Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
• • 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
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  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2641—Polyacrylates; Polymethacrylates
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  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/38—Polysaccharides or derivatives thereof
  • C04B24/383—Cellulose or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
  • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
  • C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules
  • C08F291/08—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules on to macromolecules containing hydroxy radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/45—Anti-settling agents
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  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/02—Well-drilling compositions
  • C09K8/04—Aqueous well-drilling compositions
  • C09K8/06—Clay-free compositions
  • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/02—Well-drilling compositions
  • C09K8/04—Aqueous well-drilling compositions
  • C09K8/14—Clay-containing compositions
  • C09K8/18—Clay-containing compositions characterised by the organic compounds
  • C09K8/22—Synthetic organic compounds
  • C09K8/24—Polymers
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  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/40—Spacer compositions, e.g. compositions used to separate well-drilling from cementing masses
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
  • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
  • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
• • 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
  • C11D3/3788—Graft polymers
• • 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
  • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
  • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
  • C04B2103/0059—Graft (co-)polymers

Definitions

• the present invention relates to graft copolymers of synthetic and naturally derived materials. More particularly, the present invention is directed towards low molecular weight graft copolymers, as well as anti-scalant and/or dispersant formulations or compositions comprising such polymers and their use in aqueous systems, including scale minimization and dispersancy.
• aqueous industrial systems require that various materials remain in a soluble, suspended or dispersed state.
• aqueous systems include boiler water or steam generating systems, cooling water systems, gas scrubbing systems, pulp and paper mill systems, desalination systems, fabric, dishware and hard surface cleaning systems, as well as downhole systems encountered during the production of gas, oil, and geothermal wells.
• the water in those systems either naturally or by contamination contains ingredients such as inorganic salts. These salts can cause accumulation, deposition, and fouling problems in aqueous systems such as those mentioned above if they are not kept in a soluble, suspended or dispersed state.
• Inorganic salts are typically formed by the reaction of metal cations (e.g., calcium, magnesium or barium) with inorganic anions (e.g., phosphate, carbonate or sulfate).
• metal cations e.g., calcium, magnesium or barium
• inorganic anions e.g., phosphate, carbonate or sulfate.
• the salts tend to be insoluble or have low solubility in water.
• the salts can precipitate from solution, crystallize and form hard deposits or scale on surfaces. This scale formation is a problem in equipment such as heat transfer devices, boilers, secondary oil recovery wells, and automatic dishwashers, as well as on substrates washed with such hard waters, causing a reduction in the performance and life of the equipment.
• inorganic particulates such as mud, silt and clay can also be commonly found in cooling water systems. These particulates tend to settle onto surfaces, thereby restricting water flow and heat transfer unless they are effectively dispersed. Synthetic polymers such as polyacrylic acid are well known as excellent dispersants for these inorganic particulates.
• Stabilization of aqueous systems containing scale-forming salts and inorganic particulates involves a variety of mechanisms. Dispersion of precipitated salt crystals in an aqueous solution is one conventional mechanism for eliminating the deleterious effect of scale-forming salts. In this mechanism, the precipitants remain dispersed, as opposed to settling or dissolving in the aqueous solution. Synthetic polymers having carboxylic acid groups function as good dispersants for precipitated salts such as calcium carbonates.
• Another stabilization mechanism is inhibiting the formation of scale-forming salts.
• synthetic polymer(s) that can increase the solubility of scale-forming salts in an aqueous system are added.
• a third stabilization mechanism involves interference and distortion of the crystal structure of the scale by introduction of certain synthetic polymer(s), thereby making the scale less adherent to surfaces, other forming crystals and/or existing particulates.
• Synthetic polymers such as polyacrylic acid have been used to minimize scale formation in aqueous treatment systems for a number of years. Synthetic polymers can also impart many useful functions in cleaning compositions. For example, polyacrylic acid is widely used as a viscosity reducer in processing powdered detergents. Synthetic polymers can also serve as anti-redeposition agents, dispersants, scale and deposit inhibitors, and/or crystal modifiers, thereby improving whiteness maintenance in the washing process.
• Cleaning formulations can contain builders such as phosphates and carbonates for boosting their cleaning performance. These builders tend to precipitate out in the form of insoluble salts such as calcium carbonate, calcium phosphate, and calcium orthophosphate. The precipitants form deposits on clothes and dishware, resulting in unsightly films and spots on these articles. Similarly, these insoluble salts can cause major problem in downhole oilfield applications. Synthetic polymers such as polyacrylic acid are widely used to minimize the scaling of insoluble salts in water treatment, oilfield and cleaning formulations.
• graft copolymers typically do not perform as well as synthetic polymers in applications such as those described above (e.g., inhibition, dispersion and/or interference). Therefore, there is a need for graft copolymers that perform at least as well as their synthetic counterparts.
• the present invention discloses low molecular weight graft copolymers that function as an effective and at least partial replacement for synthetic polymers (e.g., polyacrylic acid) used in dispersancy applications in aqueous treatment systems. Additionally, the present invention discloses graft copolymers having a high degree of the natural component or constituent. Finally, the present invention discloses low or slightly colored graft copolymers and the processes for preparing these copolymers.
• synthetic polymers e.g., polyacrylic acid
• Low molecular weight graft copolymers according to the present invention are effective at minimizing a number of different scales, including phosphate, sulfonate, carbonate and silicate based scales.
• the scale-minimizing polymers are useful in a variety of systems, including water treatment compositions, oil field related compositions, cement compositions, cleaning formulations and other aqueous treatment compositions.
• Polymers according to the present invention have been found to be particularly useful in minimizing scale by dispersing precipitants, inhibiting scale formation, and/or interference and distortion of crystal structure.
• low molecular weight graft copolymer may be produced by grafting synthetic monomers onto hydroxyl-containing natural moieties.
• the resulting materials provide the performance of synthetic polymers while making use of lower cost, readily available and environmentally friendly materials derived from renewable sources. These materials can be used in water treatment, detergent, oil field and other dispersant applications.
• the low molecular weight graft copolymer is useful as a dispersant in water treatment and oilfield applications.
• the polymer is present in an amount of about 0.001% to about 25% by weight of the composition.
• the present invention further provides a process for making lighter color graft copolymers. In one aspect, this can be achieved by carrying out the polymerization reaction at acidic pH. Additionally, use of copper salts and lower feed times in the process allows for production of products low in color.
• the present invention provides for low molecular weight graft copolymers having a synthetic component formed from at least one or more olefinically unsaturated carboxylic acid monomers or salts thereof, and a natural component formed from a hydroxyl-containing natural moiety.
• the number average molecular weight of the graft copolymer is about 100,000 or less, and the weight percent of the natural component in the graft copolymer is about 5 wt % or greater based on total weight of the graft copolymer.
• the synthetic component in graft copolymers according to the present invention is further formed from one or more monomers having a nonionic, hydrophobic and/or sulfonic acid group, wherein the one or more monomers are incorporated into the copolymer in an amount of about 50 weight percent or less based on total weight of the graft copolymer. In another aspect, the one or more monomers are incorporated into the copolymer in an amount of about 10 weight percent or less based on total weight of the graft copolymer.
• the hydroxyl-containing natural moiety of the graft copolymer can be water soluble. In another aspect, the hydroxyl-containing natural moiety is degraded.
• the carboxylic acid monomer of the graft copolymer can be, for example, acrylic acid, maleic acid, methacrylic acid or mixtures thereof In one aspect, the carboxylic acid monomer is acrylic acid. In another aspect, the carboxylic acid monomer is acrylic acid and maleic acid.
• the weight percent of the natural component in the graft copolymer can be about 50 wt % or greater based on total weight of the graft copolymer.
• the natural component include glycerol, citric acid, maltodextrins, pyrodextrins, corn syrups, maltose, sucrose, low molecular weight oxidized starches and mixtures thereof.
• the present invention is directed towards cleaning compositions comprising the graft copolymer according to the present invention.
• the graft copolymer can be present in the cleaning composition in an amount of from about 0.01 to about 10 weight %, based on total weight of the cleaning composition.
• the cleaning composition can include one or more adjuvants.
• the cleaning composition can be a detergent composition, with the graft copolymer having a Gardner color of about 12 or less.
• the detergent composition can be a powdered detergent or unit dose composition.
• the detergent composition can be an autodish composition.
• the detergent composition can be a zero phosphate composition.
• the present invention is also directed towards a method of reducing spotting and/or filming in the rinse cycle of an automatic dishwasher by adding to the rinse cycle a rinse aid composition comprising a graft copolymer according to the present invention.
• the present invention is directed towards a method of improving sequestration, threshold inhibition and soil removal in a cleaning composition by adding a graft copolymer according to the present invention to a cleaning composition.
• the present invention is directed towards water treatment systems comprising graft copolymers according to the present invention.
• the graft copolymer can be present in the system in an amount of at least about 0.5 mg/L.
• the present invention is directed towards a method of dispersing and/or minimizing scale in an aqueous system by adding a graft copolymer according to the present invention to a water treatment system.
• the present invention is directed towards a method of dispersing pigments and/or minerals in an aqueous system by adding a dispersant composition comprising a graft copolymer according to the present invention to the aqueous system.
• the minerals dispersed include, for example, titanium dioxide, kaolin clays, modified kaolin clays, calcium carbonates and synthetic calcium carbonates, iron oxides, carbon black, talc, mica, silica, silicates, aluminum oxide or mixtures thereof.
• the present invention is directed towards a method of dispersing soils and/or dirt from hard and/or soft surfaces by treating the hard and/or soft surfaces with a cleaning composition comprising a graft copolymer according to the present invention.
• the present invention is directed towards a method of dispersing soils and/or dirt in aqueous systems by treating the aqueous system with an aqueous treatment composition comprising a graft copolymer according to the present invention.
• the present invention also provides for a process for producing low molecular weight graft copolymers having a synthetic component and a natural component.
• the process includes degrading the natural component to a number average molecular weight of about 100,000 or less, reacting the natural component with a free radical initiating system having a metal ion to generate free radicals on the natural component, and polymerizing the free radical-containing natural component with a synthetic component.
• the resultant low molecular weight graft copolymer has a Gardner color of about 12 or less.
• the process can also include polymerizing the free radical-containing natural component with the synthetic component at ambient pressure and a reaction temperature of about 40° C. to about 130° C.
• the metal ion in the free radical initiating system can be a Cu (II) salt. In one aspect, polymerization can occur at a pH of about 6 or less.
• Low molecular weight graft copolymers according to the present invention are produced by grafting synthetic monomers onto hydroxyl-containing naturally derived materials.
• hydroxyl-containing naturally derived materials range from small molecules such as glycerol, citric acid, lactic acid, tartaric acid, gluconic acid, glucoheptonic acid, monosaccharides and disaccharides such as sugars, to larger molecules such as oligosaccharides and polysaccharides (e.g., maltodextrins and starches). Examples of these include sucrose, fructose, maltose, glucose, and saccharose, as well as reaction products of saccharides such as mannitol, sorbitol and so forth.
