US2892796A - Detergent composition containing phosphated alkyl glyceryl ether corrosion and tarnish inhibitor - Google Patents

Detergent composition containing phosphated alkyl glyceryl ether corrosion and tarnish inhibitor Download PDF

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Publication number
US2892796A
US2892796A US614186A US61418656A US2892796A US 2892796 A US2892796 A US 2892796A US 614186 A US614186 A US 614186A US 61418656 A US61418656 A US 61418656A US 2892796 A US2892796 A US 2892796A
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Prior art keywords
glyceryl ether
alkyl glyceryl
alkyl
detergent composition
corrosion
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US614186A
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English (en)
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Homer W Mccune
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to BE561095D priority Critical patent/BE561095A/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US614186A priority patent/US2892796A/en
Priority to GB30849/57A priority patent/GB846499A/en
Priority to DEP19413A priority patent/DE1079773B/de
Priority to FR1186366D priority patent/FR1186366A/fr
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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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids

Definitions

  • the present invention relates to heavily built synthetic detergents and specifically to a novel compound for preventing the builders in such detergents from attacking metals.
  • Some calcium sequestrants if not inhibited, will corrode aluminum and zinc, and tarnish coppery alloys like German silver. I have discovered that a certain class of preparations will inhibit these effects.
  • These preparations are phosphated alkyl glyceryl ethers wherein the alkyl groups are from 14 carbons to 18 carbons inclusive in chain length.
  • the phosphation may be carried out with from 1 to 3 atoms of phosphorus from a phosphating agent, per mole of alkyl glyceryl ether.
  • the phosphated alkyl glyceryl ether is useful in amounts from about /2% to about 20% of the calcium sequestrant. It is effective above 20% but no additional protection is achieved.
  • the corrosion of aluminum by alkalis is well known, but the corrosion by sequestrants is almost unrecognized. Sequestrants corrode aluminum much worse than nonsequestering alkaline materials even at the same pH.
  • the instant invention contemplates the reduction of corrosion by sequestrants whether these are used as such, ,or whether they are employed as builders in synthetic detergent compositions.
  • the corrosive calcium sequestrants against which the phosphated alkyl glyceryl ether is effective are the water soluble salts of tripolyphosphoric acid, ethylene diamine tetra acetic acid, hydroxy ethyl ethylene diamine triacetic acid, and nitro triacetic acid.
  • the amino polycarboxylic compounds containing at least 3 acetate radicals are normally used in the form of their sodium salts as are the tripolyphosphates.
  • the starting compound for the alkyl glyceryl ether phosphate of the present invention is alkyl chloroglyceryl ether, prepared by reacting epichlorohydrin with a fatty alcohol.
  • the chlorine is hydrolyzed oif of the compound, producing principally- H In practice, not all of the chlorine is removed. Up to about-25% of the hydrolyzed material may be present as chloroether.
  • the hydrolyzed chloroether is then reacted with POCl or other phosphating agents later described and the reaction product neutralized with sodium hydroxide or other suitable alkali.
  • the product contained 8.24% of combined phosphorus. If the phosphation has formed a phosphate ester at each of the two hydroxyls of the alkyl glyceryl ether the phosphate content would have been 10.6. This deficiency of phosphorus may in part be explained by the fact that the chlorine content was 1.29% indicating that not all of the terminal chlorine atoms were bydrolyzed off the chloroether.
  • Standard corrosion test-The aluminum strips were cut from The Aluminum Company of America 35 grade aluminum. This contains about 1.2% manganese.
  • the strips were 3 inches long, inch wide and 0.041 inch thick. They were polished with steel wool, followed by wet pumice, and then washed with water and alcohol. After air drying they were weighed on an analytical balance. They were immersed in 200 milliliters of test solution in a 250 ml. Erlenmeyer flask. The strips were leaning at an angle to the bottom of the flask of about 40. The flasks were held at F. for three hours, unless otherwise noted. After the tests the strips were removed, washed in water and immersed in concentrated nitric acid for 3 minutes to remove products of corrosion. They were then washed in water and alcohol, air dried and weighed again.
  • compositions containing sodium triphosphate will be protected against corrosion of many of the metals used in washing machines and the tarnishing of coppery alloys by phosphated alkyl glyceryl ether.
