US3852213A - Chelating compositions and detergent compositions pertaining to same - Google Patents
Chelating compositions and detergent compositions pertaining to same Download PDFInfo
- Publication number
- US3852213A US3852213A US00217225A US21722572A US3852213A US 3852213 A US3852213 A US 3852213A US 00217225 A US00217225 A US 00217225A US 21722572 A US21722572 A US 21722572A US 3852213 A US3852213 A US 3852213A
- Authority
- US
- United States
- Prior art keywords
- compositions
- chelating
- water
- calcium
- detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
Definitions
- citric acid, gluconic acid and glucoheptonate Thereare numerous problems associated with the use of the polyphosphates and NTA,.particularly in the area of pollution of streams, rivers and other drinking water sources while serious health problems, including death, have been reported in connection with the use of EDTA, NTA, HEDTA and DTPA.
- the use of citric acid, gluconic acid and glucoheptonate has also not proven successful because of the low chelating power of these agents and the requirement that they be used in large concentrations.
- PVM/MA copolymers As chelating agents in detergent and cleaning formulations. It is well known that such copolymers are non-toxic to both animals, fish and humans. Unfortunately, however, hydrolyzed PVM/MA copolymers have not been capable of chelating metal ions to the degree required for commercial acceptance.
- compositions comprising PVM/MA and borax are capable of chelating metal ions such as calcium, magnesium, iron, and manganese to a degree not possible with the PVM/MA copolymers alone, such compositions constituting commercially acceptable chelates.
- a feature of the invention is the provision of compositions comprising 3 30 percent borax and 97 70 percent PVM/MA.
- borax designates hydrated sodium tetrabo'rate'ln the preferred practice of the invention, borax sodium tetraborate is used either in its refined or crude state. Typical analyses of these two particular borates are as follows:
- boron compounds include inorganic alkali metal boron compounds, i.e., alkali metal borates, NaBO .2I-I O, Na B- O .5H O, NaBO Ll-I O, NaBO .4H O, K B O .5H O, LiBO .8I-I O and their corresponding acids as well as organic borate esters such as boron acetate, tricyclohexyl borate, tri-n-dodecyl borate, tri-(Z- ethylhexyl) borate, etc.
- alkali metal boron compounds i.e., alkali metal borates, NaBO .2I-I O, Na B- O .5H O, NaBO Ll-I O, NaBO .4H O, K B O .5H O, LiBO .8I-I O and their corresponding acids as well as organic borate esters such as boron acetate, tricyclohe
- the PVM/ MA copolymers employed in the compositions of the invention are known materials and are characterized by the following unit structural formula:
- mers suitable for use in this invention have a specific viscosity of from about 0.1. to about 3.5 and, preferably, have a specific viscosity of from about 0.1 to about 0.5.
- the specific viscosity is determined from a solution of l gram of the copolymer in ml. of methylethyl ketone at 25C. As is well known in the art, molecular weight is directlyrelated tothe specific viscosity.
- compositions comprising the PVM/ MA copolymer and borax or other suitable boron compound-to complex calcium, magnesium and other polyvalent metal ions is determined by analytical procedures in which the complexing agent is titrated with calcium in the presence of an indicator.
- the first chelating agent to be introduced to the chemical industry in the United States was EDTA. This compound was widely adopted because of its then unique ability to complex calcium and magnesium, as well as other polyvalent metal ions. Until the introduction of NTA by Hampshire Chemical Corporation, only ethylenediamine or substituted ethylenediamine-based chelating agents were suitable for use as amino acid sequestering agents for calcium and magnesium.
- the analytical procedure currently used throughout the chemical industry to test ethylenediamine-based chelating agents is one in which the complexing agent is titrated with calcium in the'presence of an indicator, which, in reality, is a precipitant for the metal ion.
- the chelating agent reacts with the metal ion as it is added to the system until the chelate is exhausted or reaches an equilibrium wherein the metal ion present is in excess of the amount required to react with the indicator it was found that the oxalate test was valid for ethylenediarnine only or substituted ethylenediamine-based compounds and that other chelating agents, most of which would not complex calcium, required other analytical procedures.
- the oxalate method I is a special case analytical method.
