Still another object of this invention is the provision of such a process which will result in phosphate ester products having improved stability to discoloration or darkening on storage. Other objects and advantages will appear as the description proceeds.

The attainment of the above objects is made possible by my discovery that lighter colored or substantially colorless products are obtained when the phosphation re action disclosed in said copending application is carried out in the presence of a small or catalytic amount of a phosphorus-containing compound selected from the group consisting of hypophosphorous acid, salts of hypophosphorous acid, phosphorous acid, and salts and esters of phosphorous acid. More particularly, my invention includes a process comprising reacting one mole of P 0 with 2 to 4.5 moles of a nonionic surface active agent having the. molecular configuration of a condensation product of at least one mole of ethylene oxide with one mole of a compound containing at least 6 carbon atoms and a reactive hydrogen atom, under substantially anhydrous conditions and at a temperature below about .110 C. in the presence of a small amount of one or a mixture of the aforementioned hypophosphorous or phosphorous acid compounds.

By the use of such compounds in the described phosphation reaction, it has been found that an unexpected and substantial improvement in the (absence of) color of the products and the resistance of such products to discoloration in storage is obtained. Products resulting from the use of the present invention generally have VCS (varnish color scale, Gardner scale, standards of 1933) values of at least one less than products of the same process carried out in the absence of the hypophosphorous or phosphorous acid compound. Products hav ing a VCS color of about 1 or less are thus made possible, as compared with VCS colors of from about 2 to 7 or more for products produced without the aid of the present invention. Further, the products of this invention have been found to resist discoloration or darkening even after storage for three to six months.

Since this invention is applicable for the improvement of the inventive process disclosed in said copending application, the entire subject matter of said copending application is incorporated herein by reference thereto. Stated otherwise, said application fully discloses nonionic surface active agents employed as reactants in the phospha-- .tion reaction, the conditions of reaction, the manner of carrying out the reaction, and the products thus produced, all of which are employed in the present process.

Briefly stated, the nonionic surface active agents em- I ployed as reactants in the present invention are well known in the art and are disclosed along with suitable methodsffortheir preparation in numerous patents and other publications. In general, they may be obtained by condensing a polyglycol ether containing the required 5 alent condensed with the reactive chain, will depend primarily'upon the particular compound with which it is condensed. As a convenient rule of thumb, an amount of alkylene oxide or equivalent should be employed which will result in a condensation product containing about 20 to 85% by weight of combined alkylene oxide. 'However, the optimum amount of alkylene oxide for attainment of the desired hydrophobic-hydrophilic balance may the molecular configuration of a condensation product of at least one mole of an alkylene oxide, preferably ethylene oxide, with one mole of a compound containing at least 6 carbon atoms and a reactive. hydrogen atom are preferably polyoxyalkylene derivatives of alkylated and polyalkylatedphenols, multi-branched chain primary aliphatic alcohols having the molecular configuration of an alcohol produced by the x0 process from a polyolefin of at least 7 carbon atoms, and straight chain aliphatic alcohols of at least 10 carbon atoms. Examples of these derivatives and other suitable nonionic surface active agents which may be phosphated in accordance with the present invention are included below. In this list, E0. means ethylene oxide and the number preceding same refers to the number of moles thereof reacted with one mole of the given reactive hydrogen-containing compound.

N onylphenol+9-l 1 E0. Nonylphenol+2 E.O.

-Dinonylphenol+7 E.O.

Dodecylphenol+l8 E.O.

Castor oil+20 E.O.

Tall oil+18 E.O.

Oleyl alcohol+20 E.O.

Lauryl alcohol+4 E.O.

Lauryl alcohol-H5 E.O.

Hexadecyl alcohol+12 E.O.

Hexadecyl alcohol-[-20 E.O.

Octadecyl alcohol+20 E.O.

Oxo tridecyl alcohol:

(From tetrapropylene)+7 E.O. (From tetrapropylene) E.O. (From tetrapropylene) E.O.

Dodecyl mercaptan+9 E.O.

Soya bean oil amine-{-10 E.0.

Rosin amine+32 E.O.

Coconut fatty acid amine+7 E.O.

Cocoa fatty acid-H0 E.O.

Dodecylbenzene sulfonamide+ 10 ED.