  • the alkyl glyceryl ethers may be phosphated with P 0 polyphosphoric acid and orthophosphoric acid; even 85% orthophosphoric is elfective in phosphating the alkyl glyceryl ethers as will be shown below.
  • the P 0 tended to produce a product of only moderate activity as a corrosion inhibitor, and the 85% orthophos phoric required 40 hours of heating to produce an eifective corrosion inhibitor, but the phosphated alkyl glyceryl ethers seem to be effective no matter how they are phosphated, as indicated by the following tests.
  • the phosphating agent and the tallow glyceryl ether were mixed in a glass tube fitted with a stirrer and con- 1 'nected to a water aspiraton
  • the stirring shaft was fitted with a. number of prongs to make the stirring more etficient.
  • the mixtures were stirred under water aspirator vacuum (about 15 mm. abs. pressure) for the times and at the temperatures shown in the table below.
  • the compounds in the acid state were added to the test solutions, where they were immediately neutralized by the alkalinity of the test solution.
  • the preparations were used in the standard corrosion test previously described.
  • the aqueous solution contained 0.18% of sodium tripolyphosphate, 0.06% of the sodium salt of keryl benzene sulfonate and 0.02% of the phosphated alkyl glyceryl ether. This is the concentration that would be achieved if an 0.03% solution were prepared from a detergent of the following composition:
  • the hardness of the water used was 7 grains CaCO equivalent per gallon and the tests were run at 60" C. The results of the corrosion test follow.
  • Average corrosion without the inhibiting phosphated glyceryl ether but with other constituents present was 14.0 mgs.
  • the acid phosphate as prepared or the neutralized product used in Example I may be used.
  • the optimum amount of phosphating agent is that which furnishes two atoms of phosphorus per mole of alkyl glyceryl ether.
  • EXAMPLE IV The eifect of most anionic detergents is slight on the inhibiting effect of phosphated glyceryl ether in water of varying hardness. The following test shows the weight loss in milligrams, in the standard test with 0.18% sodium tripolyphosphate, 0.06% anionic, 0.02% phosphated alkyl glyceryl ether.
  • the figure shows the range over which the phosphate'd alkyl glyceryl ether is effective as a corrosion inhibitor.
  • the curve is about flattened out at 0.030% but it is obvious that up to 20% of the sodium tripolyphosphate concentration (20% of 0.l8%).036% would be useful. While this test was made at a pH of 9.5, tests conducted at other pHs show that the phosphated alkyl glyceryl ethers are effective at a wide range of pH values.
  • alkyl glyceryl ether phosphates are not eifective to inhibit corrosion when used in amounts less than 1% by weight of thesodium tripolyphosphate, they are effective as a tarnish inhibitor for German silver in lesser amounts.
  • the tarnishing of German silver was no more noticeable than when 0.02% benzotriazole was substituted for the alkyl glyceryl ether phosphate in the same formula.
  • EXAMPLE V 50.0 parts by weight sodium tripolyphosphate 17.5 parts by weight anionic detergent (about equal proportions of sodium alkyl sulfate wherein the alkyl is about 65% dodecyl radicals, the remainder being decyl and tetradecyl; and sodium polypropylene benzene sulfonate wherein the polypropylene averages about 12 carbon atoms 15. parts by weight sodium sulfate 6.0 parts by weight sodium silicate 11.3 parts by weight water and miscellaneous .25 part 'by weight alkyl (tallow) glyceryl ether phosphate Since the benzotriazole as described in US. Letters Patents 2,618,606 and 2,618,608 is one of the most effec tive tarnish inhibitors used with sodium tripolyphosphate,
  • this example shows that the alkyl glyceryl ether phosphate will be effective in amounts as small as 0.5% of the sodium tripolyphosphate.
  • the type of synthetic detergent that is present with the calcium sequestrant has only a moderate effect on the inhibiting effect of the alkyl glyceryl ether phosphate.
  • Sterox CD made by Monsanto is a tall oilxethylene oxide condensate about nine moles of ethylene oxide being condensed with one mole of tall oil.
  • Pluronic F68 (Wyandotte) is a condensate of ethylene oxide with a hydrophobic base formed by condensing propylene oxide With propylene glycol.
  • the molecular weight is about
  • RXMA the anionics and nonionics which can be compounded with calcium sequestrants and be improved by the addition of alkyl glyceryl ether phosphate
  • the anionics may be denoted by the formula RXMA where R is the hydrophobe, usually from 10 to 20 carbons,-and may be (1) fatty acid including acid chloride, (2) alcohol, and (3) alkylaryl;
  • X is the linkage, which may be (1) direct, (2) ester, (3) ether, (4) amide, (5) polyethenoxy (at least ten different types), and (6) multiple;
