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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
• • 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
  • C11D1/66—Non-ionic compounds
• • 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
  • C11D3/044—Hydroxides or bases
• • 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
  • 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
  • C11D3/08—Silicates
• • 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
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/361—Phosphonates, phosphinates or phosphonites
• • 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
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/06—Hydroxides
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/12—Carbonates bicarbonates
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
  • C11D7/14—Silicates
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• This invention relates generally to cleaning compositions. More specifically, the invention relates to cleaning compositions that exhibit reduced scaling, for instance in warewash applications.
• Warewash formulations typically make use of high levels of caustic or ash to buffer the pH of the washing liquor at the high end of the alkaline region. These systems may also use low concentrations of surfactant (to emulsify food soil and prevent water spotting), phosphonates (as threshold inhibitors to prevent calcium carbonate scale from forming), bleach (to sanitize ware and control spotting on glassware) and polyacrylate dispersants (to keep inorganic scale formation and deposition in check).
• surfactant to emulsify food soil and prevent water spotting
• phosphonates as threshold inhibitors to prevent calcium carbonate scale from forming
• bleach to sanitize ware and control spotting on glassware
• polyacrylate dispersants to keep inorganic scale formation and deposition in check.
• dishware such as glasses, plates and tableware, that are heavily encrusted with inorganic scaling.
• Soluble silicates are known to provide corrosion inhibition of various substrates during the dishwashing process. They are also effective chelants of magnesium ions. The negative associated with utilizing silicates in warewash, however, is the formation of magnesium silicate scale, which is usually very difficult to remove/clean once deposited on dishware.
• compositions that are effective at inhibiting scale/spotting in warewash applications are desirable in the industry.
• compositions as described herein which contain a sulfonate polymer and a water soluble silicate, exhibit favorable cleaning properties.
• the composition overcomes the shortcomings previously experienced with conventional polyacrylate polymers and soluble silicates, such as unsatisfactory cleaning and increased magnesium scaling, particularly when used in the harsh conditions of warewashing. Accordingly, in one aspect, there is provided a composition useful for cleaning.
• the composition comprises: a polymer comprising polymerized units of (i) an ethylenically unsaturated carboxylic acid monomer or salt thereof, (ii) an ethylenically unsaturated sulfonic acid monomer or salt thereof, and optionally (iii) one or more further ethylenically unsaturated monomers or salt thereof, the polymer having a Mw from 2000 to 100,000; a water soluble silicate; an alkaline source; and optionally a surfactant.
• a method of cleaning an article in a warewashing machine comprises: applying to the article a composition as described herein.
• numeric ranges for instance as in “from 2 to 10,” are inclusive of the numbers defining the range (e.g., 2 and 10).
• ratios, percentages, parts, and the like are by weight.
• Mw refers to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and polyacrylic acid standards. GPC techniques are discussed in detail in Modem Size Exclusion Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly; Wiley-lnterscience, 1979, and in A Guide to Materials Characterization and Chemical Analysis, J. P.
• ethylenically unsaturated is used to describe a molecule or moiety having one or more carbon-carbon double bonds, which renders it polymerizable.
• ethylenically unsaturated includes monoethylenically unsaturated (having one carbon-carbon double bond) and multi-ethylenically unsaturated (having two or more carbon-carbon double bonds).
• (meth)acrylic refers to acrylic or methacrylic.
• Weight percentages (or wt %) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition.
• Percentages of monomer units in the polymer are percentages of solids weight, i.e., excluding any water present in a polymer emulsion.
• the invention provides a composition
• a composition comprising: a polymer comprising polymerized units of (i) an ethylenically unsaturated carboxylic acid monomer or salt thereof, (ii) an ethylenically unsaturated sulfonic acid monomer or salt thereof, and optionally (iii) one or more further monomers or salt thereof, the polymer having a Mw from 2000 to 100,000; a water soluble silicate; an alkaline source; and optionally a surfactant.
• the ethylenically unsaturated carboxylic acid monomer or salt thereof of the polymer is acrylic acid, methacrylic acid, their salts, or mixtures thereof.
• a preferred ethylenically unsaturated carboxylic acid monomer is acrylic acid.