• glycerol is a by-product of biodiesel production. Glycerol is also a by-product of oils and fats used in the manufacture of soaps and fatty acids. It can also be produced by fermentation of sugar. Citric acid is produced industrially by fermentation of crude sugar solutions. Lactic acid is produced commercially by fermentation of whey, cornstarch, potatoes, molasses, etc. Tartaric acid is one byproduct of the wine making process.
• Polysaccharides useful in the present invention can also be derived from plant, animal and microbial sources.
• examples of such polysaccharides include starch, cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectin and gellan.
• Starches include those derived from maize and conventional hybrids of maize, such as waxy maize and high amylose (greater than 40% amylose) maize, as well as other starches such as potato, tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth, including conventional hybrids or genetically engineered materials.
• hemicellulose or plant cell wall polysaccharides such as D-xylans. Examples of plant cell wall polysaccharides include arabino-xylans such as corn fiber gum, a component of corn fiber.
• Useful polysaccharides should be water soluble during the reaction. This implies that the polysaccharides either have a molecular weight low enough to be water soluble or can be hydrolyzed in situ during the reaction to become water soluble. For example, non-degraded starches are not water soluble. However, degraded starches are water soluble and can be used.
• hydroxyl-containing natural materials include oxidatively, hydrolytically or enzymatically degraded monosaccharides, oligosaccharides and polysaccharides, as well as chemically modified monosaccharides, oligosaccharides and polysaccharides.
• Chemically modified derivatives include carboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes, alkyl glycosides, alkyl-hydroxyalkyls, carboxy-alkyl ethers and other derivatives.
• the polysaccharide can be chemically modified before, during or after the grafting reaction.
• degraded polysaccharides according to the present invention can have a number average molecular weight of about 100,000 or lower.
• the number average molecular weight (Mn) of the low molecular weight graft copolymer is about 25,000 or less.
• the degraded polysaccharides have a number average molecular weight of about 10,000 or less.
• Polysaccharides useful in the present invention further include pyrodextrins.
• Pyrodextrins are made by heating acidified, commercially dry starch to a high temperature. Extensive degradation occurs initially due to the usual moisture present in starch. However, unlike the above reactions that are done in aqueous solution, pyrodextrins are formed by heating powders. As moisture is driven off by the heating, hydrolysis stops and recombination of hydrolyzed starch fragments occur. This recombination reaction makes these materials distinct from maltodextrins, which are hydrolyzed starch fragments. The resulting pyrodextrin product also has much lower reducing sugar content, as well as color and a distinct odor.
• maltodextrins are polymers having D -glucose units linked primarily by ⁇ -1,4 bonds and a dextrose equivalent (‘DE’) of less than about 20.
• Dextrose equivalent is a measure of the extent of starch hydrolysis. It is determined by measuring the amount of reducing sugars in a sample relative to dextrose (glucose). The DE of dextrose is 100, representing 100% hydrolysis. The DE value gives the extent of hydrolysis (e.g., 10 DE is more hydrolyzed than 5 DE maltodextrin).
• Maltodextrins are available as a white powder or concentrated solution and are prepared by the partial hydrolysis of starch with acid and/or enzymes.
• Polysaccharides useful in the present invention can further include corn syrups.
• Corn syrups are defined as degraded starch products having a DE of 27 to 95.
• specialty corn syrups include high fructose corn syrup and high maltose corn syrup.
• Monosaccharides and oligosaccharides such as galactose, mannose, sucrose, ribose, trehalose, lactose, etc., can be used.
• Polysaccharides can be modified or derivatized by etherification (e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride), esterification (e.g., via reaction with acetic anhydride, octenyl succinic anhydride (‘OSA’)), acid hydrolysis, dextrinization, oxidation or enzyme treatment (e.g., starch modified with ⁇ -amylase, ⁇ -amylase, pullanase, isoamylase or glucoamylase), or various combinations of these treatments. These treatments can be performed before or after the graft copolymerization process.
• etherification e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride
• esterification e.g., via reaction with acetic anhydride, octenyl succinic anhydride (‘OSA’)
• the natural component of the low molecular weight graft copolymer is glycerol, citric acid, maltodextrins and/or low molecular weight oxidized starches.
• Low molecular weight graft copolymers according to the present invention are grafted using olefinically unsaturated carboxylic acid monomers as the synthetic component.
• olefinically unsaturated carboxylic acid monomers include, for example, aliphatic, branched or cyclic, mono- or dicarboxylic acids, the alkali or alkaline earth metal or ammonium salts thereof, and the anhydrides thereof.
• olefinically unsaturated carboxylic acid monomers include but are not limited to acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloro-acrylic acid, ⁇ -cyano acrylic acid, ⁇ -methyl-acrylic acid (crotonic acid), ⁇ -phenyl acrylic acid, ⁇ -acryloxy propionic acid, sorbic acid, ⁇ -chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, ⁇ -styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, and 2-acryloxypropionic acid.
• Moieties such as maleic anhydride or acrylamide that can be derivatized to an acid containing group can be used.
• Combinations of olefinically unsaturated carboxylic acid monomers can also be used.
• the olefinically unsaturated carboxylic acid monomer is acrylic acid, maleic acid, or methacrylic acid, or mixtures thereof.
• These optional monomers can be a monomer with a non-ionic, hydrophobic or sulfonic acid group.
• the monomer can be incorporated into the copolymer at about 50 or less weight percent based on total weight of the low molecular weight graft copolymer.
• the optional monomer can be added at about 10 or less weight percent of the graft copolymer.
• the optional monomer can be added at about 4 or less weight percent of the graft copolymer.
• optional monomers with sulfonic acid groups include 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid and combinations thereof.
• optional hydrophobic monomers include saturated or unsaturated alkyl, hydroxyalkyl, alkylalkoxy groups, arylalkoxy, alkarylalkoxy, aryl and aryl-alkyl groups, alkyl sulfonate, aryl sulfonate, siloxane and combinations thereof.
• hydrophobic monomers examples include styrene, ⁇ -methyl styrene, methyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octyl acrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-methyl styrene, 4-propyl styrene,
• optional non-ionic monomers include C 1 -C 6 alkyl esters of (meth)acrylic acid and the alkali or alkaline earth metal or ammonium salts thereof, acrylamide and the C 1 -C 6 alkyl-substituted acrylamides, the N-alkyl-substituted acrylamides and the N-alkanol-substituted acrylamides, hydroxyl alkyl acrylates and acrylamides.
• the C 1 -C 6 alkyl esters and C 1 -C 6 alkyl half-esters of unsaturated vinylic acids such as maleic acid and itaconic acid
• C 1 -C 6 alkyl esters of saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid and valeric acid.
• the nonionic monomers are selected from the group consisting of methyl methacrylate, methyl acrylate, hydroxyethyl(meth)acrylate and hydroxypropyl(meth)acrylate.
• Low molecular weight copolymers according to the present invention perform similar to their synthetic counterparts, even at relatively high levels of the natural component within the copolymer.
• the natural component of the low molecular weight graft copolymer can be from about 10 to about 95 weight % based on total weight of the polymer. In one aspect, the range is from about 20 to about 85 weight % of the natural component based on total weight of the polymer. In another aspect, the weight percent of the natural component in the low molecular weight graft copolymer is about 40 wt % or greater based on total weight of the polymer. In even another aspect, the weight percent of the natural component in the low molecular weight graft copolymer is about 60 wt % or greater. In another aspect, the weight percent of the natural component in the low molecular weight graft copolymer is about 80 wt % or greater.
• materials described in the art tend to drop in performance when the amount of natural component is increased. This level depends on the monomers used and the end use application of the product. For example, in the case of acrylic acid grafted materials used in dispersant application, low molecular weight copolymers according to the present invention perform similar to their synthetic counterpart, even when the level of natural component is greater than 50, and even 65 weight percent of the polymer (see, e.g., Examples 6 and 7 infra), whereas graft copolymers found in the art do not (see, e.g., Comparative Example 1 infra).
• the number average molecular weight (Mn) of the low molecular weight graft copolymer is less than 100,000. In another aspect, the number average molecular weight of the low molecular weight graft copolymer is less than 25,000. In another aspect, the number average molecular weight of the polymer is less than 10,000. Optimum molecular weight depends on the monomers used in the grafting process and end use application. For example, acrylic acid grafted materials have been found to be excellent dispersants at Mn of less than 10,000.
• the natural component has a number average molecular weight of about 100,000 or lower. In another aspect, the natural component has a number average molecular weight of about 10,000 or lower.
• Natural component include materials such as maltodextrins and corn syrups having a DE of about 5 or greater. In another aspect, natural components have a DE of about 10 or greater.
• Low molecular weight graft copolymers according to the present invention have been found to be excellent dispersants in a wide variety of aqueous systems. These systems include but are not limited to water treatment, cleaning formulations, oilfield and pigment dispersion. These systems are described in further detail below. In another aspect, the low molecular weight graft copolymers have been found to be excellent sizing agents for fiberglass, non-wovens and textiles.
• Low molecular weight graft copolymers according to the present invention can also be used in a variety of cleaning formulations.
• Such formulations include both powdered and liquid laundry formulations such as compact and heavy duty detergents (e.g., builders, surfactants, enzymes, etc.), automatic dishwashing detergent formulations (e.g., builders, surfactants, enzymes, etc.), light-duty liquid dishwashing formulations, rinse aid formulations (e.g., acid, nonionic low foaming surfactants, carrier, etc.) and/or hard surface cleaning formulations (e.g., zwitterionic surfactants, germicide, etc.).
• compact and heavy duty detergents e.g., builders, surfactants, enzymes, etc.
• automatic dishwashing detergent formulations e.g., builders, surfactants, enzymes, etc.
• light-duty liquid dishwashing formulations e.g., rinse aid formulations (e.g., acid, nonionic low foaming surfactants, carrier,
• the graft copolymers can be used as viscosity reducers in processing powdered detergents. They can also serve as anti-redeposition agents, dispersants, scale and deposit inhibitors, and crystal modifiers, providing whiteness maintenance in the washing process.
• adjunct ingredient in any suitable amount can be used in the cleaning formulations described herein.
• Useful adjunct ingredients include, but are not limited to, aesthetic agents, anti-filming agents, antiredeposition agents, anti-spotting agents, beads, binders, bleach activators, bleach catalysts, bleach stabilizing systems, bleaching agents, brighteners, buffering agents, builders, carriers, chelants, clay, color speckles, control release agents, corrosion inhibitors, dishcare agents, disinfectant, dispersant agents, draining promoting agents, drying agents, dyes, dye transfer inhibiting agents, enzymes, enzyme stabilizing systems, fillers, free radical inhibitors, fungicides, germicides, hydrotropes, opacifiers, perfumes, pH adjusting agents, pigments, processing aids, silicates, soil release agents, suds suppressors, surfactants, stabilizers, thickeners, zeolite, and mixtures thereof.
• the cleaning formulations can further include builders, enzymes, surfactants, bleaching agents, bleach modifying materials, carriers, acids, corrosion inhibitors and aesthetic agents.