Decyl sulfonamide+6 E.O.

Oleic acid+5 E.O.

Polypropylene glycol (30 oxypropylene units) +10 -E.O.

In carrying out the phosphation reaction in accordance with this invention, the P 0 is preferably added gradually, with vigorous agitation, to the nonionic surface active agent in liquid form. If the latter agent is a solid at room temperature, it should be heated to above its melting point. Addition of the nonionic surface active agent to the P 0 is inadvisable since this has been found to result in the formation of tar and the like and to prevent the reaction from proceeding to completion. The reaction is exothermic and in some cases cooling is necessary to prevent the temperature from going above about 110 C. since this tends to produce discolored and darkened products. The reaction proceeds continuously during addition of the P 0 and solution thereof in the nonionic surface active agent, and is substantially 90% complete or more by the time all of the P 0 has been added. The few particles of solid P 0 remaining in the reaction medium may be removed at this point if time is of the essence, but it is preferred in the interests of economy to allow the reaction to proceed for an 4 5 hours or more at ambient temperatures up to about "C. until all of the P 0 has dissolved indicating complete reaction between the reactants involved. Vigorous agitation during the reaction is highly desirable to facilitate and expedite completion of the reaction.

It is an advantageous feature of this invention that the P 0 may be employed in dry, solid form as a granular powder or other finely divided or particulate form, for reaction with the above defined nonionic surface active agents. However, if desired, the P 0 may first be dispersed in an inert organic diluent such asbenzene, xylene, ether, pentane, or low and high boiling hydrocarbon fractions.

After completion of the reaction, the reaction mixture may be cooled and discharged. If carried out under rigid anhydrous conditions the product should consist of a mixture of the primary and secondary phosphate esters of the nonionic surface active agent combined, depending upon the proportions of reactants, in some instances with a small proportion of unreacted nonionic surface active agent. Any small amount of water present in the reaction mixture will result protanto in the formation. of some phosphoric acid in the product. The degree of esterification in the product may be determined by potentiometric titration or by titration with alkali to methyl orange and then to phenolphthalein.

As referred to above, the essence of my invention resides in the addition to the reaction medium of a small amount of hypophosphorous or phosphorous acid compound. Generally, about 0.01 to 5% and preferably about 0.1 to 2% of such compound, based on the weight of the nonionic surface active agent being phosphated is sufficient to provide the desired improvements with respect to prevention of color degradation of the prodnets and improvement in resistance of the products to 'color degradation in storage. Hypophosphorous acid and its alkali metal salts, e.g. sodium and potassium salts are generally preferred although any metal, alkaline earth metal, ammonium or amine salt of hypophosphorous acid or phosphorous acid may be employed, in addition to phosphorous acid per so. When hypophosphorous acid is employed, it is preferred to use a 30 to 50% aqueous solution thereof although aqueous solutions of this acid and other of the water soluble hypophosphorous and phosphorous acid compounds may be employed in the form of aqueous solutions ranging in concentration from less than 5 up to 70% or more. It should be borne in mind that the reaction should be carried out under subs't'antially anhydrous conditions and accordingly the water introduced in such solutions should be held to a minimum.

The salts of hypophosphorous acid and phosphorous acid employed herein may be in their hydrated or dehydrated form. As examples of such salts, there may be mentioned aluminum, cadmium, sodium, potassium, lithium, calcium, strontium, barium, magnesium, ammonium, mono-, di-, and tri-methylamine, -ethylamine, -propyl'amine, -ethanolamine, and -propanolamine, pyridinyl, and morpholinyl phosphites and hypophosphites.

Esters of phosphorous acid may also be employed. These esters may be described as mono-, di-, and trialkyl, -aryl, and -cyeloalkyl phosphites. It will be understood that mixed esters are included. As some specific examples of such esters in which the esterifying group generally contains from about 1 to 20 carbon atoms, there may be mentioned ethyl phosphite, lauryl phosphite, OX0 tridecyl phosphite (the esterifying alcohol having the molecular configuration of an alcohol produced from tetra propylene or triisobutylene by the 0x0 process), stearyl phosphite, phenyl phosphite, cyclohexyl phosphite, the corresponding diand tri-substituted phosphites, ethyl phenyl phosphite, ethyl diphenyl phosphite, lauryl cyclohexyl phosphite, dipropyl phenyl phosphite, and the like.