- the oxalate indicator because of the great insolubility of calcium oxalate, gives a premature end point with NTAwhich masks its useful chelating power. if a true indication of NTAs chelating ability is to be measured accurately, either Schwartzenbachs method which is accurate with any chelating agent or the calcium titration with a Na CO5 indicator is required to be used.
- the oxalate titration method is a good method-of control, the oxalate method is not suitable for all types of sequestering or chelating agents. Oxalate is useful, however, for comparing the relative sequestering power of ethylenediamine-based chelating agents.
- the three basic methods presently used to evaluate the sequestering power of chelating agents include the following:
- compositions of the invention can be used for thechemical treatment of water to prevent the formation of insoluble calcium and magnesium soaps and other hard water ions from precipitating in systems using large quantities of water.
- the softening of water both for industrial and non-industrial use is improved not only with respect to washing operations but also in avoiding the deposition of scale in boilers, condensers, heat exchangers or-conditioning systems and the like.
- compositionsof the invention can also be used for the treatment of water for the purpose of clarifying the same. Addition of the compositions of the invention to turbid river. water, for instance, results in the removal by sequestering of the substances giving rise to the turbidity.
- the PVM/ MA bo'rax compositions of the invention can be incorporated into detergents resulting in improved detergency, i.e., enhanced cleaning capacity.
- the compositions of the invention can be incorporated into liquid and solid detergents where the essential ingredients are, in addition to the compositions of the invention, at least one organicwater-soluble detergent surface active material.
- the detergent surface active compounds which can be used within the compositions of the invention include anionic, non-ionic, zwitterionic, ampholytic detergent compounds and mixtures thereof.
- anionic detergent compounds include both soap and non-soap detergent compounds.
- suitable soaps are sodium, potassium, ammonium and alkylol ammonium salts of higher fatty acids (C
- anionic organic non-soap detergent compounds are the water-soluble salts, alkali metal salts. of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid radical.
- Non-ionic synthetic detergents may be broadly defined as aliphatic or alkylaromatic in nature which do not ionize in water solution. This includes the wellknown class of non-ionic synthetic detergents marketed under the trade name of Pluronic.” These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol.
- Ampholytic synthetic detergents can be broadly de-- scribed as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
- This class of compounds include sodium-3- dodecylaminopropionate and sodium-3- dodecylaminopropanesulfonate.
- Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary amino compounds in which the aliphatic radical may be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
- Examplesof compounds in this group are 3- (N,N-dimethyl-N-hexade cylammonio)propanel sulfonate and 3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxy-propane-1-sulfonate.
- organic surfactants can be used singly or in combination.
- the detergent compositions can be formulated in any of the commercially desirable composition forms, for example, granulated, foam, liquid or tablet.
- compositions of, the invention can contain the conventional ingredients in minor amounts, such as soil redeposition inhibitors, such as soluble sodium carboxymethylcellulose, corrosion and tarnish inhibitors, such as soluble silicates, benzotriazole or ethylenethio-urea, sodium sulfate and sodium carbonate.
- soil redeposition inhibitors such as soluble sodium carboxymethylcellulose
- corrosion and tarnish inhibitors such as soluble silicates, benzotriazole or ethylenethio-urea
- sodium sulfate and sodium carbonate such as sodium sulfate and sodium carbonate.
- EXAMPLE 1 4.5 grams of PVM/MA copolymer were dissolved 'in 85 grams of water at l50-l60F. 2.5 grams of borax were then added and the resultant solution allowed to cool.
- the ability of the resultant material to chelate calcium was determined by'using the calcium carbonate titration procedure above set out and amounted to 100 mg. CaCo per gram of composition.
- EXAMPLE 2 12.5 grams of PVM/MA were dissolved in 87 grams of water at 150% l60F 0.5 grams of borax were then added and the resultant material allowed tocool. The ability of the composition to chelate calcium was determined by the carbonate method above described and amounted to 100 mg. of calcium carbonate per gram of composition.
- EXAMPLE 3 EXAMPLE 4 grams of PVM/MA in powder form were dryblended with 20 grams of borax. 1 gram of the resultant mix was dissolved in hot water having a temperature of l501 60F. When tested for chelating ability, according to the calcium carbonate method,'this mixture was capable of chelating 627 mg. calcium carbonate per gram of composition.