• the ethylenically unsaturated carboxylic acid monomer or salt thereof comprises at least 50 weight percent, preferably at least 70 weight percent; and no more than 95 weight percent, preferably no more than 93 weight percent of the polymer. In some embodiments, the amount of the ethylenically unsaturated carboxylic acid monomer or salt thereof is from 50 to 95 weight percent, alternatively from 70 to 93 weight percent, of the polymer.
• the ethylenically unsaturated sulfonic acid monomer or salt thereof of the polymer is 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2- (meth)acrylamido-2-methylpropane sulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxy, 2-hydroxy 1-propane sulfonic acid (HAPS), 2-sulfoethyl(meth)acrylic acid, 2- sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, and 4- sulfobutyl(meth)acrylic acid, a salt thereof, or mixtures of two or more thereof.
• a preferred ethylenically unsaturated sulfonic acid monomer or salt thereof is 2-acrylamido-2- methylpropane sulfonic acid sodium salt.
• the ethylenically unsaturated sulfonic acid monomer or salt thereof comprises at least 5 weight percent, preferably at least 7 weight percent; and no more than 50 weight percent, preferably no more than 30 weight percent of the polymer. In some embodiments, the amount of the ethylenically unsaturated sulfonic acid monomer or salt thereof is from 5 to 50 weight percent, alternatively from 7 to 30 weight percent, of the polymer.
• one or more further ethylenically unsaturated monomers or their salts may be employed in the synthesis of the polymer.
• optional monomers include, without limitation acrylate esters (e.g., Ci-C 6 alkyl acrylate esters) and (substituted) amides (e.g., Ci-C 6 alkyl acryl amides).
• Preferred optional monomers include ethyl acrylate, butyl acrylate, tert-butyl acrylamide, and maleic anhydride.
• the optional monomer(s) preferably may comprise between 2 and 22 weight percent of the polymer.
• the polymer has a Mw of at least 8,000, preferably at least 9,000, preferably at least 10,000, preferably at least 11,000, preferably at least 12,000; and preferably no more than 70,000, preferably no more than 50,000, preferably no more than 30,000, preferably no more than 25,000. In some embodiments, the Mw ranges from 2,000 to 50,000.
• the polymer for use in the composition of the invention is derived from polymerized units of 50 to 95 weight percent (preferably 70 to 93 weight percent) acrylic acid and from 5 to 50 weight percent (preferably 7 to 30 weight percent) 2- acrylamido-2-methylpropane sulfonic acid sodium salt.
• the polymer has a Mw from 10,000 to 20,000, more preferably 14,000 to 18,000.
• the polymer is derived from polymerized units of 50 to 95 weight percent (preferably 55 to 82 weight percent) acrylic acid and from 5 to 50 weight percent (preferably 18 to 45 weight percent) 2-acrylamido-2-methylpropane sulfonic acid sodium salt.
• the polymer has a Mw from 10,000 to 20,000, more preferably 11,000 to 18,000.
• the polymer is derived from polymerized units of 60 to 90 weight percent (preferably 66 to 80 weight percent) acrylic acid and from 5 to 20 weight percent (preferably 10 to 17 weight percent) 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and 5 to 20 weight percent (preferably 10 to 17 weight percent) of ethyl acrylate.
• the polymer has a Mw from 25,000 to 45,000, more preferably 30,000 to 40,000.
• the polymer is derived from polymerized units of 50 to 90 weight percent (preferably 55 to 82 weight percent) acrylic acid and from 5 to 40 weight percent (preferably 10 to 35 weight percent) 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and 5 to 20 weight percent (preferably 8 to 17 weight percent) of t-butyl acrylamide.
• the polymer has a Mw from 2,000 to 10,000, more preferably 4,000 to 8,000.
• the polymer is derived from polymerized units of 50 to 95 weight percent (preferably 70 to 93 weight percent) acrylic acid and from 5 to 50 weight percent (preferably 7 to 30 weight percent) 2-hydroxy 1 -propane sulfonic acid sodium salt.
• the polymer has a Mw from 15,000 to 25,000, more preferably 19,000 to 22,000.
• the polymer is derived from polymerized units of 50 to 95 weight percent (preferably 85 to 95 weight percent) acrylic acid and from 5 to 50 weight percent (preferably 5 to 15 weight percent) 4-styrenesulfonic acid sodium salt.
• the polymer has a Mw from 2,000 to 10,000, more preferably 5,000 to 8,000.