In accordance with this invention, the hypophosphorous or phosphorous acid compound is preferably admixed with additional period of time which may range from /2 'to 75. fhc'non-ioni'c'surface active agent prior to additionthe'reto of the P if desired, however, such compound may be added simultaneously with the addition of the P 0 or, if anhydrous, may be admixed with the P 0 prior to its addition to the nonionic surface active agent. It Will accordingly be understood that the hypophosphorous or '6 measurable by this method the highest being 18. Products prepared with the use of the additives referred to in the table sustained no change in color after 3 to 6 months storage.

phosphorous acld compound or mixture thereof may be 5 It will be understood that all parts and proportlons added at the start of the reactionmr continuously, or ,m-g to 3 111 the PP claims y termittently as the reaction proceeds. weight unless otherwise indicated.

OH- 205 VCS Ex. Nonionic agent ionic parts Parts Additive color parts 1-----. Nonylphenol+2 E.O 2, 288 284 Control 2 Cs mCs 4( 2 4)n0 9 (in 2, 288 284 3. 4 Hypophosphorous acid (50%). 1 3 Nonylphenol+4 E.O 2,355 213 Control 4 CrHCsH4(OC2H4)4OH 4 do 2, 355 213 4. 2 Hypophosphorous acid (50%). 1 5 Nonylphenol+6 E.0 484 47. 3 Control 4 C9H nOc 4(0C2 4)aOH 6 do 484 47. 3 1. 0 Hypophosphorous acid (50%) 1 7 do 484 47. 3 0. 5 Sodium hypophosphite 1 8 do 484 47. 3 2.0 Triphenyl phosphite 2 9 Nonylphenol+10 E.O 1, 821 108 Control 4 D 19 fl 4( 2 -)10 1n rln l, 821 108 7. 0 Hypophosphorous acid (30%). 1 11 Nonylphcnol+100 E.O 605 11.9 Control 2 Cr mCs 4(OCzH4)1ooOH 1 2 do 605 11. 9 1. 2 Hypophosphorous acid (50%)- 1 13"--- Dinonyl hcnol+7 E.O 327 23. 6 Control 5 O1 saCs a(O C2H4)1OH V 14 do 327 23. 6 1 0 Hypophosphorous acid (30%). 1 15"--- Dodecyzlfihenol+6 E.O 1,052 94.4 Control 4 C1 2aCc 4(0C2 4)sOH V 16 dn 1, 052 94. 4 3.0 Hypophosphorous acid (50%)- 1 17-- 0x0 tn'decyl alcohol +3 13.0 166 23. 7 Control 7 C;3H21(0C2H4)20H 18 d0 166 23. 7 1.0 Hypophosphorous acid (50%)- 2 1 1 166 23. 7 1.0 Phosphorous acid 2 20---..- Lauryl alcohol+4 E.O 724 71 Control 7 O12H25(OO2H4)40H 21 (ln 724 71 1. 3 Hypophosphorous acid (50%) 1 1 From tetrapropylene by the 0x0 process.

The products of this invention may be supplied in free unneutralized form, or in the form of the partially or completely neutralized salts containing as cations alkali metals, alkaline earth metals, metals, ammonium and organic amines. Use in the form of such salts is in some instances preferred or necessary, as for example when employed in alkaline surface active and other compositions. It is to be understood that such salts are to be regarded as the equivalent of the present products in their free form. As examples of suitable cations, there may be mentioned sodium, potassium, lithium, calcium, strontium, barium, magnesium, iron, tin, cadmium, aluminum, antimony chromium, manganese, mercury, nickel, silver, zinc, ammonium and aliphatic, alicyclic, aromatic, and heterocyclic organic amines such as the mono-, di-, and tri-methylamines, -ethylamines,-propylamines,-laurylamines, -stearylamines, -ethanolamines, propanolamines,- butanolamines, -hexanolamines,- cyclohexylamines, -phenylamines, pyridylamine, morpholinylamine, and the like.