- composition of the invention was incorporated in conventional dyeing, bleaching and scouring agents for use in the treatment of cotton and cotton-polyester materials.
- the materials of the invention were, in each instance, found to be at least the equivalent of the EDTA and'the polyphosphates for the purpose investigated. e
- Triton X-l00 (condensation product of isooctyl phenol 10 moles of ethylene oxide) 20 Water balance This composition performed extremely well in hard water laundry usage as well as in hard water dish washing usage.
Abstract
Description
Claims (1)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00217225A US3852213A (en) | 1972-01-12 | 1972-01-12 | Chelating compositions and detergent compositions pertaining to same |
CA160,432A CA1009112A (en) | 1972-01-12 | 1973-01-03 | Chelating compositions and detergent compositions pertaining to same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00217225A US3852213A (en) | 1972-01-12 | 1972-01-12 | Chelating compositions and detergent compositions pertaining to same |
Publications (1)
Publication Number | Publication Date |
---|---|
US3852213A true US3852213A (en) | 1974-12-03 |
Family
ID=22810171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00217225A Expired - Lifetime US3852213A (en) | 1972-01-12 | 1972-01-12 | Chelating compositions and detergent compositions pertaining to same |
Country Status (2)
Country | Link |
---|---|
US (1) | US3852213A (en) |
CA (1) | CA1009112A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0018344A1 (en) * | 1979-04-09 | 1980-10-29 | THE PROCTER & GAMBLE COMPANY | Method and composition to inhibit staining of porcelain surfaces by manganese, and toilet tank dispenser using this composition |
US4302350A (en) * | 1979-04-09 | 1981-11-24 | The Procter & Gamble Company | Method and composition to inhibit staining of porcelain surfaces by manganese |
US4532047A (en) * | 1984-06-29 | 1985-07-30 | Nalco Chemical Company | Silica inhibition: prevention of silica deposition by addition of low molecular weight organic compounds |
US4552665A (en) * | 1984-05-04 | 1985-11-12 | Calgon Corporation | Stabilization of soluble manganese and its reaction products |
US4584104A (en) * | 1984-06-29 | 1986-04-22 | Nalco Chemical Company | Silica inhibition: prevention of silica deposition by boric acid/orthorborate ion |
US5141675A (en) * | 1990-10-15 | 1992-08-25 | Calgon Corporation | Novel polyphosphate/azole compositions and the use thereof as copper and copper alloy corrosion inhibitors |
US5597514A (en) * | 1995-01-24 | 1997-01-28 | Cortec Corporation | Corrosion inhibitor for reducing corrosion in metallic concrete reinforcements |
US5599433A (en) * | 1995-01-17 | 1997-02-04 | Beckman Instruments, Inc. | Capillary electrophoresis of glycosylated proteins |
US5614028A (en) * | 1993-03-17 | 1997-03-25 | Betzdearborn Inc. | Method of cleaning and passivating a metal surface with acidic system and ethoxylated tertiary dodecyl mercaptan |
US5750053A (en) * | 1995-01-24 | 1998-05-12 | Cortec Corporation | Corrosion inhibitor for reducing corrosion in metallic concrete reinforcements |
US6136219A (en) * | 1999-07-01 | 2000-10-24 | Decker; Stephen W. | Composition for water clarification |
CN106745849A (en) * | 2016-12-22 | 2017-05-31 | 新疆环境工程技术有限责任公司 | A kind of Integrated Films system-specific antisludging agent |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3623991A (en) * | 1969-06-10 | 1971-11-30 | Chemed Corp | Descaling detergent composition |
US3674699A (en) * | 1970-02-11 | 1972-07-04 | Hooker Chemical Corp | Noncorrosive cleaning composition and process |
US3700599A (en) * | 1970-09-25 | 1972-10-24 | Economics Lab | Composition for mechanically cleaning hard surfaces |
-
1972
- 1972-01-12 US US00217225A patent/US3852213A/en not_active Expired - Lifetime
-
1973