• Suitable builders include, but are not limited to, alkali metals, ammonium and alkanol ammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, nitrilotriacetic acids, polycarboxylates, (such as citric acid, mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl oxysuccinic acid, and water-soluble salts thereof), phosphates (e.g., sodium tripolyphosphate), and mixtures thereof.
• Suitable enzymes include, but are not limited to, proteases, amylases, cellulases, lipases, carbohydrases, bleaching enzymes, cutinases, esterases, and wild-type enzymes.
• Suitable surfactants include, but are not limited to, nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, and mixtures thereof.
• Suitable bleaching agents include, but are not limited to, common inorganic/organic chlorine bleach (e.g., sodium or potassium dichloroisocyanurate dihydrate, sodium hypochlorite, sodium hypochloride), hydrogen-peroxide releasing salt (such as, sodium perborate monohydrate (PB1), sodium perborate tetrahydrate (PB4)), sodium percarbonate, sodium peroxide, and mixtures thereof.
• Suitable bleach-modifying materials include but are not limited to hydrogen peroxide-source bleach activators (e.g., TAED), bleach catalysts (e.g. transition containing cobalt and manganese).
• Suitable carriers include, but are not limited to: water, low molecular weight organic solvents (e.g., primary alcohols, secondary alcohols, monohydric alcohols, polyols, and mixtures thereof), and mixtures thereof.
• Suitable acids include, but are not limited to, acetic acid, aspartic acid, benzoic acid, boric acid, bromic acid, citric acid, formic acid, gluconic acid, glutamic acid, hydrochloric acid, lactic acid, malic acid, nitric acid, sulfamic acid, sulfuric acid, tartaric acid, and mixtures thereof.
• Suitable corrosion inhibitors include, but are not limited to, soluble metal salts, insoluble metal salts, and mixtures thereof.
• Suitable metal salts include, but are not limited to, aluminum, zinc (e.g., hydrozincite), magnesium, calcium, lanthanum, tin, gallium, strontium, titanium, and mixtures thereof.
• Suitable aesthetic agents include, but are not limited to, opacifiers, dyes, pigments, color speckles, beads, brighteners, and mixtures thereof.
• the cleaning formulations described herein can be useful as automatic dishwashing detergent (‘ADD’) compositions (e.g., builders, surfactants, enzymes, etc.), light-duty liquid dishwashing compositions, laundry compositions such as, compact and heavy-duty detergents (e.g., builders, surfactants, enzymes, etc.), rinse aid compositions (e.g., acids, nonionic low-foaming surfactants, carriers, etc.), and/or hard surface cleaning compositions (e.g., zwitterionic surfactants, germicides, etc.).
• Cleaning formulations according to the present invention include both phosphate and zero-phosphate formulations.
• Suitable adjunct ingredients are disclosed in one or more of the following: U.S. Pat. Nos. 2,798,053; 2,954,347; 2,954,347; 3,308,067; 3,314,891; 3,455,839; 3,629,121; 3,723,322; 3,803,285; 3,929,107, 3,929,678; 3,933,672; 4,133,779; 4,141,841; 4,228,042; 4,239,660; 4,260,529; 4,265,779; 4,374,035; 4,379,080; 4,412,934; 4,483,779; 4,483,780; 4,536,314; 4,539,130; 4,565,647; 4,597,898; 4,606,838; 4,634,551; 4,652,392; 4,671,891; 4,681,592; 4,681,695; 4,681,704; 4,686,063; 4,702,857; 4,968,451; 5,332,528
• cleaning formulations according to the present invention can include from 0% to about 99.99% by weight of the formulation of a suitable adjunct ingredient. In another aspect, the cleaning formulations can include from about 0.01% to about 95% by weight of the formulation of a suitable adjunct ingredient.
• the cleaning formulations can include from about 0.01% to about 90%, or from about 0.01% to about 80%, or from about 0.01% to about 70%, or from about 0.01% to about 60%, or from about 0.01% to about 50%, or from about 0.01% to about 40%, or from about 0.01% to about 30%, or from about 0.01% to about 20%, or from about 0.01% to about 10%, or from about 0.01% to about 5%, or from about 0.01% to about 4%, or from about 0.01% to about 3%, or from about 0.01% to about 2%, or from about 0.01% to about 1%, or from about 0.01% to about 0.5%, or alternatively from about 0.01% to about 0.1%, by weight of the formulation of a suitable adjunct ingredient.
• Cleaning formulations can be provided in any suitable physical form. Examples of such forms include solids, granules, powders, liquids, pastes, creams, gels, liquid gels, and combinations thereof.
• Cleaning formulations used herein include unitized doses in any of a variety of forms, such as tablets, multi-phase tablets, gel packs, capsules, multi-compartment capsules, water-soluble pouches or multi-compartment pouches.
• Cleaning formulations can be dispensed from any suitable device. Suitable devices include, but are not limited to, wipes, hand mittens, boxes, baskets, bottles (e.g., pourable bottles, pump assisted bottles, squeeze bottles), multi-compartment bottles, jars, paste dispensers, and combinations thereof.
• cleaning formulations can be provided in a multi-compartment, water-soluble pouch comprising both solid and liquid or gel components in unit dose form.
• the use of different forms can allow for controlled release (e.g., delayed, sustained, triggered or slow release) of the cleaning formulation during treatment of a surface (e.g., during one or more wash and/or rinse cycles in an automatic dishwashing machine).
• the pH of these formulations can range from 1 to 14 when the formulation is diluted to a 1% solution. Most formulations are neutral or basic, meaning in the pH range of 7 to about 13.5. However, certain formulations can be acidic, meaning a pH range from 1 to about 6.5.
• Copolymers according to the present invention can also be used in a wide variety of cleaning formulations containing phosphate-based builders. These formulations can be in the form of a powder, liquid or unit doses such as tablets or capsules, and can be used to clean a variety of substrates such as clothes, dishes, and hard surfaces such as bathroom and kitchen surfaces. The formulations can also be used to clean surfaces in industrial and institutional cleaning applications.
• the polymer can be diluted in the wash liquor to end use level.
• the polymers are typically dosed at 0.01 to 1000 ppm in the aqueous wash solutions.
• Optional components in detergent formulations include, but are not limited to, ion exchangers, alkalies, anticorrosion materials, anti-redeposition materials, optical brighteners, fragrances, dyes, fillers, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, soil removal agents, soil release agents, fabric softening agent and opacifiers. These optional components can comprise up to about 90% by weight of the detergent formulation.
• the polymers of this invention can be incorporated into hand dish, autodish and hard surface cleaning formulations.
• the polymers can also be incorporated into rinse aid formulations used in autodish formulations.
• Autodish formulations can contain builders such as phosphates and carbonates, bleaches and bleach activators, and silicates. These polymers can also be used in reduced phosphate formulations (i.e., less than 1500 ppm in the wash) and zero phosphate autodish formulations. In zero-phosphate autodish formulations, removal of the phosphates negatively affects cleaning, as phosphates provide sequestration and calcium carbonate inhibition.
• Graft copolymers according to the present invention aid in sequestration and threshold inhibition, and therefore are suitable for use in zero-phosphate autodish formulations.
• the above formulations can also include other ingredients such as enzymes, buffers, perfumes, anti-foam agents, processing aids, and so forth.
• Hard surface cleaning formulations can contain other adjunct ingredients and carriers.
• adjunct ingredients include, without limitation, buffers, builders, chelants, filler salts, dispersants, enzymes, enzyme boosters, perfumes, thickeners, clays, solvents, surfactants and mixtures thereof.
• use levels can be about 0.01 weight % to about 10 weight % of the cleaning formulation. In another embodiment, use levels can range from about 0.1 weight % to about 2 weight % of the cleaning formulation.
• Foulants are loose, porous, insoluble materials suspended in water. They can include such diverse substances as particulate matter scrubbed from the air, migrated corrosion products, silt, clays and sand suspended in the makeup water, organic contaminants (oils), biological matter, and extraneous materials such as leaves, twigs and wood fibers from cooling towers. Fouling can reduce heat transfer by interfering with the flow of cooling water. Additionally, fouling can reduce heat transfer efficiency by plugging heat exchangers. Low molecular weight graft copolymers according to the present invention are excellent dispersants for foulants, and can minimize their deleterious effects in water treatment applications.
• Water treatment includes prevention of calcium scales due to precipitation of calcium salts such as calcium carbonate, calcium sulfate and calcium phosphate. These salts are inversely soluble, meaning that their solubility decreases as the temperature increases. For industrial applications where higher temperatures and higher concentrations of salts are present, this usually translates to precipitation occurring at the heat transfer surfaces. The precipitating salts can then deposit onto the surface, resulting in a layer of calcium scale. The calcium scale can lead to heat transfer loss in the system and cause overheating of production processes. This scaling can also promote localized corrosion.
• calcium salts such as calcium carbonate, calcium sulfate and calcium phosphate.
• Calcium phosphate unlike calcium carbonate, is generally not a naturally occurring problem.
• orthophosphates are commonly added to industrial systems (and sometimes to municipal water systems) as a corrosion inhibitor for ferrous metals, typically at levels between 2.0-20.0 mg/L. Therefore, calcium phosphate precipitation can not only result in those scaling problems previously discussed, but can also result in severe corrosion problems as the orthophosphate is removed from solution.
• industrial cooling systems require periodic maintenance wherein the system must be shut down, cleaned and the water replaced. Lengthening the time between maintenance shutdowns saves costs and is desirable.
• One way to lengthen the time between maintenance in a water treatment system is to use polymers that function in either inhibiting formation of calcium salts or in modifying crystal growth.
• Crystal growth modifying polymers alter the crystal morphology from regular structures (e.g., cubic) to irregular structures such as needlelike or florets. Because of the change in form, crystals that are deposited are easily removed from the surface simply by mechanical agitation resulting from water flowing past the surface.
• Low molecular weight graft copolymers according to the present invention are particularly useful at inhibiting calcium phosphate based scale formation such as calcium orthophosphate. Further, these inventive copolymers also modify crystal growth of calcium carbonate scale.
• Copolymers according to the present invention can be added to the aqueous systems neat, or they can be formulated into various water treatment compositions and then added to the aqueous systems.
• the copolymers can be used at levels as low as 0.5 mg/L.
• the upper limit on the amount of copolymer used depends upon the particular aqueous system treated. For example, when used to disperse particulate matter, the copolymer can be used at levels ranging from about 0.5 to about 2,000 mg/L.
• the copolymer can be used at levels ranging from about 0.5 to about 100 mg/L. In another embodiment the copolymer can be used at levels from about 3 to about 20 mg/L, and in another embodiment from about 5 to about 10 mg/L.
• the low molecular weight graft copolymers can be incorporated into an aqueous treatment composition that includes the graft copolymer and other aqueous treatment chemicals. These other chemicals can include, for example, corrosion inhibitors such as orthophosphates, zinc compounds and tolyltriazole.
• the amount of inventive copolymer utilized in water treatment compositions can vary based upon the treatment level desired for the particular aqueous system treated. Water treatment compositions generally contain from about 0.001 to about 25% by weight of the low molecular weight graft copolymer. In another aspect, the copolymer is present in an amount of about 0.5% to about 5% by weight of the aqueous treatment composition.
