WO2001074915A1 - Composition a base de dispersion de polymeres ampholytiques et procede d'utilisation - Google Patents

Composition a base de dispersion de polymeres ampholytiques et procede d'utilisation Download PDF

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Publication number
WO2001074915A1
WO2001074915A1 PCT/US2001/008103 US0108103W WO0174915A1 WO 2001074915 A1 WO2001074915 A1 WO 2001074915A1 US 0108103 W US0108103 W US 0108103W WO 0174915 A1 WO0174915 A1 WO 0174915A1
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Prior art keywords
water
ampholytic polymer
polymer
aqueous dispersion
dispersion
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PCT/US2001/008103
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English (en)
Inventor
Shih-Ruey T. Chen
Nichlolas Vozza
James E. Rak
Randy Loeffler
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Calgon Corporation
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Priority to AU45703/01A priority Critical patent/AU4570301A/en
Publication of WO2001074915A1 publication Critical patent/WO2001074915A1/fr

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • 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
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • 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
    • C09K8/02—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5428—Polymers characterized by specific structures/properties characterized by the charge amphoteric or zwitterionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised

Definitions

  • the present invention relates to novel aqueous dispersions of ampholytic polymers and the process for preparing such aqueous dispersions.
  • aqueous dispersions of ampholytic polymers are useful in personal care, waste water, paper processing and thickening applications.
  • US Patent No. 5,605,970 discloses and claims a method for the manufacture of a particular anionic water-soluble polymer in dispersion form.
  • This disclosure teaches that certain anionic polymers, incorporating hydrophobically modified monomers, can be prepared using dispersion polymer methods.
  • This patent specifically teaches the manufacture of acrylic acid-ethylhexylacrylate polymers. The ethylhexylacrylate monomer adds a hydrophobic character to the polymer, causing the polymer to become insoluble in certain brine solutions. While these polymers, and the methods for their manufacture are useful, the incorporation of a hydrophobic monomer into a water soluble polymer, where water solubility is desirable is not always advantageous in the final use of the polymer.
  • US Patent No. 5,837,776 discloses aqueous dispersions of water soluble nonionic and anionically charged vinyl and allyl addition polymers which are obtained by polymerizing in the presence of an anionically charged water-soluble polymer stabilizer in a saturated salt solution. While these polymers, and the methods for their manufacture are useful, the incorporation of the anionically charged water-soluble polymer stabilizer into various end uses can have a negative impact on the performance attributes of dispersed polymer leading to less than optimum performance. Also, the presence of so much salt in the resulting polymer solution has a negative effect on solution viscosity as well as polymer performance in some instances.
  • polymers outlined above are used in many application areas due to the interaction of polyelectrolyte with substrates that carry a charge.
  • the basic science that explains polymer - surface interactions can be applied to many end use applications, such as paper coating, conditioning hair and skin, waste-water clarification, suspension stabilization, as well as fluid loss control in oil field cementing and drilling operations.
  • keratin refers to human or animal hair, skin and/or nails.
  • ingredients must have adequate adherent properties, so that they are not only adsorbed initially, but are also retained on exposure to water. This property is referred to as "substantivity", i.e., the ability of a material to be adsorbed onto keratin, or in the case of hair, resisting removal by water rinse-off.
  • Hair is composed of keratin, a sulfur-containing fibrous protein.
  • the isoelectric point of keratin, and more specifically of hair, is generally in the pH range of 3.2-4.0. Therefore, at the pH of a typical shampoo, hair carries a net negative charge. Consequently, cationic polymers have long been used as conditioners in shampoo formulations, or as a separate treatment, in order to improve the wet and dry combability of the hair.
  • the substantivity of the cationic polymers for negatively charged hair along with film formation facilitates detangling during wet hair combing and a reduction in static flyaway during dry hair combing.
  • Cationic polymers generally also impart softness and suppleness to hair.
  • cationic polymers When cationic polymers are added to shampoos (or to skin care products such as cleaning compositions) containing anionic surfactants, formation of highly surface active association complexes generally takes place, which imparts improved foam stability to the shampoo. Maximum surface activity and foam stability, or lather, are achieved at near stoichiometric ratios of anionic surfactant: cationic polymer, where the complex is least water soluble.
  • cationic conditioners exhibit some incompatibility at these ratios. Compatibility gives a commercially more desirable clear formulation, while incompatibility leads to a haze or precipitation, which is aesthetically less desirable in some formulations.