- 1973-01-03 CA CA160,432A patent/CA1009112A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3623991A (en) * | 1969-06-10 | 1971-11-30 | Chemed Corp | Descaling detergent composition |
US3674699A (en) * | 1970-02-11 | 1972-07-04 | Hooker Chemical Corp | Noncorrosive cleaning composition and process |
US3700599A (en) * | 1970-09-25 | 1972-10-24 | Economics Lab | Composition for mechanically cleaning hard surfaces |
Non-Patent Citations (1)
Title |
---|
Gantrez An Geneve Aniline & Film Corp., N.Y., N.Y., page 16 relied on, pub. 1961. * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0018344A1 (en) * | 1979-04-09 | 1980-10-29 | THE PROCTER & GAMBLE COMPANY | Method and composition to inhibit staining of porcelain surfaces by manganese, and toilet tank dispenser using this composition |
US4302350A (en) * | 1979-04-09 | 1981-11-24 | The Procter & Gamble Company | Method and composition to inhibit staining of porcelain surfaces by manganese |
US4552665A (en) * | 1984-05-04 | 1985-11-12 | Calgon Corporation | Stabilization of soluble manganese and its reaction products |
US4532047A (en) * | 1984-06-29 | 1985-07-30 | Nalco Chemical Company | Silica inhibition: prevention of silica deposition by addition of low molecular weight organic compounds |
US4584104A (en) * | 1984-06-29 | 1986-04-22 | Nalco Chemical Company | Silica inhibition: prevention of silica deposition by boric acid/orthorborate ion |
US5141675A (en) * | 1990-10-15 | 1992-08-25 | Calgon Corporation | Novel polyphosphate/azole compositions and the use thereof as copper and copper alloy corrosion inhibitors |
US5614028A (en) * | 1993-03-17 | 1997-03-25 | Betzdearborn Inc. | Method of cleaning and passivating a metal surface with acidic system and ethoxylated tertiary dodecyl mercaptan |
US5599433A (en) * | 1995-01-17 | 1997-02-04 | Beckman Instruments, Inc. | Capillary electrophoresis of glycosylated proteins |
US5597514A (en) * | 1995-01-24 | 1997-01-28 | Cortec Corporation | Corrosion inhibitor for reducing corrosion in metallic concrete reinforcements |
US5750053A (en) * | 1995-01-24 | 1998-05-12 | Cortec Corporation | Corrosion inhibitor for reducing corrosion in metallic concrete reinforcements |
US6136219A (en) * | 1999-07-01 | 2000-10-24 | Decker; Stephen W. | Composition for water clarification |
CN106745849A (en) * | 2016-12-22 | 2017-05-31 | 新疆环境工程技术有限责任公司 | A kind of Integrated Films system-specific antisludging agent |
Also Published As
Publication number | Publication date |
---|---|
CA1009112A (en) | 1977-04-26 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GAF CHEMICALS CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:DORSET INC.;REEL/FRAME:005251/0071 Effective date: 19890411 |
|
AS | Assignment |
Owner name: DORSET INC., A DE CORP. Free format text: CHANGE OF NAME;ASSIGNOR:GAF CORPORATION, A DE CORP.;REEL/FRAME:005250/0940 Effective date: 19890410 |
|
AS | Assignment |
Owner name: CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE Free format text: SECURITY INTEREST;ASSIGNOR:GAF CHEMICALS CORPORATION, A CORP. OF DE;REEL/FRAME:005604/0020 Effective date: 19900917 |
|
AS | Assignment |
Owner name: ISP INVESTMENTS INC. Free format text: CHANGE OF NAME;ASSIGNOR:ISP 3 CORP.;REEL/FRAME:005949/0051 Effective date: 19910508 Owner name: ISP 3 CORP Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GAF CHEMICALS CORPORATION;REEL/FRAME:005949/0001 Effective date: 19910508 |
|
AS | Assignment |
Owner name: GAF BUILDING MATERIALS CORPORATION Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION);REEL/FRAME:006243/0208 Effective date: 19920804 Owner name: GAF CHEMICALS CORPORATION Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION);REEL/FRAME:006243/0208 Effective date: 19920804 Owner name: SUTTON LABORATORIES, INC. Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION);REEL/FRAME:006243/0208 Effective date: 19920804 |