• Low molecular weight graft copolymers according to the present invention can be used in any aqueous system wherein stabilization of mineral salts is important, such as in heat transfer devices, boilers, secondary oil recovery wells, automatic dishwashers, and substrates that are washed with hard water.
• These graft copolymers can stabilize many minerals found in water, including, but not limited to, iron, zinc, phosphonate, and manganese. These copolymers also disperse particulates found in aqueous systems.
• Low molecular weight graft copolymers according to the present invention can be used to inhibit scales, stabilize minerals and disperse particulates in many types of processes.
• processes include sugar mill anti-scalant, soil conditioning, treatment of water for use in industrial processes such as mining, oilfields, pulp and paper production, and other similar processes, waste water treatment, ground water remediation, water purification by processes such as reverse osmosis and desalination, air-washer systems, corrosion inhibition, boiler water treatment, as a biodispersant, and chemical cleaning of scale and corrosion deposits.
• One skilled in the art can conceive of many other similar applications for which the low molecular weight graft copolymer could be useful.
• Scale formation is a major problem in oilfield applications.
• Subterranean oil recovery operations can involve the injection of an aqueous solution into the oil formation to help move the oil through the formation and to maintain the pressure in the reservoir as fluids are being removed.
• the injected water either surface water (lake or river) or seawater (for operations offshore) can contain soluble salts such as sulfates and carbonates. These salts tend to be incompatible with ions already present in the oil-containing reservoir (formation water).
• the formation water can contain high concentrations of certain ions that are encountered at much lower levels in normal surface water, such as strontium, barium, zinc and calcium.
• partially soluble inorganic salts such as barium sulfate and calcium carbonate often precipitate from the production water. This is especially prevalent when incompatible waters are encountered such as formation water, seawater, or produced water.
• Barium sulfate or other inorganic supersaturated salts such as strontium sulfate can precipitate onto the formation forming scale, thereby clogging the formation and restricting the recovery of oil from the reservoir. These salts can form very hard, insoluble scales that are difficult to prevent. The insoluble salts can also precipitate onto production tubing surfaces and associated extraction equipment, limiting productivity, production efficiency and compromising safety. Certain oil-containing formation waters are known to contain high barium concentrations of 400 ppm and higher. Since barium sulfate forms a particularly insoluble salt, the solubility of which declines rapidly with increasing temperature, it is difficult to inhibit scale formation and to prevent plugging of the oil formation and topside processes and safety equipment.
• Dissolution of sulfate scales is difficult, requiring high pH, long contact times, heat and circulation, and therefore is typically performed topside. Alternatively, milling and, in some cases, high-pressure water washing can be used. These are expensive, invasive procedures and require process shutdown.
• Use of low molecular weight graft copolymers according to the present invention can minimize these sulfate scales, especially downhole.
• Biodegradability in oil field applications is typically measured by OECD 306b testing, which is conducted in sea water. If the test sample is found to be greater than 60% biodegradable in 28 days, it is termed to be ‘readily biodegradable’, and if it is found to be greater than 20% biodegradable in 28 days, it is termed to be ‘inherently biodegradable’. Graft copolymers typically derive their biodegradable profile from their hydroxyl-containing natural moiety.
• graft copolymers according to the present invention can have at least about 20% by weight of hydroxyl-containing natural moiety, based on total weight of the graft copolymer. In another aspect, the graft copolymers have at least about 60% by weight. In order to be useful in oil field applications, performance of these graft copolymers should be similar to that of their synthetic counterparts, even with these high levels of hydroxyl-containing natural moieties.
• Graft copolymers according to the present invention can be used in a number of oil field applications such as cementing, drilling mud, general dispersancy and spacer fluid applications. These applications are described in some detail below.
• Water encountered in the oilfield can be very brackish. Often, the water encountered in oilfield applications is sea water or brines from the formation. Hence, useful polymers should be soluble in a variety of brines and brackish waters. Brines can be sea water containing, for example, about 3.5% by weight or more NaCl. Severe brines can contain, for example, up to 3.5% by weight KCl, up to 25% by weight NaCl, and/or up to 20% by weight CaCl 2 . Therefore, in order to be useful, polymers should be soluble in these systems for them to be effective, for example, as scale inhibitors. Typically, the higher the solubility of the graft copolymer in the brine, the higher its compatibility will be.
• graft copolymers according to the present invention are soluble at about 5 to about 1000 ppm levels in sea water. In another aspect these graft copolymers are soluble up to about 10,000 ppm levels. In even another aspect these graft copolymers are soluble up to about 100,000 ppm levels.
• graft copolymers according to the present invention are soluble at about 5 to about 1000 ppm levels in moderate calcium brine. In one aspect they are soluble up to about 10,000 ppm levels. In even another aspect they are soluble up to about 100,000 ppm levels.
• graft copolymers according to the present invention are soluble at about 5 to about 1000 ppm levels in severe calcium brine. In one aspect they are soluble up to about 10,000 ppm levels. In another aspect they are soluble up to about 100,000 ppm levels.
• a number of synthetic anionic polymers are not brine compatible.
• graft copolymers according to the present invention are extremely brine compatible. Without limiting the present invention, it is believed that this is because the hydroxyl-containing natural moiety adds non-ionic character to the graft copolymers, thereby enhancing their compatibility in these brine systems.
• Graft copolymers according to the present invention can have at least about 20% by weight of the hydroxyl-containing natural moiety, based on total weight of the graft copolymer. In another aspect, the copolymer can have at least about 60% by weight of the hydroxyl-containing natural moiety, based on total weight of the copolymer, for brine compatibility.
• the pH of the system typically is 5 and higher.
• the maleic acid constituent can be at least about 10 mole % of the synthetic component. In another aspect the maleic acid constituent is at least about 20 mole % of the synthetic component.
• compositions of synthetic seawater, moderate and severe calcium brines, which are typical brines encountered in the oilfield are listed in Table 1 below.
• a variety of procedures involving hydraulic cement compositions are utilized in the construction and repair of wells such as oil, gas and water wells.
• a pipe such as casing is disposed in the well bore and a hydraulic cement composition is pumped into the annular space between the walls of the well bore and the exterior of the pipe.
• the cement composition is allowed to set in the annular space whereby an annular cement sheath is formed therein which bonds the pipe to the walls of the well bore and prevents the undesirable flow of fluids into and through the annular space.
• hydraulic cement compositions are often utilized to plug holes or cracks in the pipe disposed in the well bore. These compositions can be also used to plug holes, cracks, voids or channels in the aforementioned cement sheath between the pipe and the well bore, as well as to plug permeable zones or fractures in subterranean formations and the like. These holes or cracks are repaired by forcing hydraulic cement compositions thereinto, which then harden and form impermeable plugs.
• Graft copolymers according to the present invention may be used as dispersants, set retarding, fluid loss or gas migration prevention additives in these cementing applications.
• the graft copolymers are made from anionic monomers containing carboxylic acid or phosphonic acid groups. Additionally, non-ionic monomers may be used to improve or enhance performance.
• Set retarded hydraulic cement compositions of this invention include hydraulic cement, sufficient water to form a slurry of the cement, and a copolymer set-retarding additive as described above.
• Various hydraulic cements can be utilized in the cement compositions, for example, Portland cement, and can be, for example, one or more of the various types identified as API Classes A-H and J cements. These cements are classified and defined in API Specification for Materials and Testing for Well Cements, API Specification 10A, 21st Edition dated Sep. 1, 1991, of the American Petroleum Institute, Washington, D.C.
• API Portland cement generally has a maximum particle size of about 90 microns and a specific surface (sometimes referred to as Blaine Fineness) of about 3900 square centimeters per gram.
• One embodiment of a cement slurry base for use in accordance with this invention includes API Class H Portland cement mixed with water to provide a density of from about 11.3 to about 18.0 pounds per gallon.
• fine particle size hydraulic cement is utilized.
• Such cement can include, for example, particles having diameters no larger than about 30 microns (‘ ⁇ m’) and Blaine Fineness no less than about 6000 square centimeters per gram.
• the fine cement particles have diameters no larger than about 17 ⁇ m.
• the particles are no larger than about 11 ⁇ m.
• the Blaine Fineness is greater than about 7000 square centimeters per gram.
• the Blaine Fineness is greater than about 10,000 square centimeters per gram. In even another aspect it is greater than about 13,000 square centimeters per gram.
• Water used in cement compositions of this invention can be water from any source provided that it does not contain an excess of compounds which adversely react with or otherwise affect other components in the cement compositions.
• Water is present in a cement composition of this invention in an amount sufficient to form a slurry of the cement, such as a slurry that is readily pumpable. Generally, water is present in an amount of from about 30% to about 60% by weight of dry cement in the composition when the cement is of normal particle size. When a cement of fine particle size as described above is used, water is present in the cement composition in an amount of from about 100% to about 200% by weight of dry cement in the composition.
• a dispersing agent such as one described in U.S. Pat. No. 4,557,763 is generally included to facilitate formation of the cement slurry and prevent the premature gelation thereof.
• Graft copolymers according to the present invention can be included in cement compositions in amounts sufficient to delay or retard setting of the compositions for time periods required to place the compositions in desired locations.
• the cement compositions When the cement compositions are utilized to carry out completion, remedial and other cementing operations in subterranean zones penetrated by well bores, the compositions must remain pumpable for periods of time long enough to place them in the subterranean zones to be cemented. Thickening and set times of cement compositions can be dependent upon temperature.
• a quantity of a copolymer set retarding additive according to the present invention is included in the cement composition so as to provide the necessary pumping time at the temperature encountered downhole. Such quantity can be determined in advance by performing thickening time tests of the type described in the above mentioned API Specification 10A.
• an aqueous solution containing a set retarding copolymer of this invention which is about 40% active is combined with a cement slurry.
• the copolymer is present in the resulting set retarded cement composition in an amount of from about 0.01% to about 5.0% by weight of dry cement in the composition.
• additives are often included in well cement compositions.
• Such other additives are well known to those skilled in the art and are added to well cement compositions to vary composition density, increase or decrease strength, control fluid loss, reduce viscosity, increase resistance to corrosive fluids, and the like.
• a cement composition meeting the specifications of the American Petroleum Institute is mixed with water and other additives to provide a cement slurry appropriate for the conditions existing in each individual well to be cemented.
• the methods of this invention for cementing a subterranean zone penetrated by a well bore are basically comprised of the steps of forming a pumpable set retarded cement composition of this invention, pumping the cement composition into the subterranean zone by way of the well bore, and then allowing the cement composition to set therein.
• a drilling fluid is circulated through the string of drill pipe, through the drill bit and upwardly to the earth's surface through the annulus formed between the drill pipe and the surface of the well bore, thereby cooling the drill bit, lubricating the drill string and removing cuttings from the well bore.
• another “performance” fluid such as slurry containing a cement composition is pumped into the annular space between the walls of the well bore and pipe string or casing.
• primary cementing the cement composition sets in the annulus, supporting and positioning the casing, and forming a substantially impermeable barrier or cement sheath that isolates the casing from subterranean zones.