  • Papermaking is a process of introducing an aqueous slurry of pulp or wood cellulosic fibers
  • a typical coating compositions for offset printing comprises 100 parts by weight of pigment, from 5 to 25, and preferably from 10 to 20, parts by weight of an adhesive, a water soluble polymer dispersing agent for the pigment, auxiliary agents and water to give a total solids concentration of about 60% by weight.
  • the adhesive is usually chosen from one or more of a protein derivative, a starch derivative, a cellulose derivative or a latex, and an example of a particular adhesive system would be 10 parts by weight of oxidized starch and 7 parts by weight of styrene-butadiene latex.
  • the pigment would normally have a particle size distribution such that at least 80% by weight, and preferably at least 90% by weight, of its particles have an equivalent spherical diameter smaller than 2 micron in order to provide a coating of good gloss and brightness.
  • the weight mean equivalent spherical diameter range for typical pigments suitable for offset coating compositions is from about 0.3 to about 0.8 micron.
  • a coating composition intended for use in preparing a coated paper for offset printing generally comprises a hydrophilic polymer material, such as a starch derivative or a cellulose derivative, in order to increase the initial viscosity of the composition and thus inhibit the penetration of the aqueous phase of the composition into the paper web.
  • the aqueous phase tends to be absorbed into the body of the paper, with the result that the local concentration of solids in the composition is increased and the composition becomes so viscous that the shear forces to which it is exposed in the paper coating apparatus render it virtually incapable of passing through the narrow clearance which exists between the applicator device and the moving web.
  • the hydrophilic polymeric material is present, the surface of the paper web is effectively sealed, thus inhibiting further penetration of the aqueous phase into the paper.
  • paper includes sheet-like masses and molded products made from natural sources, synthetics such as polyamides, polyesters, rayon and polyacrylic resins as well as from mineral fibers such as asbestos and glass. In addition, paper made from combinations of cellulosic and synthetic materials are applicable herein. Paperboard is also included within the broad term "paper”.
  • ink jet recording method In an ink jet recording method, recording is generally carried out by jetting fine drops of ink using a variety of mechanisms so as to form images on a recording paper. Therefore, the recording method of ink jet type has advantages in that it is less noisy, can provide full-color prints with ease and enables high-speed printing, compared with the recording method of dot impact type.
  • cast-coated paper In contrast to the recording media on the market in which films or the like are used as substrate, cast-coated paper uses low-priced paper as a substrate and can be prepared in a relatively simple process, so that it has the advantage of a substantially lower cost. Further, as the recording side of cast- coated paper can be rendered glossy, the cast-coated paper is suitable for ink jet recording paper which can give a feeling of high quality and can provide high grade recorded images at a lower price.
  • drilling fluids Another area in which polyelectrolytes provide benefit is in drilling fluids. It is well known that in perforating earthen formations to tap subterranean deposits such as gas or oil, that perforation is accomplished by well drilling tools and a drilling fluid. These rotary drilling systems consist of a drilling bit fitted with appropriate ' teeth ' , then a set of pipes assembled rigidly together end to end, the diameter of which 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 being drilled. As the drill bit attacks and goes through the geological strata, 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 serves to cool and lubricate the drill bit, to raise the drilling cuttings to the surface of the ground, and to seal 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 wherein the sand and drill cuttings are separated, with or without screening.
  • the fluid is then again pumped into the drill pipe by a mud pump.
  • Some of the most serious problems encountered in producing and maintaining effective clay-based aqueous drilling fluids are caused by the interaction of the mud with the earth formation being drilled. These interactions include contamination of the mud by formation fluids, incorporation into the mud of viscosity producing and inert drilled solids, chemical contamination by drilled solids, or by the infiltration of sea-water and/or fresh water.
  • Hydraulic cement compositions are used for carrying out various operations in oil, gas and water wells including, but not limited to construction and completion operations such as primary cementing and remedial operations such as squeeze cementing.
  • Primary cementing involves the placement of a hydraulic cement composition into the annular space between the walls of a well bore and the exterior of a pipe such as casing disposed therein. The cement composition is pumped into the annular space and allowed to set into an annular cement sheath therein whereby the pipe is bonded to the walls of the well bore by the set cement.
  • cement refers to portland cement, concrete and other mixtures of calcium oxide and sand.
  • Squeeze cementing techniques usually involve the undesirable movement of oil, gas or water through small holes or cracks in pipe disposed in the well bore; holes, cracks, voids or channels in the annular cement sheath between the pipe and the well bore; annular spaces between the cement sheath and the pipe or the walls of the well bore and permeable zones or fractures in subterranean formations.
  • Such holes, cracks, etc. are plugged by squeezing hydraulic cement compositions therein which harden and form impermeable plugs.