  • M is the hydrophilic group, which may be a (l) sulfate, (2) sulfonate and (3) phosphate; and
  • A is the alkali group including (1) sodium, (2) potassium, (3) lithium, (4) ammonia, (5) substituted ammonia, (6) magnesium, and (7) calcium.
  • the nonionic synthetic detergents have a hydrophobe similar to the hydrophobe in the anionics, but somewhat more diverse in structure and have an active carboxyl or hydroxyl group.
  • the hydrophobe is usually linked directly to the hydrophilic group although a linkage group is present in some nonionics.
  • the hydrophilic group is usually ethylene ether containing 5 to 30 ethylene oxide radicals although propylene oxide and mixtures of ethylene oxide and a propylene oxide may be used.
  • the ethylene oxide will react with hydroxyl on the hydrophobe to form an ether linkage or with a carboxyl on the hydrophobe to form an ester linkage.
  • carboxyl or bydroxyl groups and with polyalkylene oxide groups containing from 5 to 30 moles, it will be perceived that the number of nonionic synthetic detergents is quite large.
  • the chemical formula for the phosphated alkyl glyceryl ether thatis the effective corrosion and tarnish inhibitor can be made by high pressure hydrogenation, which saturates the double bonds of. the tallow as well as con- -verting the tallow to the alcohol. These may also be made by low pressure hydrogenation of the tallow, followed by sodium reduction to form the alcohol. Both are called hydrogenated.
  • the phosphated'alk yl glyceryl ethers of this invention should contain alkyl radicals-of 14m 18 carbons, either singly or-in mixtures, and. any suchothers, or mixtures thereof, may be substituted in any of the 'foregoing specific examples with comparable results.
  • a detergent composition comprising a calcium scquestrant selected from the group consisting of watersoluble salts of tripolyphosphoric acid, of ethylene diamine tetra acetic acid, of hydroxy ethyl ethylene diamine triacetic acid, of nitrilo triacetic acid, and mixtures there of, and the reaction product of an alkyl glyceryl ether, containing from14 to 18 carbon atomsin-thealkyl chain, with an amount of inorganic phosphating agent sufiicient to supply at least one gram-atomic weight of phosphorous per gram-molecular weightof alkyl glyceryl ether, the said reaction product being present in an amount from about /2% to about 20% by weight of the calcium seqnestrant, the said detergentcomposition being inhibited from tarnishing coppery alloys and corroding aluminum and zinc by the said reaction product; a i
  • the detergent composition of claim 1 wherein the tarnish and corrosion inhibiting agent is the reaction product of the alkyl glyceryl ether with an amount of phosphating agent sufficient to supply two gram-atomic weights of phosphorous per gram-molecular weight of ether, and the said reaction product contains about 8% phosphorous by weight. 1 l a 7 5.
  • the detergent composition of claim 4 wherein the phosphating agent is phosphorous 'oxychloride and is present in the amount of two 'mole's per mole of the alkyl glyceryl ether.
  • a detergent composition inhibited'frorn tarnishing coppery alloys and from corroding aluminum and zinc which comprises a calcium sequestrant selected from the group consisting of the water-soluble salts of tripolyphosphoric acid, of ethylene diamine tetra acetic acid, of hydroxy ethyl ethylene diamine triacetic acid, of nitrilo triacetic acid, and mixtures thereof, anon soap' anionic organic synthetic detergent, and -'the 'reactionproduct of an alkyl glyceryl ether, contai fil glfrom 14 "to'1 8 carbon atoms in the alkyl chain, with'an amount of inorganic phosphating agent sufiicient to supply atleast one gramatomic weight of phosphorous per gram-molecular weight of alkyl glyceryl ether, the said reaction product being present in an amount from about%% to about 20% by weight of the calcium sequestrant.
  • a calcium sequestrant selected from the group consisting of the
  • a detergent composition inhibited from tarnishing coppery alloys and from corroding aluminum and zinc which comprises a calcium sequestrant selected from the group consisting of the water-soluble salts of tripolyphosphoric acid,.of ethylene diamine tetra acetic acid, of hydroxy ethyl ethylene diamine triacetic acid, of nitrilo triacetic acid, and mixtures thereof, a non-soap nonionic organic syntheticjdetergent, and the reaction product of an alkyl glyceryl ether, containing from 14 to 18 carbon atoms in the alkyl chain, with an'amount of inorganic phosphating agent sufficient to supply at least one gramatomic weight of phosphorous per gram-molecular weight of alkyl glyceryl ether, the said reaction product being present in an amount from about V2% to about 20% by weight of the calcium sequestrant.
  • a calcium sequestrant selected from the group consisting of the water-soluble salts of tripolyphosphoric acid