• a spacer fluid is a fluid used to displace a performance fluid such as a drilling fluid in a well bore before introduction into the well bore of another performance fluid, such as a cement slurry.
• Spacer fluids are often used in oil and gas wells to facilitate improved displacement efficiency when pumping new fluids into the well bore. Spacer fluids are also used to enhance solids removal during drilling operations, to enhance displacement efficiency and to physically separate chemically incompatible fluids. For instance, in primary cementing, the cement slurry is separated from the drilling fluid and partially dehydrated gelled drilling fluid may be removed from the walls of the well bore by a spacer fluid pumped between the drilling fluid and the cement slurry. Spacer fluids may also be placed between different drilling fluids during drilling fluid change outs or between a drilling fluid and a completion brine.
• the present invention provides improved spacer fluids that can be interposed between the drilling fluid in the wellbore and either a cement slurry or a drilling fluid which has been converted to a cementitious slurry.
• the spacer fluid serves as a buffer between the drilling fluid and the cement slurry, as well as a flushing agent for evacuating the drilling fluid from the wellbore, thereby resulting in improved displacement efficiency of the drilling fluid removal and improved bonding of the cementitious slurry to surfaces in the wellbore such as the casing or drillpipe wall surfaces.
• the spacer fluid of the present invention comprises a graft copolymer dispersant and one or more additional components selected from surfactants, viscosifiers and weighting materials to form a theologically compatible fluid between the drilling fluid and the cementitious slurry.
• the present invention also provides a method of using the spacer fluid.
• a spacer fluid having a graft copolymer dispersant is introduced into the wellbore, and a completion fluid, such as cement slurry, is introduced to displace the spacer fluid.
• drilling fluids Any fluids used in a well bore during drilling operations may be termed a drilling fluids.
• the term is generally restricted to those fluids that are circulated in the bore hole in rotary drilling.
• the rotary system of drilling requires the circulation of a drilling fluid in order to remove the drilled cuttings from the bottom of the hole and thus keep the bit and the bottom of the hole clean.
• Drilling fluids are usually pumped from the surface down through a hollow drill pipe to the bit and the bottom of the hole and returned to the surface through the annular space outside the drill pipe. Any caving from the formations already drilled and exposed in the bore hole must be raised to the surface together with the drill cuttings by mud circulation.
• the casings and larger drill cuttings are separated from the mud at the surface by flowing the mud through a moving screen of a shale shaker and then settling in mud pits.
• the flowing drilling fluid cools the bit and the bottom of the hole.
• the mud usually offers some degree of lubrication between the drill pipe and the wall of the hole. Flows of oil, gas and brines into the well bore are commonly prevented by overbalancing or exceeding formation pressures with the hydrostatic pressure of the mud column.
• drilling mud One function of drilling mud is the maintenance and preservation of the hole already drilled.
• the drilling fluid should permit identification of drill cuttings and identification of any shows of oil or gas in the cuttings. It should also allow for the use of the desired logging materials and other well completion practices. Finally, the drilling fluid should not impair the permeability of any oil or gas bearing formations penetrated by the well.
• drilling fluids are drilling mud, which are suspensions of solids in liquids or in liquid emulsions.
• the densities of such systems are adjusted to between about 7 and about 21 lbs/gal, or about 0.85 to about 2.5 specific gravity. Where water is used as the liquid phase, the lower limit of the density is about 8.6 to about 9 lbs/gal.
• Filtration quality may be controlled by having a portion of the solids consist of particles of such small size and nature that very little of the liquid phase will escape through the filter cake of solids formed around the bore hole.
• Control over viscosity and gel forming character of such suspensions is achieved within limits by the amount and kind of solids in the suspension and by the use of chemicals for reducing the internal resistance of such suspensions so that they will flow easily and smoothly.
• the vast majority of drilling mud is suspension of clays and other solids in water, and is referred to as water based mud.
• Oil based mud is suspensions of solids in oil. High flash point diesel oils are commonly used in the liquids phase and the finely dispersed solid is obtained by adding oxidized asphalt. Common weighting agents are used to increase the density. Viscosity and thixotropic properties are controlled by surfactants and other chemicals. Oil based mud is used for special purposes such as preventing the caving of certain shale, as well as completion mud for drilling into sensitive sands that would be damaged by water.
• Water based mud includes a liquid phase, water and emulsion, a colloidal phase (e.g., clays), an inert phase (e.g., barite weight material and fine sand), and a chemical phase consisting of ions and substances in solution, which influence and control the behavior of colloidal materials such as clays.
• a colloidal phase e.g., clays
• an inert phase e.g., barite weight material and fine sand
• a chemical phase consisting of ions and substances in solution, which influence and control the behavior of colloidal materials such as clays.
• Colloidal materials produce higher viscosities in a mud for removing cuttings and caving from the hole and for suspending the inert materials such as finely ground barite.
• An example of one such material is bentonite, which is a rock deposit.
• the desirable material in the rock is montmorillonite.
• these clays produce mud that has low filtration loss.
• Special clays are used in mud saturated with salt water (e.g., attapulgite).
• Starch and sodium carboxymethyl cellulose are used as auxiliary colloids for supplementing the mud properties produced by the clays.
• Inert solids in drilling mud include silica, quartz and other inert mineral grains. These inert materials are finely ground weight material and lost circulation material.
• a commonly used weight material is barite, which has a specific gravity of 4.3. Barite is a soft mineral and therefore minimizes abrasion on the pump valves and cylinders. It is insoluble and relatively inexpensive and therefore is widely used.
• Lost circulation materials are added to the mud when losses of whole mud occur in crevices or cracks in exposed rocks in the well bore. Commonly used loss circulation materials include shredded cellophane flakes, mica flakes, cane fibers, wood fibers, ground walnut shells and perlite.
• the chemical phase of water based mud controls the colloidal phase particularly in the case of bentonite type clays.
• the chemical phase includes soluble salts which enter the mud from the drill cuttings and the disintegrated portions of the hole and those present in the make up water added to the mud.
• the chemical phase also includes soluble treating chemicals for reducing viscosity and gel strength of the mud. These chemicals include inorganic materials such as caustic soda, lime, bicarbonate of soda and soda ash. Phosphates such as sodium tetraphosphate may be used to reduce mud viscosities and gel strengths.
• the mud system contains calcium sulfate, a fluid loss reducing agent such as sodium carboxymethyl cellulose, and suitable surfactants.
• surfactants include a primary surfactant for controlling the rheological properties (viscosity and gelation) of the mud, a defoamer and an emulsifier.
• Perforation of earthen formations in order to tap subterranean deposits such as gas or oil is accomplished by well drilling tools and a drilling fluid.
• These rotary drilling systems consist of a drilling bit fitted with appropriate ‘teeth’, a set of pipes assembled rigidly together end to end, wherein the diameter of the piping is smaller than that of the drilling bit.
• This whole rigid piece of equipment—drill bit and drill pipe string— is driven into rotation from a platform situated above the well.
• the crushed mineral materials must be cleared away from the bottom of the hole to enable the drilling operation to continue.
• Aqueous clay dispersion drilling fluids are recirculated down through the hollow pipe, across the face of the drill bit, and upward through the hole.
• the drilling fluid cools and lubricates the drill bit, raises the drilling cuttings to the surface of the ground, and seals the sides of the well to prevent loss of water and drilling fluids into the formation through which the drill hole is being bored.
• the mud is passed through a settling tank or trough where sand and drill cuttings are separated, with or without screening.
• the fluid is then pumped again into the drill pipe by a mud pump.
• Copolymers according to the present invention can be used for scale inhibition where the scale inhibited is, for example, calcium carbonate, halite, calcium sulfate, barium sulfate, strontium sulfate, iron sulfide, lead sulfide and zinc sulfide and mixtures thereof.
• the scale inhibited is, for example, calcium carbonate, halite, calcium sulfate, barium sulfate, strontium sulfate, iron sulfide, lead sulfide and zinc sulfide and mixtures thereof.
• Halite is the mineral form of sodium chloride, commonly known as rock salt.
• the copolymers can have greater than 80% inhibition to be effective under practical end use conditions. In one aspect, the copolymers can have greater than 90% inhibition.
• the amount of copolymer needed to perform at this level depends on the scale to be inhibited. For example, calcium carbonate inhibitors can be be dosed at less than about 50 ppm. In one aspect, calcium carbonate inhibitors can be be dosed at less than about 20 ppm. In even another aspect, calcium carbonate inhibitors can be be dosed at less than about 10 ppm. Barium sulfate inhibitors can be dosed at, for example, less than about 100 ppm.
• barium sulfate inhibitors can be dosed at less than about 20 ppm. In even another aspect, barium sulfate inhibitors can be dosed at less than about 10 ppm. It is also a major advantage to have the same polymer inhibit more than one type of scale, such as combination of calcium carbonate and barium sulfate, or calcium carbonate and calcium phosphate, at less than about 100 ppm, or, in another aspect, less than 50 ppm.
• Copolymers of this invention can have to a number average molecular weight of less than 100,000. In another aspect, they can have a number average molecular weight of less than 10,000, and, in even another aspect, less than 5,000.
• Scaling not only causes a restriction in pore size in the reservoir rock formation matrix (also known as ‘formation damage’), thereby reducing the rate of oil and/or gas production, but also blockage of tubular and pipe equipment during surface processing.
• a method of inhibiting scaling in an aqueous system This is accomplished by adding a graft copolymer according to the present invention to the aqueous system.
• the scale inhibitor can be injected, squeezed (as described later on), or added topside to the produced water.
• the invention is also directed towards a mixture of the graft copolymer and a carrier fluid.
• carrier fluid include water, glycol, alcohol or oil.
• the carrier fluid is water, brines or methanol. Methanol is often used to prevent formation of water methane ice structures downhole.
• the graft copolymers of this invention are soluble in methanol.
• the scale inhibiting polymers can be introduced into the well bore in the methanol line. This is particularly advantageous when there is fixed number of lines that run into the wellbore, thereby eliminating the need for another line.
• Graft copolymers of this invention can have at least about 10% by weight saccharide functionality, based on total weight of the copolymer, to be soluble in methanol. In another aspect the graft copolymers have at least about 20% by weight saccharide functionality.
• aqueous systems include cooling water systems, water flood systems, and produced water systems.
• the aqueous environment may also be in crude oil systems or gas systems, and may be deployed downhole, topside, pipeline or during refining.
• the aqueous system may include CO 2 , H 2 S, O 2 , brine, condensed water, crude oil, gas condensate, or any combination of the said or other species.
• Copolymers of this invention may be deployed continuously or intermittently in a batch-wise manner into the aqueous system.
• copolymers according to the present invention are added topside and/or in a squeeze treatment.
• a squeeze treatment also called a “shut-in” treatment
• the scale inhibitor is injected into the production well, usually under pressure, “squeezed” into the formation, and held there.
• the scale inhibitor is injected several feet radially into the production well, where it is retained by adsorption and/or formation of a sparingly soluble precipitate.
• the inhibitor slowly leaches into the produced water over a period of time and protects the well from scale deposition.