  • the cement compositions are often subjected to high temperatures, particularly when the cementing is carried out in deep subterranean zones.
  • the high temperatures can cause premature setting of the cement compositions, i.e., the compositions can not be pumped for long enough times before setting to place them in the zones to be cemented.
  • This requires the use of set retarding additives in the cement compositions which extend the setting times of the compositions so that adequate pumping time is provided in which to place or displace the compositions into desired subterranean zones.
  • polymers have been used to improve the properties of the substrate or minimize adverse consequences. For example if the substrate is hair, polymers have been used to improve the detangling and combing of hair after shampooing.
  • Polymers are added to waste-water, as in the case of raw sewage for instance, to coagulate and flocculate solid matter and separate it from the carrier liquid.
  • polymers are used to provide faster dewate ng of the sheet, which leads to faster, more economical machine utilization.
  • Polymers are also added during paper manufacture to improve the strength, or resistance to tearing, of the resulting sheet.
  • Polymers are also added to paper coatings to improve the gloss of the sheet and to provide a surface that results in fast drying well defined dots from the ink jet printing process.
  • Polymers are added to drilling fluids and cementing compositions to aid in performance and minimize water loss to the surrounding rock formation.
  • the polymer In all of these applications, the polymer must be substantive to the substrate,' meaning that it will adhere or adsorb onto the substrate surface and not be easily removed. Although many polymers are used in the aforementioned applications, there still remains a shortcoming in that high molecular weight polymers are either supplied in a difficult to handle dry from or are dispersed in an undesirable hydrocarbon liquid or saturated salt solution.
  • composition according to the present invention is an aqueous dispersion of an ampholytic polymer that comprises: (A) about 50% to about 99%, by weight water;
  • (C) about 0% to about 0.5% by weight of a preservative; wherein the dispersion has a pH of from about 1 to about 6 and has a bulk viscosity at 25°C of less than 100,000 cps and wherein the ampholytic polymer of (B) comprises: about 1% to about 45%, on a molar basis, of one or more cationic monomers selected from the group consisting of (a) diallyl dialkyl ammonium halides of the general formula:
  • R 1 is independently an alkyl group from Ci to C 36 and X " is a halide, (b) substituted acrylamides of the general formula:
  • R 1 and X " are as defined above, R 2 is H, methyl or ethyl, and R 3 is a linear or branched alkyl C 2 to C ⁇ 2 group, and (c) substituted acrylates of the general formula: CH, CR 2
  • AA acrylic acid
  • MAA methacrylic acid
  • AMPSA acrylamidomethyl propane sulfonic acid
  • MAMPSA methacrylamidomethyl propane sulfonic acid
  • CA crotonic acid
  • MAH acrylic acid
  • S sodium vinyl sulfonate
  • AGiy acrylamidoglycolic acid
  • AMBA acrylamidomethyl butanoic acid
  • SSA styrene sulfonic acid
  • non-ionic monomers selected from the group of acrylamide (Am), methacrylamide (MAm), n-alkyl acrylamide (NAAm), n-alkyl methacrylamide (NAMAm), vinyl pyrrolidone (VP), vinyl acetate (VP), vinyl alcohol (VOH), alkyl esters of acrylic acid and alkyl esters of methacrylic acid.
  • Am acrylamide
  • MAm methacrylamide
  • NAAm n-alkyl acrylamide
  • NAMAm n-alkyl methacrylamide
  • VP vinyl pyrrolidone
  • VP vinyl acetate
  • VH vinyl alcohol
  • the method according to the present invention is a method of producing the aqueous dispersion of an ampholytic polymer above and comprises the steps of:
  • composition above can be added to various aqueous systems to improve the performance of such systems. These systems comprise keratin treating systems, drilling muds, paper furnishes, cementing compositions, and waste water clarification systems. The above composition can also be added to various aqueous systems as a thickener.
  • aqueous dispersion of an ampholytic polymers of the present invention and compositions containing such polymers are novel and unexpected due to the unique ability for these dispersions to deliver relatively high active polymer from an aqueous carrier which is substantially free of salts and/or hydrocarbon liquids.
  • the monomers used in making the ampholytic polymers of the invention are soluble in water, however, when the polymerization is performed at a low pH (less than 6), the resulting polymer precipitates and forms an aqueous dispersion without the aid of saturated salt solution or hydrocarbon liquids. This feature unexpectedly permits the preparation of dispersions of such high solid content i.e. as high as 50% based on weight.
  • the monomer and the initiator are both soluble in the polymerization medium, but the medium is a poor solvent for the resulting polymer. Accordingly, the reaction mixture is homogeneous at the onset, and the polymerization is initiated in a homogeneous solution.