• the polymer is derived from polymerized units of 50 to 90 weight percent (preferably 60 to 82 weight percent) acrylic acid, from 5 to 25 weight percent (preferably 8 to 20 weight percent) 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and 10 to 30 weight percent (preferably 10 to 22 weight percent) of maleic anhydride.
• the polymer has a Mw from 10,000 to 20,000, more preferably 12,000 to 16,000.
• the composition of the invention contains at least 0.5 weight percent, alternatively at least 3 weight percent, or alternatively at least 5 weight percent of the polymer, based on the total weight of the composition. In some embodiments, the amount of polymer is up to 12 weight percent, alternatively up to 10 weight percent, or alternatively up to 8 weight percent, based on the total weight of the composition.
• the polymer may be used in combination with other polymers useful for controlling insoluble deposits in warewashers, including, e.g., polymers comprising combinations of residues of acrylic acid, methacrylic acid, maleic acid or other diacid monomers, esters of acrylic or methacrylic acid including polyethylene glycol esters, styrene monomers, AMPS and other sulfonated monomers, and substituted acrylamides or methacrylamides.
• the polymer of this invention may be produced by any of the known techniques for
• Dispersant polymers for use in the invention are commercially available from various sources, and/or they may be prepared using literature techniques.
• low- molecular weight dispersant polymers may be prepared by free-radical polymerization.
• a preferred method for preparing these polymers is by homogeneous polymerization in a solvent.
• the solvent may be water or an alcoholic solvent such as 2-propanol or 1 ,2- propanediol.
• the free-radical polymerization is initiated by the decomposition of precursor compounds such as alkali persulfates or organic peracids and peresters.
• the activation of these precursors may be by the action of elevated reaction temperature alone (thermal activation) or by the admixture of redox-active agents such as a combination of iron(II) sulfate and ascorbic acid (redox activation).
• redox-active agents such as a combination of iron(II) sulfate and ascorbic acid (redox activation).
• a chain-transfer agent is typically used to modulate polymer molecular weight.
• One class of preferred chain-transfer agents employed in solution polymerizations is the alkali or ammonium bisulfites.
• the polymer may be in the form of a water-soluble solution polymer, slurry, dried powder, or granules or other solid forms.
• the composition of the invention contains a water soluble silicate. Suitable silicates typically have a water solubility of at least 10 g/100 mL at 25 °C, preferably at least 15 g/100 mL at 25 °C. Exemplary water soluble silicates for use in the invention include alkali metal silicates, preferably sodium silicate, sodium disilicate, sodium metasilicate, or mixtures thereof. A particularly suitable water soluble silicate is hydrous sodium silicate, available from PQ Corporation as BRITESIL® H20.
• the composition of the invention contains at least 1 weight percent, alternatively at least 3 weight percent, or alternatively at least 5 weight percent of the water soluble silicate, based on the total weight of the composition.
• the amount of water soluble silicate is up to 10 weight percent, alternatively up to 8 weight percent, alternatively up to 7 weight percent, or alternatively up to 5 weight percent, based on the total weight of the composition.
• composition of the invention also contains an alkaline source.
• alkaline sources include alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonate, sesquicarbonate, sodium, lithium, or potassium hydroxide, or mixtures of the foregoing.
• Sodium hydroxide is preferred.
• the composition contains at least 20 weight percent, alternatively at least 40 weight percent, or alternatively at least 60 weight percent of the alkaline source, based on the total weight of the composition. In some embodiments, the amount of alkaline source is up to 80 weight percent, alternatively up to 70 weight percent, or alternatively up to 65 weight percent, based on the total weight of the composition.
• the composition of the invention contains from 0.5 to 12 weight percent of the polymer, from 1 to 10 weight percent of the water soluble silicate, and from 20 to 80 weight percent of the alkaline source, based on the total weight of the composition.
• inclusion of the polymer and water soluble silicate at certain weight ratios has the effect of overcoming the shortcomings previously experienced with conventional polyacrylate polymers and water soluble silicates, such as unsatisfactory cleaning and increased magnesium scaling, for instance when used in the harsh conditions of warewashing.
• the composition contains the polymer and the water soluble silicate at a weight ratio of 6:1 to 1:3, alternatively 4:1 to 1:3, alternatively 3:1 to 1:3, alternatively 2:1 to 1:2, or alternatively 1:1.