• the “shut-in” treatment needs to be done regularly (e.g., one or more times a year) if high production rates are to be maintained.
• the treatment constitutes the “down time” when no production takes place.
• Copolymers of this invention are particularly good for this type of squeeze scale inhibition due to their saccharide functionality, which can be absorbed onto the formation and released over time.
• Polymers according to the present invention can be used as a dispersant for minerals in applications such as paper coatings, paints and other coating applications. These particulates are found in a variety of applications, including but not limited to, paints, coatings, plastics, rubbers, filtration products, cosmetics, food and paper coatings.
• minerals that can be dispersed by the inventive polymers include titanium dioxide, kaolin clays, modified kaolin clays, calcium carbonates and synthetic calcium carbonates, iron oxides, carbon black, talc, mica, silica, silicates, and aluminum oxide.
• the more hydrophobic the mineral the better polymers according to the present invention perform in dispersing particulates.
• the low molecular weight graft copolymer can be used as a binder for fiberglass.
• Fiberglass insulation products are generally formed by bonding glass fibers together with a synthetic polymeric binder.
• Fiberglass is usually sized with phenol-formaldehyde resins or polyacrylic acid based resins.
• the former has the disadvantage of releasing formaldehyde during end use.
• the polyacrylic acid resin system has become uneconomical due to rising crude oil prices. Hence, there is a need for renewal sizing materials in this industry.
• the low molecular weight graft polymers of this invention are a good fit for this application. They can be used by themselves or in conjunction with the with the phenol formaldehyde or polyacrylic acid binder system.
• the binder composition is generally applied by means of a suitable spray applicator to a fiber glass mat as it is being formed or soon after it is formed and while it is still hot.
• the spray applicator aids in distributing the binder solution evenly throughout the formed fiberglass mat.
• the polymeric binder solution tends to accumulate at the junctions where fibers cross each other, thereby holding the fibers together at these junctions.
• Solids are typically present in the aqueous solution in amounts of about 5 to 25 percent by weight of total solution.
• the binder can also be applied by other means known in the art, including, but not limited to, airless spray, air spray, padding, saturating, and roll coating.
• the resultant high-solids binder-coated fiberglass mat is allowed to expand vertically due to the resiliency of the glass fibers.
• the fiberglass mat is then heated to cure the binder.
• curing ovens operate at a temperature of from 130° C. to 325° C.
• the binder composition of the present invention can be cured at lower temperatures of from about 110° C. to about 150° C.
• the binder composition can be cured at about 120° C.
• the fiberglass mat is typically cured from about 5 seconds to about 15 minutes. In one aspect the fiberglass mat is cured from about 30 seconds to about 3 minutes.
• the cure temperature and cure time also depend on both the temperature and level of catalyst used.
• the fiberglass mat can then be compressed for shipping.
• An important property of the fiberglass mat is that it returns substantially to its full vertical height once the compression is removed.
• the low molecular weight graft polymer based binder produces a flexible film that allows the fiberglass insulation to bounce back after a roll is unwrapped for use in walls/ceilings.
• Fiberglass or other non-wovens treated with the copolymer binder composition is useful as insulation for heat or sound in the form of rolls or batts; as a reinforcing mat for roofing and flooring products, ceiling tiles, flooring tiles, as a microglass-based substrate for printed circuit boards and battery separators; for filter stock and tape stock and for reinforcements in both non-cementatious and cementations masonry coatings.
• the present invention provides a process for making graft copolymers at a lighter color.
• the graft copolymers are made using a redox system of a metal ion and hydrogen peroxide.
• the graft copolymers are made using free radical initiating systems such as ceric ammonium nitrate and Fe (II)/H 2 O 2 (see, Würzburg, O. B., M ODIFIED S TARCHES: P ROPERTIES AND U SES, Grafted Starches, Chpt. 10, pp. 149-72, CRC Press, Boca Raton (1986)).
• Fe (II) can be substituted with other metal ions such as Cu (II), Co (III), Mn (III) and others. Of these ions, Cu (II) appears to be the most effective and gives low molecular weight products.
• the amount of metal ions required depends on the metal ion used, the amount of H 2 O 2 used, the monomers to be grafted and the relative amount of natural component to synthetic monomer.
• the amount of metal ion needed can exceed 10, and in some cases 100, ppm based on moles of monomer, which is much higher than the 1 to 2 ppm typically used.
• the amount of metal ion can be given in terms of ppm as moles of the metal ion per total moles of monomer. For example, in the case of Fe (II), 10 ppm or greater moles of Fe based on moles of monomers can be used.
• 100 ppm or greater moles of Fe based on moles of monomers can be used.
• Cu (II) 1 ppm or greater moles of Cu based on moles of monomers can be used.
• 10 ppm or greater moles of Cu based on moles of monomers can be used.
• 100 ppm or greater moles of Cu based on moles of monomers can be used.
• Higher amounts of metal ion are needed when lower amount of H 2 O 2 are used.
• higher levels of the metal ion are needed when the amount of the natural component is high, for example, about 50 weight percent or greater of the total weight of natural component and synthetic monomer.
• the Cu (II) system is more effective than Fe (II) systems at lowering molecular weight (see, e.g., Examples 2 and 3).
• low molecular weight graft copolymers are produced having a Gardner color of 12 or less.
• polymerization is carried out at acidic pH, and Fe(II) and hydrogen peroxide are typically used as the initiating system.
• copper salts can be used instead of iron to produce lower color materials.
• lower feed times are used to produce products with low color. For example, comonomers like acrylic acid are fed in over a period of 5 to 6 hours to react with the sluggish maleic acid. Lowering the feed times to 3 to 4 hours and using Cu (II) salts such as copper sulfate lowers the color.
• polymerization occurs at low pH. In one aspect, polymerization occurs at a pH of about 6 or below. In another aspect, polymerization occurs at a pH of about 5 or below. In even another aspect, polymerization occurs at a pH of about 3 or below.
• Monomers such as maleic acid are sluggish in polymerization reactions. They need a certain amount of neutralization to react. They are typically added to the initial charge and neutralized at the same time. This leads to very dark colored materials. It is better to add the maleic in the initial charge. However, the maleic should not be completely neutralized in the initial charge. Caustic needs to be added slowly during the reaction so that the polymerization reaction is carried out under acidic pH conditions. Part of the neutralization agent may be added to the initial charge and the rest may be added in a feed. Alternatively, the maleic acid may be co-fed along with the neutralizing agent such as NaOH. Also, most of the products are neutralized at the end of the reaction. They need to be neutralized to below 6 to maintain a low color.
• the neutralizing agent such as NaOH
• reaction temperature ranges at ambient pressure can be about 40° C. to 130° C. In another aspect, the temperature range is 80° C. to 100° C. Higher temperatures can be used when the reaction (which is usually in an aqueous medium) occurs at pressures above ambient.
• Molecular weights of all the graft copolymers in the Examples below were determined by aqueous Gel Permeation Chromatography (‘GPC’) using a series of polyacrylic acid standards.
• the method uses 0.05M sodium phosphate (0.025M NaH 2 PO 4 and 0.025M Na 2 HPO 4 ) buffered at pH 7/0 with NaN 3 as the mobile phase.
• the columns used in this method are: TSKgel PWx1 Guard column, TSKgel; G6000PWx1, G4000PWx1, G3000PWx1, G2500PWx1 set at a temperature of 32° C.
• Flow rate is 1 mL per minute, and the injection volume is 450 ⁇ L.
• the instrument is calibrated using five different polyacrylic acids standards injected at five different concentrations: PAA1K (2.0 mg/mL), PAA5K (1.75 mg/mL), PAA85K (1.25 mg/mL), PAA495K (0.75 mg/mL), and PAA1700K (0.2 mg/mL), all from American Polymer Standards Corporation.
• Molecular weight of starting polysaccharides in the Examples below was determined by aqueous Gel Permeation Chromatography (GPC) using a series of hydroxyl ethyl starch standards.
• the method uses 0.05M sodium phosphate (0.025M NaH 2 PO 4 and 0.025M Na 2 HPO 4 ) buffered at pH 7/0 with NaN 3 as the mobile phase.
• the columns used in this method are: TSKgel PWx1 Guard column, TSKgel; G6000PWx1, G4000PWx1, G3000PWx1, and G2500PWx1 set at a temperature of 32° C.
• the flow rate is 1 mL/min and injection volume is 450 ⁇ L.
• the instrument is calibrated using five different hydroxyethyl starch standards injected at five different concentrations: HETA10K (2.0 mg/mL), HETA17K (1.75 mg/mL), HETA40K (1.25 mg/mL), HETA95K (0.75 mg/mL), and HETA205K (0.2 mg/mL), all from American Polymer Standards Corporation.
• maltodextrin Cargill MDTM 01960 dextrin, having a DE of 11 and a number average molecular weight of 14,851 as determined by aqueous GPC described above
• FAS ferrous ammonium sulfate
• An initiator solution comprising 3.6 grams of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour. The polymer was then neutralized to a pH of 5 by adding 18 grams of a 50% solution of NaOH. The final product was a clear water white solution having a Gardner color of 1. The number average molecular weight of this polymer was 159,587 as determined by aqueous GPC process noted above.
• the polymer was then neutralized to a pH of 5 by adding 18 grams of a 50% solution of NaOH.
• the final product was a clear water white solution having a Gardner color of 1.
• the number average molecular weight of this polymer was 101,340 as determined by aqueous GPC process noted above.
• the copolymer in Comparative Example 2 above was reproduced in the same manner with the exception that instead of 0.00075 grams of FAS, 0.075 grams of FAS was used (100 times the level of FAS used in Comparative Example 1, or 0.19 mmoles of FAS and 400 ppm as moles of Fe based on moles of acrylic acid monomer).
• the final product was a dark amber solution having a Gardner color of 12.
• the number average molecular weight of this polymer was 5,265 as determined by aqueous GPC.
• This example illustrates that higher levels of Fe(II) (400 ppm instead of 4) are required to lower the molecular weight compared to Comparative Example 1. However, this leads to darker colored materials as evidenced by the significant jump in Gardner color from 1 to 12.
• the copolymer in Comparative Example 1 above was reproduced in the same manner with the exception that instead of 0.00075 grams of FAS, 0.75 grams of FAS was used (1,000 times the level of FAS used in Comparative Example 1, or 1.9 mmoles FAS and 4000 ppm as moles of Fe based on moles of acrylic acid monomer).
• the final product was a very dark amber solution having a Gardner color of 18.
• the number average molecular weight of this polymer was 5,380 as determined by aqueous GPC. (This Mn is within experimental error and may indicate a limit of how low a Mn can be reached with increasing levels of Fe.)
• the copolymer in Comparative Example 1 above was reproduced in the same manner with the exception that instead of 0.00075 grams of FAS, 0.048 grams of Cu (II) sulfate pentahydrate was used (0.19 mmoles Cu (II) sulfate pentahydrate and 400 ppm as moles of Cu based on moles of acrylic acid monomer, or the same amount of Cu used as Fe used in Example 1).
• the final product was a clear yellow solution having a Gardner color of 9.