  • phase separation occurs at an early stage. This leads to nucleation and the formation of primary particles called "precursors". The particles are believed to be swollen by the polymerization medium and/or the monomer, leading to the formation of spherical particles having a size in the region of about.0.1-10.0 microns.
  • the variables that are usually controlled are the monomer and the initiator, solvency of the dispersion medium, and the reaction temperature. It has been found that these variables can have a significant effect on the particle size, the molecular weight of the final polymer particles, and the kinetics of the polymerization process.
  • the pH of the aqueous medium is determining variable for polymer solubility and, therefore, for the dispersion polymerization process.
  • the pH affects the solvency of the aqueous dispersion medium for the resulting polymer.
  • the solvency of the dispersion medium increases, (a) the oligomers will grow to a larger MW before they become a precursor nuclei, (b) the anchoring of the stabilizer moiety will probably be reduced and (c) the particle size increases.
  • the initiator concentration is increased, it has been observed that the final particle size increases.
  • ampholytic water soluble dispersion polymers can be prepared which are stable, of high molecular weight, and which do not necessarily contain monomers having a hydrophobic character or rely on high salt levels in the aqueous medium.
  • this invention is directed to the manufacture of ampholytic water soluble polymers, in dispersion form, which do not necessarily require the inclusion of a hydrophobically modified monomer or saturated salt solution.
  • This invention is directed to a composition, and method for the manufacture of high molecular weight, ampholytic, water soluble vinyl addition polymers in aqueous dispersion form.
  • the unique aspect of the polymers of this invention is that the polymers are prepared without the inclusion of a monomer which would decrease the water solubility of the resultant polymer material, that is to say that there is no inclusion of a monomer which would have hydrophobic characteristics.
  • aqueous dispersions of water soluble ampholytic polymers can be prepared without the inclusion of a hydrophobic monomer component or saturated salt solution component.
  • the method of producing an aqueous dispersion of an ampholytic polymer according to the present invention comprises the steps of:
  • the method according to the present invention preferably entails a further step of adding a preservative to the dispersion when the temperature is less than about 50° C.
  • the preparation is generally conducted at a pH between about 1 and about 6 but this pH is more preferably between about 2 and about 5, with a pH of about 2 to about 4.5 being most preferred.
  • novel aqueous dispersions of ampholytic water-soluble polymers of the present invention comprises:
  • (B) about 1 % to about 50%, preferably about 10% to about 45%, and most preferably about 15% to about 40% by weight of an ampholytic polymer; and .
  • (C) about 0% to about 0.5%, preferably 0% to about 0.4%, and most preferably about 0.01 % to about 0.35% by weight of a preservative.
  • the dispersion of the present invention preferably has a bulk viscosity at 25°C of less than 100,000 cps, more preferably less than 70,000 cps, and most preferably less than 50,000 cps.
  • the ampholytic polymer of (B) comprises:
  • R 1 is independently an alkyl group from Ci to C 36 and X " is a halide, (b) substituted acrylamides of the general formula:
  • R 1 , R 2 , R 3 , and X " are as defined above;
  • NAAm n-alkyl methacrylamide
  • NAMAm n-alkyl methacrylamide
  • VP vinyl pyrrolidone
  • VP vinyl acetate
  • VH vinyl alcohol
  • the weight average molecular weight of said polymer is preferably from about 1 ,000 to 10,000,000, more preferably from 10,000 to 8,000,000 and most preferably from 50,000 to 7,000,000.
  • the mole ratio of i):ii) is from 1 :25 to 1 :1 , preferably 1 :10 to 1 :1 , and most preferably 1 :5 to 1 :1.1.
  • the preservative (C) is selected from the list of methyl paraben, propyl paraben, butyl paraben, , benzoic acid and its corresponding sodium, potassium and ammonium salts, chloromethyl isothiazoiinone and methyl isothiazolinone, DMDM Hydantoin, imidazolidinyl urea, Quaternium 15, diazolinyl urea, bromo nitro propane diol, formaldehyde, sorbic acid and its corresponding sodium, potassium and ammonium salts, and dibromodicyanobutane.
  • the water-soluble polymer dispersions may be prepared by conventional solution polymerization techniques, as indicated below.
  • the appropriate weights for the desired mol percentages of i), ii), and iii are charged to a glass reactor equipped with a stirring means.
  • the desired amount of water is then added to the reactor with vigorous stirring to give the desired total monomer concentration, which is generally about 5-50% by weight.