• the weight ratio of polymer to water soluble silicate is from 2:1 to 1:1, alternatively from 2:1 to 1.2:1.
• the composition of the invention may contain one or more surfactants.
• Typical surfactant levels depend on the particular surfactant(s) used; preferably the total amount of surfactants is from 0.5 wt % to 15 wt%, preferably at least 0.7 wt%, preferably at least 0.9 wt%; preferably no more than 10 wt%, preferably no more than 7 wt%, preferably no more than 4 wt%, preferably no more than 2 wt%.
• the surfactant may be anionic, cationic, or nonionic.
• Exemplary nonionic surfactants include, without limitation, alkoxylate surfactants, particularly those based on ethylene oxide, propylene oxide, and/or butylene oxide.
• Examples include compounds having the formula RO-(M)x-(N)n-OH or R-0-(M)x- (N)y-O-R' in which M and N are units derived from alkylene oxides (of which one is ethylene oxide), x and y are integers from 0 to 20, provided at least one of them is not zero, R represents a C6-C22 linear or branched alkyl group, and R' represents a group derived from the reaction of an alcohol precursor with a C6- C22 linear or branched alkyl halide, epoxyalkane, or glycidyl ether.
• M is derived from ethylene oxide
• N is derived from butylene oxide.
• the composition may contain other optional components, for instance, oxygen and/or chlorine bleaches, bleach activators, enzymes, foam suppressants, colors, fragrances, builders, antibacterial agents and fillers.
• Fillers in tablets or powders are inert, water- soluble substances, typically sodium or potassium salts, e.g., sodium or potassium sulfate and/or chloride, and typically are present in amounts ranging from 0 wt% to75 wt%.
• Fillers in gel formulations may include those mentioned above and also water. Fragrances, dyes, foam suppressants, enzymes and antibacterial agents usually total no more than 5 wt% of the composition.
• the composition can be formulated in any typical form, e.g., as a tablet, powder, block, monodose, sachet, paste, liquid or gel.
• the compositions are useful for cleaning ware, such as eating and cooking utensils, dishes, in an automatic warewashing machine. They may also be used for cleaning other hard surfaces, such as showers, sinks, toilets, bathtubs, countertops, and the like.
• composition can be used under typical operating conditions. For instance, when used in an automatic warewashing machine, typical water temperatures during the washing process preferably are from 60 °C to 75 °C and typical rinse water temperatures during the rinse process preferably are from 75 °C to 88 °C. Typical concentrations for the
• compositions are from 500 to 2000 ppm in the wash liquor. With selection of an appropriate product form and addition time, the composition may be present in the prewash, main wash, penultimate rinse, final rinse, or any combination of these cycles.
• Acrylic Acid/ AMPS sodium salt copolymer (Polymer B in the examples below) may be prepared by a person of ordinary skill in the art using known methods. A typical procedure is as follows.
• a chain regulator solution of 6.7 grams sodium metabisulfite dissolved in 27 grams deionized water is added to a syringe for addition to the kettle.
• a promoter solution of 0.6 grams of a 0.15% iron sulfate heptahydrate solution is added to a vial and set aside.
• the promoter solution is added.
• the sodium bisulfite solution cofeed is begun, adding to the kettle over 105 minutes.
• the monomer and initiator cofeeds are started.
• the monomer feed is added over 110 minutes and initiator cofeed added over 112 minutes at 72°C.
• Polymer Molecular Weight may be measured by gel permeation chromatograph (GPC) using known methodology, for instance with the following typical parameters:
• degasser variable injection size autosampler, and column heater, or equivalent.
• Sample concentration Typically, 10 mg sample into 5 mL 20 mM AQGPC mobile phase solution.
• polymers as described in the examples below may be prepared by a person skilled in the art substantially as described above, with appropriate modifications to reagents and conditions.
• the additional monomers e.g., ethyl acrylate or butyl acrylamide
• the appropriate monomer may be simply exchanged for AMPS in the above synthesis.
• the maleic anhydride may be added to the kettle prior to the beginning of the feeds.
• Table 1 generally shows the ingredients used to prepare the tested formulations. Typically, a formulation is prepared by physically dry blending the ingredients. Table 1. Formulation Variables - Caustic Based Scenario
• PBTC 2-phosphonobutane-l, 2, 4-tricarboxylic acid.