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US614186A 1956-10-05 1956-10-05 Detergent composition containing phosphated alkyl glyceryl ether corrosion and tarnish inhibitor Expired - Lifetime US2892796A (en)

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Application Number Priority Date Filing Date Title
BE561095D BE561095A (enrdf_load_stackoverflow) 1956-10-05
US614186A US2892796A (en) 1956-10-05 1956-10-05 Detergent composition containing phosphated alkyl glyceryl ether corrosion and tarnish inhibitor
GB30849/57A GB846499A (en) 1956-10-05 1957-10-02 Improvements in non-corrosive synthetic detergent compositions
DEP19413A DE1079773B (de) 1956-10-05 1957-10-02 Wasch- und Reinigungsmittel
FR1186366D FR1186366A (fr) 1956-10-05 1957-10-04 Nouvelles compositions détersives

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BE (1) BE561095A (enrdf_load_stackoverflow)
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FR (1) FR1186366A (enrdf_load_stackoverflow)
GB (1) GB846499A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3351558A (en) * 1966-09-06 1967-11-07 Procter & Gamble Detergent composition containing organic phosphonate corrosion inhibitors
US4347194A (en) * 1980-06-25 1982-08-31 The Dow Chemical Co. Polyhydroxyl polyether compounds containing phosphorus
US7118685B1 (en) * 1999-07-13 2006-10-10 Kao Corporation Polishing liquid composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356613A (en) * 1966-09-27 1967-12-05 Procter & Gamble Built detergent compositions containing a synergistic mixture of stp, nta, and sodium silicate
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same
US3483033A (en) * 1966-08-23 1969-12-09 John A Casey Evaporator scale prevention in sugar manufacture

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2224695A (en) * 1938-11-25 1940-12-10 Carl F Prutton Inhibitor
US2618603A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors
US2744128A (en) * 1952-02-29 1956-05-01 Shell Dev Olefinically unsaturated phosphates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2224695A (en) * 1938-11-25 1940-12-10 Carl F Prutton Inhibitor
US2618603A (en) * 1949-02-04 1952-11-18 Procter & Gamble Detergent compositions containing metal discoloration inhibitors
US2744128A (en) * 1952-02-29 1956-05-01 Shell Dev Olefinically unsaturated phosphates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3001945A (en) * 1959-04-29 1961-09-26 Procter & Gamble Liquid detergent composition
US3351558A (en) * 1966-09-06 1967-11-07 Procter & Gamble Detergent composition containing organic phosphonate corrosion inhibitors
US4347194A (en) * 1980-06-25 1982-08-31 The Dow Chemical Co. Polyhydroxyl polyether compounds containing phosphorus
US7118685B1 (en) * 1999-07-13 2006-10-10 Kao Corporation Polishing liquid composition
US20060240672A1 (en) * 1999-07-13 2006-10-26 Kao Corporation Polishing liquid composition
US7604751B2 (en) 1999-07-13 2009-10-20 Kao Corporation Polishing liquid composition

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GB846499A (en) 1960-08-31
FR1186366A (fr) 1959-08-21
BE561095A (enrdf_load_stackoverflow)
DE1079773B (de) 1960-04-14

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