  • the monomer mixture may then be adjusted to a pH of about 2.0 to about 6.0 with dilute NaOH, heated to an appropriate initiation temperature, and purged with nitrogen for at least thirty minutes. Polymerization is then initiated by adding a free radical initiator. After the peak exotherm is reached, additional dilution water and sodium bisulfite are added to scavenge any unreacted monomers.
  • Any free radical initiator may be used, examples include peroxides, azo initiators and redox systems.
  • the polymerization may also be initiated photochemically.
  • the preferred catalysts are sodium persulfate or a mixture of ammonium-persulfate and any azo type initiator, such as 2,2'-azobis-(2,4- dimethyl-4-methoxyvaleronitrile), 2,2'-azobisisobutyronitrile or 4,4'-azobis(4- cyanovaleric acid).
  • the polymerization is characterized by the fact that it begins as a clear, colorless solution and becomes hazy to cloudy as the polymerization progresses and the dispersed polymer phase forms. The final dispersion is milky in appearance and free flowing.
  • a preferred composition for the ampholytic polymer (B) in the aqueous dispersion of water-soluble ampholytic polymer of the present invention comprises wherein the ampholytic polymer (B) is comprised of monomers of (i) cationic monomers that are selected from the group consisting of (a) diallyl dimethyl ammonium chloride and (b) methacrylamidopropyl trimethyl ammonium chloride; (ii) anionic monomers selected from the group consisting of acrylic acid, methacrylic acid and acrylamidomethylpropane sulfonic acid; and (iii) nonionic monomers selected from the group consisting of acrylamide, methyl acrylate and stearyl methactylate.
  • cationic monomers that are selected from the group consisting of (a) diallyl dimethyl ammonium chloride and (b) methacrylamidopropyl trimethyl ammonium chloride
  • anionic monomers selected from the group consisting of acrylic acid, methacrylic acid and
  • a particularly preferred composition for the ampholytic polymer (B) in the aqueous dispersion of water-soluble ampholytic polymer of the present invention is 30 mol % of diallyl dimethyl ammonium chloride as cationic monomer (i), 35 mol % of acrylic acid as anionic monomer (ii), and 35 mol % of acrylamide as nonionic monomer (iii).
  • aqueous dispersions of water-soluble ampholytic polymers of the present invention are used as compositions for treating hair, skin and nails by incorporating them in a cosmetically acceptable medium in amounts of from 0.1-10% by weight of said terpolymer, and preferably in an amount of from 0.5 to 5% by weight of said water soluble polymer.
  • compositions can be presented in various forms, i.e., various cosmetically acceptable media, such as a liquid, cream, emulsion, gel, thickening lotion or powder; they can contain water and also any cosmetically acceptable solvent, in particular monoalcohols, such as alkanols having 1 to 8 carbon atoms, like ethanol, isopropanol, benzyl alcohol and phenylethyl alcohol, polyalcohols, such as alkylene glycols, like glycerins, ethylene glycol and propylene glycol, and glycol ethers, such as mono-, di- and tri-ethylene glycol monoalkyl ethers, for example ethylene glycol monomethyl ether, ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, used singly or in a mixture.
  • solvents can be present in proportions of up to as much as 70% by weight, relative to the weight of the total composition.
  • compositions can also be packaged as an aerosol, in which case they can be applied either in the form of an aerosol spray or in the form of an aerosol foam.
  • propellant gas ⁇ for these aerosols it is possible to use, in particular, dimethyl ether, carbon dioxide, nitrogen, nitrous oxide and volatile hydrocarbons, such as butane, isobutane, propane and, possibly, chlorinated and fluorinated hydrocarbons, although the latter are falling into increasing environmental disfavor.
  • compositions can also contain electrolytes, such as aluminum chlorhydrate, alkali metal salts, e.g., sodium, potassium or lithium salts, these salts preferably being halides, such as the chloride or bromide, and the sulphate, or salts with organic acids, such as the acetates or lactates, and also alkaline earth metal salts, preferably the carbonates, silicates, nitrates, acetates, gluconates, pantothenates and lactates of calcium, magnesium and strontium.
  • electrolytes such as aluminum chlorhydrate, alkali metal salts, e.g., sodium, potassium or lithium salts, these salts preferably being halides, such as the chloride or bromide, and the sulphate, or salts with organic acids, such as the acetates or lactates, and also alkaline earth metal salts, preferably the carbonates, silicates, nitrates, acetates, gluconates, pantothen
  • compositions can also be presented in the form of a powder or of lyophilisates to be diluted before use.