• the number average molecular weight of this polymer was 3,205 as determined by aqueous GPC. This shows that using Cu instead of Fe produces a lower molecular weight copolymer.
• an acceptable yellow color (Gardner 9 instead of 12), which is much lighter than the dark amber color of Example 1, is obtained by using the Cu salt instead of Fe and neutralizing to a pH of about 5.
• the copolymer in Comparative Example 2 above was reproduced in the same manner with the exception that instead of 0.00075 grams of FAS, 0.0022 grams of Cu (II) sulfate pentahydrate was used (0.0088 mmoles Cu (II) sulfate pentahydrate, which is the same molar level as the FAS used in Comparative Example 2).
• the final product was a dark amber solution having a Gardner color of 11.
• the number average molecular weight of this polymer was 4,865 as determined by aqueous GPC. This shows that using Cu instead of Fe produces a lower molecular weight copolymer.
• a solution containing 140 grams of acrylic acid (1.94 moles) and 141.9 grams of water was added to the reactor over a period of 5 hours. The amount of natural component was 50 weight % of total natural component and synthetic monomers.
• An initiator solution comprising 75 grams of 35% hydrogen peroxide and 25 grams of sodium persulfate dissolved in 80 grams of deionized water was simultaneously added to the reactor over a period of 6 hours. Simultaneously, 75 grams of 50% NaOH dissolved in 100 grams of water was added over 6 hours and 15 minutes so that the maleic acid is partially neutralized during the polymerization process. The reaction product was held at 98° C. for an additional hour. The polymer was then neutralized by adding 70 grams of a 50% solution of NaOH. The final product was a very dark amber solution with a Gardner color of 17 and a pH of 4.6. The number average molecular weight of this polymer was 1,360 as determined by aqueous GPC. The residual acrylic acid was 546 ppm and the residual maleic acid was 252 ppm.
• An initiator solution comprising 75 grams of 35% hydrogen peroxide and 25 grams of sodium persulfate dissolved in 80 grams of deionized water was simultaneously added to the reactor over a period of 6 hours. Simultaneously, 75 grams of 50% NaOH dissolved in 100 grams of water was added over 6 hours and 15 minutes partially neutralizing the maleic acid during the polymerization process. The reaction product was held at 98° C. for an additional hour. The polymer was then neutralized by adding 70 grams of a 50% solution of NaOH. The final product was a very dark amber solution having a Gardner color of 18 and a pH of 4.6. The number average molecular weight of this polymer was 1,340 as determined by aqueous GPC. The residual acrylic acid was 588 ppm and the residual maleic acid was 460 ppm.
• a reactor containing 120 grams of water and 94 grams of Cargill Sweet Satin Maltose (80% solution) and 0.048 grams of Cu(II) sulfate pentahydrate (0.19 mmoles, of 553 ppm as moles of Cu based on moles of acrylic acid monomer) was heated to 98° C.
• a solution containing 25 grams of acrylic acid (0.347 moles) and 30 grams of water was added to the reactor over a period of 45 minutes.
• An initiator solution comprising 3.6 grams of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour.
• the polymer was then neutralized by adding 18 grams of a 50% solution of NaOH (0.225 moles) for a 65% neutralization of the acrylic acid groups.
• the final product was a clear golden yellow solution with a Gardner color of 7 and a pH of 5.1.
• the number average molecular weight of this polymer was 2,024 as determined by aqueous GPC.
• the polymer solution was stable for months with no signs of phase separation.
• a reactor containing 120 grams of water and 106 grams of Cargill Sweet Satin Maltose (80% solution) and 0.048 grams of Cu(II) sulfate pentahydrate (0.19 mmoles, or 923 ppm as moles of Cu based on the moles of acrylic acid monomer) was heated to 98° C.
• a solution containing 15 grams of acrylic acid (0.208 moles) and 30 grams of water was added to the reactor over a period of 45 minutes.
• An initiator solution comprising 3.6 grams of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour.
• the polymer was then neutralized by adding 7.5 grams of a 50% solution of NaOH (0.09 moles) for a 45% neutralization of the acrylic acid groups.
• the final product was a clear golden yellow solution with a Gardner color of 7 and a pH of 4.9.
• the number average molecular weight of this polymer was 1,255 as determined by aqueous GPC.
• the polymer solution was stable for months with no signs of phase separation.
• a reactor containing 120 grams of water, 119 grams of Cargill Sweet Satin Maltose (80% solution) and 0.048 grams of Cu(II) sulfate pentahydrate (0.19 mmoles Cu(II) sulfate pentahydrate, or 2736 ppm as moles of Cu based on moles of acrylic acid monomer) was heated to 98° C.
• a solution containing 5 grams of acrylic acid (0.069 moles) and 30 grams of water was added to the reactor over a period of 45 minutes.
• An initiator solution comprising 3.6 grams of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour.
• the polymer was then neutralized by adding 2.5 grams of a 50% solution of NaOH (0.031 moles) for a 45% neutralization of the acrylic acid groups.
• the final product was a clear golden yellow solution having a Gardner color of 7 and a pH of 4.9.
• the number average molecular weight of this polymer was below the detectable limit of the GPC.
• the polymer solution was stable for months with no signs of phase separation.
• a solution containing 140 grams of acrylic acid (1.94 moles) was added to the reactor over a period of 5 hours. The amount of natural component was 50 weight percent of the natural component and the synthetic monomers.
• An initiator solution comprising 75 grams of 35% hydrogen peroxide and 25 grams of sodium persulfate dissolved in 80 grams of deionized water was simultaneously added to the reactor over a period of 6 hours.
• the reaction product was held at 98° C. for an additional hour.
• the polymer was then neutralized by adding 70 grams of a 50% solution of NaOH.
• the fmal product was a very dark amber solution with a Gardner color of 15.
• the number average molecular weight of this polymer was 4,038 as determined by aqueous GPC.
• An initiator solution comprising of 4.7 grams of sodium persulfate and 38.7 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water was added to the reactor at the same time and over the same period as the monomer solution.
• the reaction product was held at 95° C. for 30 minutes.
• 0.3 grams of erythorbic acid dissolved in 0.6 grams of water and 4 grams of a 41% bisulfite solution were simultaneously added to scavenge the residual monomer.
• the final product was a clear light amber solution and had 44% solids.
• An initiator solution comprising of 4.8 grams of sodium persulfate and 38.7 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water was added to the reactor over a period of 5.5 hours. The reaction product was held at 95° C. for 30 minutes. 0.3 grams of erythorbic acid dissolved in 0.6 grams of water and simultaneously, 4 grams of a 41% bisulfite solution was added to scavenge the residual monomer. The final product was a clear light amber solution and had 35% solids. The number average molecular weight of this polymer as measured by aqueous GPC was 1755.
• An initiator solution comprising of 2.4 grams of sodium persulfate and 19.4 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water was added to the reactor over a period of 5.5 hours. The reaction product was held at 95° C. for 30 minutes. 0.3 grams of erythorbic acid dissolved in 0.6 grams of water and simultaneously, 4 grams of a 41% bisulfite solution was added to scavenge the residual monomer. The final product was a clear light amber solution and had 44% solids. The number average molecular weight of this polymer as measured by aqueous GPC was 1280.
• Copolymers from the above Examples were tested for anti-redeposition properties in a generic powdered detergent formulation.
• the powdered detergent formulation was as follows:
• the test was conducted in a full scale washing machine using 3 cotton and 3 polyester/cotton swatches. Soil consisting of 17.5 g rose clays 17.5 g bandy black clay and 6.9 g oil blend (75:25 vegetable/mineral) was used. The test was conducted for 3 cycles using 100 g powder detergent per wash load. The polymers were dosed in at 1.0 wt % of the detergent. The wash conditions used were temperature of 33.9° C. (93° F.), 150 ppm hardness and a 10 minute wash cycle.
• Delta whiteness index is calculated using the L, a, b values above.
• Example 18 Example 19 Ingredient Wt % Wt % Wt % Anionic surfactant 22 20 10.6 Non-ionic surfactant 1.5 1.1 9.4 Cationic surfactant — 0.7 — Zeolite 28 — 24 Phosphate — 25 — Silicate 8.5 Sodium 27 14 9 carbonate/bicarbonate Sulfate 5.4 15 11 Sodium silicate 0.6 10 — Polyamine 4.3 1.9 5 Brighteners 0.2 0.2 — Sodium perborate 1 Sodium percarbonate 1 — — Sodium hypochlorite 1 Suds suppressor 0.5 0.5 — Bleach catalyst 0.5 — Polymer of Example 1 1 Polymer of Example 2 5 Polymer of Example 3 2 Water and others Balance Balance Balance Balance
• Citric acid 50% solution
• Phosphoric acid 1.0 C 12 -C 15 linear alcohol ethoxylate with 3 moles of EO 5.0 Alkyl benzene sulfonic acid 3.0
• Polymer of Example 1 1.0 Water 78.0
• water-soluble polymers are incorporated into a water treatment composition that includes the water-soluble polymer and other water treatment chemicals.
• Other water treatment chemicals include corrosion inhibitors such as orthophosphates, zinc compounds and tolyl triazole.
• the level of inventive polymer utilized in water treatment compositions is determined by the treatment level desired for the particular aqueous system treated.
• Water soluble polymers generally comprise from 10 to 25 percent by weight of the water treatment composition.
• Conventional water treatment compositions are known to those skilled in the art, and exemplary water treatment compositions are set forth in the four formulations below. These compositions containing the polymer of the present invention have application in, for example, the oil field.
• Formulation 1 Formulation 2 11.3% of Polymer of Ex. 1 11.3% Polymer of Ex. 3 47.7% Water 59.6% Water 4.2% HEDP 4.2% HEDP 10.3% NaOH 18.4% TKPP 24.5% Sodium Molybdate 7.2% NaOH 2.0% Tolyl triazole 2.0% Tolyl triazole pH 13.0 pH 12.64 Formulation 3 Formulation 4 22.6% of Polymer of Ex. 2 11.3% Polymer of Ex.
• Example 4 The polymers in Example 4 and Comparative Example 2 were tested for anti-redeposition performance.
• the data below indicates that the polymer of Example 4 was far superior to that of Comparative Example 2 in anti-redeposition properties. Further, the performance of polymer 4 proved superior to a commercial synthetic Na polyacrylate (Alcosperse 602N), which is an industry standard for this application.
• Example 4 One wash anti-redeposition data using commercial Sun liquid detergent.
• the test protocol is described in Example 4.
• Lower Delta WI (whiteness index) numbers are better.
• the data indicate that the low molecular weight graft copolymer of Example 4 produced using the Cu catalyst has superior anti-redeposition properties compared to the graft copolymer of Comparative Example 2 using the same amount of Fe.
• Comparative Example 2 polymer performs similar to the control, which does not have any polymer.
• the low molecular weight graft copolymer of this invention performs similar to the industry standard synthetic polyacrylic acid.
• a reactor containing a mixture of 450 grams of water, 100 grams of maleic anhydride (1.02 moles), 300 grams of 80% solution of Cargill Sweet Satin Maltose, 0.0022 grams of Cu(II) sulfate pentahydrate and 75 grams of a 50% solution of NaOH was heated to 98° C.