The examples in the following table are only illustrative of the present invention and are not to be regarded as limitative. In each of these examples, the nonionic surface active agent is first charged to a reactor equipped with an agitator. If the charge is solid at room temperature, it is heated to melt the same. The additive referred to in the table is then added to and dissolved in the nonionic surface active agent with vigorous agitation. The solid granular P 0 is then charged to the reactor with vigorous agitation over a period ranging from about 5 minutes to about 1 hour and usually about 15 minutes. After the initial exothermic reaction subsides, the reaction mixture is heated to 100 C. and held at this temperature for about 5 hours after which the mixture is cooled and discharged. A sample of the reaction mixture is titrated with alkali to methyl orange and then to phenolphthalein as a control on the esterification.

I The VCS color readings are measured in the prescribed manner. A reading of one is the lowest color reading Thisinvention has been disclosed with respect to certain preferred embodiments and there will become obvious to persons skilled in the art various modifications, equivalents or variations thereof Which are intended to be included within the spirit and scope of this invention.

I claim:

1.- In a process comprising reacting 1 mole of P 0 with 2 to 4.5 moles of a nonionic surface active agent having the molecular configuration of a condensation product of atleast one mole of ethylene oxide with one mole of a compound containing about 6 to 150 carbon atoms and a reactive hydrogen atom and selected from the group consisting of phenol, alkyl phenols, aliphatic alcohols, fatty acids, fatty amines, fatty amides, rosin amines, long chain sulfonamides, long chain-substituted aryl sulfonamides, and high molecular weight mercaptans under substantially anhydrous conditions and at a temperature below about C. down to about room temperature, the improvement comprising carrying out the reaction in the presence of a small amount of a phosphorus-containing compound selected from the group consisting of hypophosphorous acid, salts of hypophosphorous acid, phosphorous acid, and salts and esters of phosphorous acid.

2. A process as defined in claim 1 wherein said reactive hydrogen-containing compound is an alkyl phenol of at least 10' carbon atoms.

3. A process as defined in claim 1 wherein said reactive hydrogen-containing compound is a multi-branched chain primary aliphatic alcohol having the molecular configuration of an alcohol produced by the 0x0 process from a polyolefin of at least 7 carbon atoms.

4. A process as defined in claim 1 wherein said reactive hydrogen-containing compound is a straight chain aliphatic alcohol of at least 10 carbon atoms.

5. A process as defined in claim 1 wherein said phosphorus-containing compound is hypophosphorous acid.

6. A process as defined in claim 1 wherein said phosphorus-containing compound is sodium hypophosphite.

7. A process as defined in claim -1 wherein said phosphorus-containing compound is phosphorous acid.

8. ,A process as defined in claim 1 wherein said phosphorus-containing compound is triphenyl 'phosphite,

9. In a process comprising gradually adding with agitation one mole of dry, solid P 0 to 2 to 4.5 moles of a nonionic surface active agent having the molecularconfiguration of a condensation product of at least one mole of ethylene oxide with one mole of a compound containing about 6 to 150 carbon-atoms and a reactive hydrogen atom and selected from the group consisting of phenol, alkyl phenols, aliphatic alcohols, fatty acids, fatty amines, fatty amides, rosin amines, long chain sulfonamides, long chain-substituted aryl sulfonamides, and high molecular weight mercaptans, and allowing the phosphation to proceed under substantially. anhydrous conditions and at a temperature below about 110 C. down to about room temperature, the improvement comprising first dissolving in'the nouionic surface active agenta small amount of a phosphorus-containing compound selected from the group consisting of hypophosphorous acid,

salts of hypophosphorous acid, phosphorous acid, and salts and esters of phosphorous acid.

10. A process as defined in claim 9 wherein said reactive hydrogen-containing compound is an alkyl phenol of at least 10 carbon atoms.

11. A process as defined in claim 9 wherein said Ieac tive hydrogen-containing compoundis a multi-hranched chain primary aliphatic alcohol having the molecular configuration of an alcohol produced by the 0x0 process from a polyolefin of at least 7 carbon atoms.

12. A process as defined in claim 9 wherein said compound is a straight chain aliphatic alcohol of at least 10 carbon atoms.