  • compositions according to the present invention can contain any other ingredient normally used in cosmetics, such as perfumes, dyestuffs which can serve to color the composition itself or the fibres of the hair, preservatives, sequestering agents, thickeners, silicones, softeners, foam synergistic agents, foam stabilisers, sun filters, peptising agents and also anionic, non-ionic, cationic or amphoteric surface-active agents or mixtures thereof.
  • compositions can be used, in particular, in the form of a shampoo, a rinsing lotion, a cream or a treatment product which can be applied before or after coloring or bleaching, before or after shampooing, before or after perming or before or after straightening, and can also adopt the form of a coloring product, a setting lotion, a brushing lotion, a bleaching product, a perming product or a straightening product.
  • a particularly preferred embodiment consists of use in the form of a shampoo for washing the hair.
  • compositions contain anionic, cationic, nonionic or amphoteric surface-active agents typically in an amount from 3 to 50% by weight, preferably 3 to 20%, and their pH is 3 to 10, preferably 4 to 9 and most preferably 4.5 to 8.5.
  • Another preferred embodiment consists of use in the form of a rinsing lotion to be applied mainly before or after shampooings.
  • These lotions are typically aqueous or aqueous-alcoholic solutions, emulsions, thickened lotions or gels.
  • the compositions can be nonionic, anionic or cationic.
  • the nonionic emulsions consist mainly of a mixture of an oil and/or a fatty alcohol with a polyoxyethyleneated alcohol, such as polyoxyethyleneated stearyl or cetyl/stearyl alcohol, and cationic surface-active agents can be added to these compositions.
  • the anionic emulsions are formed essentially from soap.
  • compositions are presented in the form of a thickened lotion or a gel, they contain thickeners in the presence or absence of a solvent.
  • the thickeners which can be used are especially carbopol, xanthan gums, sodium alginates, gum arabic and cellulose derivatives, and it is also possible to achieve thickening by means of a mixture of polyethylene glycol stearate or distearate or by means of a mixture of a phosphoric acid ester and an amide.
  • the concentration of thickener is suitably 0.05 to 15% by weight.
  • the compositions are presented in the form of a styling lotion, shaping lotion or setting lotion, they generally comprise, in aqueous, alcoholic or aqueous- alcoholic solution, the aqueous dispersions of water-soluble ampholytic polymers defined above.
  • compositions of the invention are intended for use in the dyeing of keratin fibres, and in particular human hair, they contain at least one oxidation dyestuff precursor and/or one direct dyestuff, in addition to the aqueous dispersion of water-soluble ampholytic polymers. They can also contain any other adjuvant normally used in this type of composition.
  • the pH of the dyeing compositions is generally 7 to 11 , and can be adjusted to the desired value by adding an alkalizing agent.
  • composition according to the present invention can also be used for waving or straightening the hair.
  • the composition contains, in addition to the aqueous dispersion of water-soluble ampholytic polymer, one or more reducing agents and, if appropriate, other adjuvants normally used in this type of composition; such compositions are intended for use conjointly with a neutralizing composition.
  • composition according to the present invention can also be used for skin care products such as those that are primarily "leave on” formulations such as moisturizing lotions, emulsions and creams and sunscreen formulations.
  • Other skin care products would include “rinse off' formulations such as bar soaps, liquid hand soaps, disinfecting soaps and shower gels.
  • These "rinse off' formulations can be comprised of a variety of surfactants as outlined above, alkali salts of fatty acids (soaps) or combinations of each.
  • a process for in which paper or paperboard having improved properties is made by forming an aqueous cellulosic paper furnish which comprises adding to the furnish an effective amount, based on the dry weight of the solids of the furnish, of aqueous dispersion of an ampholytic polymer, as described above.
  • This amount can typically be from 0.1 to 25 pounds per ton on a dry basis, based on furnish.
  • aqueous dispersions of water-soluble ampholytic polymers of the instant invention can generally be successfully added to aqueous cellulosic furnishes over the entire pH range customarily employed in the papermaking process.
  • the composition of the instant invention is added to aqueous cellulosic furnishes having a pH from about 3 to 10. Therefore, it will be appreciated by those skilled in the art that the composition of the instant invention may be added to aqueous cellulosic paper furnishes that are acid, alkaline, or neutral in character.
  • an acid furnish has a pH range from about 3.0 to 5.5
  • an alkaline furnish has a pH range from about 7.0 to greater than about 10.0
  • a neutral furnish has a pH range of from about 5.5 to 7.0.
  • the instant invention is also directed to a method for drilling a well in a subterranean formation comprising circulating into the well, during drilling an aqueous drilling fluid, the improvement wherein said aqueous drilling fluid comprises: (a) an aqueous clay dispersion; and
  • the clay dispersion may be any finely divided solid which is capable of being dispersed or suspended in an aqueous liquid vehicle.