• a solution containing 140 grams of acrylic acid (1.94 moles) in 50 grams of water was added to the reactor over a period of 5 hours.
• the mole percent of maleic in the synthetic part of the copolymer was 34.4.
• the amount of natural component was 50 weight percent, based on total weight percent of natural component and synthetic monomers.
• a reactor containing a mixture of 200 grams of water, 8 grams of maleic anhydride (0.08 moles), 160 grams of Cargill maltodextrin MD 1956 (DE 7.5) and 11.8 grams of a 50% solution of NaOH was heated to 98° C.
• a shot of 0.0018 grams of ferrous ammonium sulfate hexahydrate was added to the reactor just before monomer and initiator feeds were started.
• a solution containing 22 grams of acrylic acid (0.31 moles) in 71 grams of water was added to the reactor over a period of 150 minutes.
• the mole percent of maleic in the synthetic part of the copolymer was 21.
• the amount of natural component was 84.2 weight percent based on total weight percent of natural component and synthetic monomers.
• each maleic anhydride group contributes 2 COOH moieties.
• a reactor containing 140 grams of water, 65 grams of Flomax 8 (oxidized starch having a Mn of 9,891, available from National Starch and Chemical, Bridgewater, N.J.) and 0.00075 grams of FAS was heated to 98° C.
• An initiator solution comprising 3.6 grams of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes.
• the reaction product was held at 98° C. for an additional hour.
• the polymer was then neutralized by adding 35 grams of a 50% solution of NaOH.
• the final product was an opaque yellow solution.
• the number average molecular weight of this polymer was 24,373 as determined by aqueous GPC.
• the efficacy of various treatments was tested for their ability to prevent the precipitation of calcium carbonate in typical cooling water conditions (a property commonly referred to as the threshold inhibition).
• This test was developed in correlation with the dynamic testing units, in order to allow for an initially quick screening test of scale threshold inhibitors for cooling water treatment.
• the ratio of calcium concentration to alkalinity is 1.000:1.448 for the chosen water. This ratio is a fairly accurate average of cooling water conditions found worldwide. One should expect that water wherein the alkalinity is proportionately less will be able to reach higher levels of calcium, and that water containing a proportionally greater amount of alkalinity will reach lower levels of calcium.
• cycle of concentration is a general term, one cycle was chosen, in this case, to be that level at which calcium concentrations equaled 100.0 mg/L Ca as CaCO 3 (40.0 mg/L as Ca).
• the complete water conditions at one cycle of concentration i.e., make-up water conditions are as follows:
• above average threshold inhibitors can reach anywhere from four to five cycles of concentration with this water before significant calcium carbonate precipitation begins. Average threshold inhibitors may only be able to reach three to four cycles of concentration before precipitating, while below average inhibitors may only reach two to three cycles of concentration before precipitation occurs. Polymer performance is generally expressed as percent calcium inhibition. This number is calculated by taking the actual soluble calcium concentration at any given cycle, dividing it by the intended soluble calcium concentration for that same given cycle, and then multiplying the result by 100.
• All chemicals used are reagent grade and weighed on an analytical balance to ⁇ 0.0005 g of the indicated value. All solutions are made within thirty days of testing. Once the solutions are over thirty days old, they are remade.
• the hardness, alkalinity, and 12% KCl solutions should be prepared in a one liter volumetric flask using DI water. The following amounts of chemical should be used to prepare these solutions—
• a 250 mL of a 10,000 mg/L active treatment solution is made up. This was done for every treatment tested.
• the pH of the solutions was adjusted to between 8.70 and 8.90 using 50% and 10% NaOH solutions by adding the weighed polymer into a specimen cup or beaker and filling with DI water to approximately 90 mL.
• the pH of this solution was then adjusted to approximately 8.70 by first adding the 50% NaOH solution until the pH reaches 8.00, and then by using the 10% NaOH until the pH equals 8.70.
• the solution was then poured into a 250 mL volumetric flask.
• the specimen cup or beaker was rinsed with DI water and this water added to the flask until the final 250 mL is reached.
• the formula used to calculate the amount of treatment to be weighed is as follows:
• the incubator shaker should be turned on and set for a temperature of 50° C. to preheat.
• 34 screw cap flasks were set out in groups of three to allow for triplicate testing of each treatment, allowing for testing of eleven different treatments. The one remaining flask was used as an untreated blank. Label each flask with the treatment added.
• alkalinity solution Using a 2.5 mL electric pipette, add 1.60 mL of alkalinity solution to each flask. This is the amount that will achieve four cycles of make-up water. The addition of alkalinity should be done while swirling the flask, so as not to generate premature scale formation from high alkalinity concentration pooling at the addition site.
• the percent inhibition is calculated for each treatment.
• the lithium is used as a tracer of evaporation in each flask (typically about ten percent of the original volume).
• the lithium concentration found in the “total” solution is assumed to be the starting concentration in all 34 flasks.
• the concentrations of lithium in the 34 shaker samples can then each be divided by the lithium concentration found in the “total” sample. These results will provide the multiplying factor for increases in concentration, due to evaporation.
• the calcium and magnesium concentrations found in the “total” solution are also assumed to be the starting concentrations in all 34 flasks.
• Example 3 The polymer of Example 3 was tested in this test at 3 cycles of concentration and compared with a commercial polyacrylate (AQUATREAT 900A from Alco Chemical). The data indicate that the low molecular weight graft copolymer was as good a calcium carbonate inhibitor in this test.
• Low molecular weight sulfonated graft copolymers are exemplified in U.S. Pat. No. 5,580,941. These materials are made using mercaptan chain transfer agents. Mercaptan chain transfer agents lower the molecular weight, but in the process generate synthetic polymers. These mercaptans stop a growing chain Equation 1 and start a new polymer chain Equation 2, illustrated in the mechanism below (Odian, P RINCIPLES OF P OLYMERIZATION, 2 nd Ed., John Wiley & Sons, p. 226, New York (1981)). This new chain is now comprised of ungrafted synthetic copolymers.
• Comparative Example 5 of the '941 patent forms a precipitate when higher molecular weight saccharide (maltodextrin with DE 20) is used. This illustrates that there is little grafting and the resulting synthetic polymer is phase separating from the maltodextrin. This does not happen with the other examples because disaccharides like sucrose are used, which are small molecules and are compatible.
• graft copolymers of the present invention can have greater than 50 wt % maltodextrin and are compatible, indicating high degree of grafting.
• a reactor containing 156 grams of water, 49 grams of maltodextrin (Cargill MDTM 01918 maltodextrin, DE of 18) and 0.0039 grams of FAS was heated to 98° C.
• a solution containing 81.6 grams of acrylic acid and 129.2 of a 50% solution of sodium 2-acrylamido-2-methyl propane sulfonate (AMPS) was added to the reactor over a period of 45 minutes.
• An initiator solution comprising 13 grams of 35% hydrogen peroxide solution in 78 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes.
• the reaction product was held at 98° C. for an additional hour.
• the polymer was then neutralized by adding 27.2 grams of a 50% solution of NaOH.
• the final product was a clear yellow solution.
• the number average molecular weight of this polymer was 68,940.
• This sample remained a clear solution showing no sign of precipitation (phase separation) even after 4 months.
• a blend of Alcosperse 545 (AA-AMPS copolymer) and Cargill MDTM 01918 maltodextrin phase separates within a day. This is similar to the phase separation seen in Comparative Example 5 of the '941 patent where a maltodextrin having a DE of 20 (a lower molecular weight dextrin than that used in our recipe) is used. This clearly indicates that the Example 5 has very little graft copolymer due to the presence of mercaptan, which leads to a lot of synthetic copolymer.
• CaCO 3 inhibition performance was evaluated according to NACETM 3076-2001 standardized test with a few modifications.
• Our modified test used 30 mL total sample size instead of 100 mL indicated in the method.
• the polymers were tested at 5, 10 and 15 ppm levels.
• the samples were tested in triplicate rather than duplicate.
• the samples were heated in heat block rather than oven or water bath and Ca concentration was determined by ICP.
• the “blank before precipitation” was made by combining 15 mL Ca Brine+15 mL of NaCl Brine plus DI water in place of polymer treatment, and the “blank after precipitation” was made by combining 15 mL Ca Brine+15 mL of Bicarbonate Brine plus DI water instead of polymer.
• An initiator solution comprising of 4.7 grams of sodium persulfate and 38.7 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water was added to the reactor at the same time as the monomer solution i.e. over a period of 4 hours.
• the reaction product was held at 95° C. for 30 minutes.
• 0.3 grams of erythorbic acid dissolved in 0.6 grams of water and simultaneously, 4 grams of a 41% bisulfite solution was added to scavenge the residual monomer.
• the final product was a clear light amber solution and had 44% solids.
• An initiator solution comprising of 4.8 grams of sodium persulfate and 38.7 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water was added to the reactor over a period of 5.5 hours. The reaction product was held at 95° C. for 30 minutes. 0.3 grams of erythorbic acid dissolved in 0.6 grams of water and simultaneously, 4 grams of a 41% bisulfite solution was added to scavenge the residual monomer. The final product was a clear light amber solution and had 35% solids. The number average molecular weight of this polymer as measured by aqueous GPC was 1755.
• An initiator solution comprising of 2.4 grams of sodium persulfate and 19.4 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water was added to the reactor over a period of 5.5 hours. The reaction product was held at 95° C. for 30 minutes. 0.3 grams of erythorbic acid dissolved in 0.6 grams of water and simultaneously, 4 grams of a 41% bisulfite solution was added to scavenge the residual monomer. The final product was a clear light amber solution and had 44% solids. The number average molecular weight of this polymer as measured by aqueous GPC was 1280.
• Example 38 The polymer of Example 38 was tested in all 3 of the brines detailed in Table 1. The data indicate that the polymer is very compatible in these brines.
• a reactor containing 150 grams of water, 90 grams of a 50% solution of NaOH, 10 grams of maltodextrin (Cargill MDTM 01960 dextrin) and 0.00075 grams of ferrous ammonium sulfate hexahydrate (‘FAS’) was heated to 98° C.
• a solution containing 90 grams of acrylic acid was added to the reactor over a period of 45 minutes.
• An initiator solution comprising 3.6 grams of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour.
• the pH of the polymer solution was 7.
• the graft copolymer of this Example with low levels of saccharide functionality (10 weight percent) was tested for brine compatibility in Brine 3. This polymer was found to be insoluble in Brine 3 when dosed at 250, 1,000, 5,000, 25,000 and 100,000 ppm levels.
• An initiator solution comprising of 5.4 grams of sodium persulfate and 45 grams of a 35% solution of hydrogen peroxide dissolved in 12.7 grams of water is added to the reactor over a period of 5.5 hours. The reaction product is held at 95° C. for 60 minutes.
• the graft copolymer of this Example with low levels of saccharide functionality (10 weight percent) is tested for brine compatibility in Brine 3.
• the polymer is found to be insoluble in Brine 3 when dosed at 250, 1,000, 5,000, 25,000 and 100,000 ppm levels.

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