13. A process as defined in claim 9 wherein said phosphorus-containing compound is hypophosphorous acid.

14, A process as defined in claim 9 wherein said phos- I References Cited in the file of this patent FOREIGN PATENTS 1,139,717 France July 4, 1957

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
FR1139717A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3117152 *Nov 6, 1961Jan 7, 1964Stamford Chemical Ind IncSubstantially neutral magnesium salt of a phosphoric acid ester of oxethylated nonylphenol
US3203895 *Mar 22, 1962Aug 31, 1965Universal Oil Prod CoLubricating oils containing amine salts of phosphates
US3235627 *Jan 31, 1963Feb 15, 1966Rohm & HaasAlkali soluble and alkali stable compositions comprised predominantly of phosphate monoesters
US3240585 *Jun 26, 1962Mar 15, 1966Gen Aniline & Film CorpEmulsifiable agricultural biocide composition
US3246997 *May 9, 1961Apr 19, 1966Gen Aniline & Film CorpPrinting emulsions
US3253895 *Mar 27, 1962May 31, 1966Lubrizol CorpPhosphorus-containing depositresistant fuel composition
US3275667 *Jan 21, 1963Sep 27, 1966Hoechst AgProcess for the manufacture of phosphate ester derivatives of polyalkylene glycols
US3310496 *Mar 12, 1965Mar 21, 1967Rohm & HaasAlkali stable and soluble surfactants
US3312624 *Mar 12, 1965Apr 4, 1967Rohm & HaasStable alkali soluble surfactants
US3317305 *Mar 14, 1963May 2, 1967Gen Aniline & Film CorpBiocidal composition containing an electrolyte plant nutrient
US3331896 *Sep 15, 1964Jul 18, 1967Gen Aniline & Film CorpMethod of preparing alkali soluble phosphate esters of hydroxylic organic compounds
US3341343 *Nov 12, 1963Sep 12, 1967Gen Anilline & Film CorpHydrophobic polymeric resin containing phosphate ester antistatic agent and process for producing antistatic properties
US3346670 *Dec 11, 1962Oct 10, 1967Gen Aniline & Film CorpMethod for the preparation of phosphate esters
US3352808 *Sep 9, 1963Nov 14, 1967Gen Aniline & Film CorpGraft copolymers of styrene and butadiene onto polyvinyl lactam homopolymers
US3963628 *Jun 7, 1974Jun 15, 1976Union Carbide CorporationOrganic phosphates, mineral oil, ethylene oxide-propylene oxide monoalkyl ether
US4077898 *Jan 17, 1977Mar 7, 1978Economics Laboratory, Inc.Iodine/phosphate ester compositions and methods of using them
US4137190 *Apr 4, 1977Jan 30, 1979Gaf CorporationDetergent composition comprising synergistic hydrotrope mixture of two classes of organic phosphate esters
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US4912245 *Jun 16, 1987Mar 27, 1990Rhone-Poulenc ChimiePhosphoric acid ester-based compositions, process for the preparation thereof
US5202056 *Dec 30, 1991Apr 13, 1993Texaco Inc.Composition of matter for oligomeric aliphatic ethers as asphaltene dispersants
US5415793 *Mar 21, 1994May 16, 1995Texaco Inc.Lubricant additive to prevent camshaft and valve train wear in high performance turbocharged engines
US6852678Nov 19, 2001Feb 8, 2005Mec International CorporationComplexes
US6858568Nov 15, 2001Feb 22, 2005Mec International CorporationMetal lubricants containing a bridge complex
US7470733 *Jan 22, 2004Dec 30, 2008Kao CorporationAdditive for hydraulic compositions
DE2412175A1 *Mar 14, 1974Sep 25, 1975Kreussler Chem FabVerfahren zum appretieren von textilien, insbesondere waehrend der chemischreinigung
EP0018492A1 *Mar 21, 1980Nov 12, 1980Hoechst AktiengesellschaftAqueous disinfectant solution
WO2010101737A1Feb 23, 2010Sep 10, 2010Lubrizol Advanced Materials, Inc.Dispersant composition
Classifications
U.S. Classification558/114, 554/78, 516/DIG.100, 504/365, 544/110, 504/363, 510/467, 516/56, 504/364, 554/40, 530/213, 987/224
International ClassificationC11D1/34, C07F9/09, C07F9/08
Cooperative ClassificationY10S516/01, C07F9/08, C11D1/345, C07F9/09
European ClassificationC07F9/08, C11D1/34C, C07F9/09