  • aqueous liquid vehicle Ordinarily, such material will include hydratable clay or colloidal clay bodies such as Wyoming bentonite, commercial medium-yield drilling clays mined in various parts of the country such as in Texas, Tennessee and Louisiana, and those produced when clay subsurface formations are drilled. Weighting materials added to increase specific gravity such as barites, iron oxide, and the like may also be included.
  • the aqueous medium may be fresh water such as is obtained from wells or streams; it may be salt water from the sea or from wells; or, it may even include oil-in-water emulsions, i.e., water which has become contaminated in some way with small quantities of oil, or to which such oil has been added to gain some desired advantage.
  • the polymers of the instant invention were found to be particularly effective in salt water and to be stable at high temperature.
  • the drilling mud containing the polymers of the instant invention show both good filtration and rheology properties.
  • the drilling muds of the invention may also contain other additives besides the polymers of the invention.
  • Materials such as caustic, quebracho, lime and the like may be added to the drilling mud at the surface while other materials such as gypsum, shale and the like may be encountered in subsurface formations during drilling operations.
  • the polymer When employed in accordance with the invention, the polymer may be added directly to the drilling mud as a dry powder, as a slurry suspended in a suitable liquid, or as a solution in water or some other suitable solvent, and they may be incorporated therein at any convenient point in the mud circulation system. It may be desirable to employ a mixing device such as a cone and jet mixer or the equivalent for incorporating the additive in the mud.
  • a mixing device such as a cone and jet mixer or the equivalent for incorporating the additive in the mud.
  • the present invention is also directed to cementing compositions that are useful in oil, gas and water well cementing operations since such compositions have reduced fluid loss to the surrounding formation.
  • Such compositions are used to cement a conduit penetrating a permeable earthen formation via introducing such composition into the space between such conduit and such formation and allowing the composition to harden.
  • These cementing compositions for use in oil, gas and water well cementing operations comprise water, hydraulic cement, and the branched ampholyte polymer of the present invention.
  • the present invention is also directed to a method for clarifying waste water containing turbidity-causing components which comprises: a) adding to said water an effective turbidity-reducing amount of the aqueous dispersion of water-soluble ampholytic polymers; b) mixing said aqueous dispersion polymer and said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity-causing components; and then c) separating the flocculated turbidity-causing components from the waste water to obtain clarified water.
  • the present invention can also be used to thicken aqueous solutions.
  • the thickening action is accomplished by adding the aqueous dispersion of ampholytic polymer composition described above to an aqueous solution and subsequently raising the pH of the aqueous solution above pH 6.
  • the ampholytic polymer will completely solubilize with the higher pH and increase the viscosity of the aqueous solution.
  • the resulting gel is allowed to set overnight.
  • 600 g of the 20% polymer gel is removed for dilution and charged to a 2-I resin kettle to which Dl water is added, mixed and heated to 80°C.
  • the resulting gel is allowed to set overnight.
  • 600 g of the 20% polymer gel is removed for dilution and charged to a 2-I resin kettle to which Dl water is added, mixed and heated to 80°C.
  • Example 3 The polymers of Example 1 and 2 were tested in a typical Shampoo.
  • the lower total work required for the shampoo using the polymer of Example 1 compared with the total work required for the shampoo using the polymer of Example 2 indicates that the polymer of Example 1 performs suprisingly better as a conditioner for hair.
  • Example 4 An aqueous clay based drilling mud is prepared using the polymer of Example 1 as outlined in Table 2.
  • the clay based gypsum drilling mud is aged for 16 hours at 325 °F and then cooled.
  • the resulting API filtrate reading is lower for the formula of the example when compared to a corresponding clay based gypsum drilling mud without polymer.
  • Example 5 A cementing composition is prepared using the polymer of Example 1 as outlined in Table 3.
  • the cementing composition is mixed into a slurry.
  • the resulting API filtrate reading (30 minute, 125 °F, 1 ,000 psi) is lower for the formula of the example when compared to a corresponding cementing composition without polymer.
  • Example 6 This example demostrates the ability of the water-soluble ampholytic polymer dispersion of Example 1 to thicken water.
  • An 11% active solution of the polymer of Example 1 was prepared and pH increased by adding sodium hydroxide solution. The viscosity of the solution was measured at 30°C for each pH.