• a Hobart AM- 15 high temperature dishwasher is used to assess the impact of inorganic scaling on Libbey-Collin glassware and plastic tumblers often found in a restaurant setting using various inventive and comparative cleaning formulations.
• the glasses are loaded into a pre-formed rack designed to readily fit into the warewash machine.
• the cleaning cycle involves a very short (35-45 second) wash cycle at elevated
• Polymer B is a copolymer based on 72 wt% acrylic acid and 28 wt% 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and having a molecular weight of 14,000 to 18,000. Polymer B falls within the polymer claimed in the invention.
• the tested formulations also either do or do not contain a water soluble silicate (Britesil H20).
• the concentration of Polymer A or Polymer B, when present, in the Table 3 formulations is 6 weight percent.
• the concentration of water soluble silicate when present is 5 weight percent.
• 3"St acrylonitrile is a styrene acrylonitrile tumbler.
• Example 1 in Table 3 demonstrates that formulations containing a conventional polyacrylate homopolymer (Polymer A) but no water soluble silicate in a caustic rich formulation, result in dishware in which glass scaling is evident after three cycles and continues to get progressively worse after 7 and 10 cycles, respectively.
• the plastic tumblers also show a high level of scale deposition.
• Example 2 demonstrates that replacing the acrylic acid homopolymer of Example 1 with an acrylic/sulfonated copolymer (Polymer B) results in comparable to slightly poorer performance profile on inorganic scaling.
• Example 3 shows that use of a water soluble silicate with the conventional Polymer A results in glassware filming scores that continue to be poor overall.
• Example 4 shows that the combination of Polymer B with the water soluble silicate, according to the invention, leads to a noticeably improved glass appearance with far less inorganic film deposition.
• the styrene acrylonitrile plastic tumbler is also far less scaled, even after 10 complete warewash cycles. Table 4.
• St Tumbler is a styrene tumbler.
• St acrylonitrile is a styrene acrylonitrile tumbler.
• Examples 5-12 in Table 4 examine the impact of polymer composition on the effectiveness of the cleaning formulation.
• Comparative Example 5 shows that in the presence of silicate, a conventional homopolymer continues to demonstrate poor overall performance on inorganic scale.
• inventive Examples 6-12 show that the presence of a sulfonated copolymer leads to a noticeably improved glass appearance with far less inorganic film deposition.
• the amount of polymer is 6 wt % and the amount of silicate is 5 wt %.
• Example 6 shows that a polymer based on 72 wt% acrylic acid and 28 wt% 2-acrylamido-2-methylpropane sulfonic acid sodium salt leads to a noticeably improved glass appearance with far less inorganic film deposition.
• the formulation in example 5 is the same formulation.
• Examples 7-12 contain silicate and an acrylic/sulfonate copolymer follows.
• Polymer C is based on 60 wt% acrylic acid and 40 wt% 2-acrylamido-2- methylpropane sulfonic acid sodium salt, having a molecular weight of 11-18 K.
• Polymer D is based on 70 wt% acrylic acid, 15 wt% 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and 15 % ethyl acrylate, having a molecular weight of 30-40 K.
• Polymer E is based on 62 wt% acrylic acid, 23 wt% 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and 15 wt% t-butyl acrylamide having a molecular weight of 4-8 K.
• Polymer F is based on 72 wt% acrylic acid and 28 wt% 2-hydroxy 1 -propane sulfonic acid sodium salt, having a molecular weight of 19-22 K.
• Polymer G is based on 90 wt% acrylic acid and 10 wt% 4-styrenesulfonic acid sodium salt having a molecular weight of 5-8 K.
• Polymer H is based on 70 wt% acrylic acid, 10 wt% 2-acrylamido-2-methylpropane sulfonic acid sodium salt, and 20 wt% maleic anhydride, having a molecular weight of 12- 16K.
• Examples 13-14 (Table 5) examine the effect of the ratio between the Polymer B and the water soluble silicate on the effectiveness of the cleaning formulations.
• the tested formulations all contain 2 weight percent of a nonionic surfactant based on ethylene oxide/butylene oxide.
• the formulations also contain the indicated amounts of Polymer B and water soluble silicate.
• Example 16 with a ratio of polymer to water soluble silicate of 2:1, demonstrated better overall filming results (reduced filming) than Examples 14 and 15.

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