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Abstract

L'invention concerne des dispersions aqueuses de polymères ampholytiques. Le pH de dispersion, compris entre 2 et 6, permet d'incorporer à la dispersion des niveaux élevés de polymères ampholytiques et de conserver une dispersion liquide, tandis que des solutions actives similaires se présenteraient sous forme de gel non liquide. L'invention concerne également l'utilisation de ce type de composition dans un milieu acceptable sur le plan cosmétique pour le traitement d'un substrat à base de kératine et pour l'épaississement de solutions aqueuses, mais aussi en tant qu'additif dans la fabrication du papier, en tant que composant dans les compositions liquides de forage, en tant que composant dans les compositions de cimentation et en tant qu'agent pour le traitement des eaux usées.
PCT/US2001/008103 2000-03-31 2001-03-14 Composition a base de dispersion de polymeres ampholytiques et procede d'utilisation WO2001074915A1 (fr)

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WO2014071354A1 (fr) * 2012-11-05 2014-05-08 Hercules Incorporated Composition comprenant un polymère de conditionnement et/ou de coiffage
CN104558406A (zh) * 2015-01-27 2015-04-29 江苏富淼科技股份有限公司 一种两性聚丙烯酰胺分散液的制备方法
CN105199057A (zh) * 2015-09-16 2015-12-30 西安石油大学 一种多功能抗高温钻井液处理剂的制备方法
CN108697820A (zh) * 2016-02-17 2018-10-23 株式会社实瞳 抗棘阿米巴接触镜用溶剂
US10240295B2 (en) * 2016-05-30 2019-03-26 Harima Chemicals, Inc. Pitch-controlling agent and pitch-controlling method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112723512B (zh) * 2020-12-29 2022-02-25 中国矿业大学(北京) 一种复合絮凝剂的制备方法和应用

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US3868328A (en) * 1972-03-09 1975-02-25 Calgon Corp Friction reducing compounds for use in hydraulic fracturing fluids
US4861499A (en) * 1987-10-13 1989-08-29 American Cyanamid Company Water-dispersible hydrophobic thickening agent
US4871594A (en) * 1987-04-07 1989-10-03 Hoechst Ag Use of aqueous cationic dispersions of synthetic resins for impregnating and priming of absorbent substrates
US5403883A (en) * 1992-05-18 1995-04-04 Roehm Gmbh Chemische Fabrik Water soluble polymer dispersions
US5413731A (en) * 1992-03-10 1995-05-09 Rohm & Haas Company Aminoacryloyl-containing terpolymers
US6110451A (en) * 1998-12-18 2000-08-29 Calgon Corporation Synergistic combination of cationic and ampholytic polymers for cleansing and/or conditioning keratin based substrates
US6180576B1 (en) * 1998-08-20 2001-01-30 Allan L. Melby Conditioning shampoo compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3868328A (en) * 1972-03-09 1975-02-25 Calgon Corp Friction reducing compounds for use in hydraulic fracturing fluids
US4871594A (en) * 1987-04-07 1989-10-03 Hoechst Ag Use of aqueous cationic dispersions of synthetic resins for impregnating and priming of absorbent substrates
US4861499A (en) * 1987-10-13 1989-08-29 American Cyanamid Company Water-dispersible hydrophobic thickening agent
US5413731A (en) * 1992-03-10 1995-05-09 Rohm & Haas Company Aminoacryloyl-containing terpolymers
US5403883A (en) * 1992-05-18 1995-04-04 Roehm Gmbh Chemische Fabrik Water soluble polymer dispersions
US6180576B1 (en) * 1998-08-20 2001-01-30 Allan L. Melby Conditioning shampoo compositions
US6110451A (en) * 1998-12-18 2000-08-29 Calgon Corporation Synergistic combination of cationic and ampholytic polymers for cleansing and/or conditioning keratin based substrates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014071354A1 (fr) * 2012-11-05 2014-05-08 Hercules Incorporated Composition comprenant un polymère de conditionnement et/ou de coiffage
US9662293B2 (en) 2012-11-05 2017-05-30 Hercules Llc Personal care composition for a keratin substrate comprising conditioning and/or styling polymer
CN104558406A (zh) * 2015-01-27 2015-04-29 江苏富淼科技股份有限公司 一种两性聚丙烯酰胺分散液的制备方法
CN105199057A (zh) * 2015-09-16 2015-12-30 西安石油大学 一种多功能抗高温钻井液处理剂的制备方法
CN108697820A (zh) * 2016-02-17 2018-10-23 株式会社实瞳 抗棘阿米巴接触镜用溶剂
US10240295B2 (en) * 2016-05-30 2019-03-26 Harima Chemicals, Inc. Pitch-controlling agent and pitch-controlling method

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AR027757A1 (es) 2003-04-09

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