WO1997003111A2 - Produits polymeres solides et leur utilisation - Google Patents

Produits polymeres solides et leur utilisation Download PDF

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Publication number
WO1997003111A2
WO1997003111A2 PCT/GB1996/001638 GB9601638W WO9703111A2 WO 1997003111 A2 WO1997003111 A2 WO 1997003111A2 GB 9601638 W GB9601638 W GB 9601638W WO 9703111 A2 WO9703111 A2 WO 9703111A2
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WO
WIPO (PCT)
Prior art keywords
water
product according
granules
matrix
soluble
Prior art date
Application number
PCT/GB1996/001638
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English (en)
Other versions
WO1997003111A3 (fr
Inventor
Simon Alexander Hanson Rose
Peter Chamberlain
Original Assignee
Allied Colloids Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allied Colloids Limited filed Critical Allied Colloids Limited
Priority to AU63660/96A priority Critical patent/AU6366096A/en
Publication of WO1997003111A2 publication Critical patent/WO1997003111A2/fr
Publication of WO1997003111A3 publication Critical patent/WO1997003111A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/16—Soil-conditioning materials or soil-stabilising materials containing organic compounds only applied in a physical form other than a solution or a grout, e.g. as platelets or granules
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • This invention relates to solid products which comprise water-soluble or water-swellable polymeric particles.
  • these may first be activated into an aqueous composition (for instance for use as a viscosifier or flocculant) or they may be scattered in particulate form (for instance as a soil conditioner or pelletisation binder) .
  • Soluble or swellable polymer particles can be made by reverse phase emulsion polymerisation to provide a relatively stable emulsion of very small (below lO ⁇ m) hydrous or anhydrous polymer particles in oil. These can be agglomerated, for instance as in W092/13912 or US 3,891,592 or the emulsion may be treated as in unpublished PCT/GB95/00283. Usually, however, the emulsion is used without treatment.
  • Direct addition of the emulsion to the suspension or other medium which is to be treated tends to be unsatisfactory, for instance because of destabilisation of the emulsion during the addition with consequential aggregation of the polymer particles, and so usually the emulsion is activated by dissolution in water in the presence of an oil-in-water emulsifier which serves as an activator and the resultant solution is then added to the medium which is to be treated.
  • Water-soluble or water-swellable polymer particles in the form of powder are usually made by reverse phase bead polymerisation followed by drying and recovery of particles or by gel polymerisation followed by drying and comminution. These methods generally provide a relatively coarse particle size typically in the range 200 to l,000 ⁇ m. However the powder will usually also include some finer particles and if desired the manufacturing technique can be conducted so as to maximise the amount of fines.
  • the powder When the powder is to be activated by mixing with water to form a stable aqueous solution of dispersion, for instance before use as a viscosifier or flocculant, it is usual practice first to expose the particles to water under conditions that allow full hydration of the particles either to form a solution of the polymeric material or to form a suspension of highly swollen particles in water.
  • Various problems can arise in handling the polymer particles prior to and during the exposure to the water. For instance the particles may tend to acquire a gel layer upon initial exposure, which gel layer may inhibit access of water and cause aggregation, thus interfering with dissolution or swelling of the particles. This problem can be minimised in many instances by appropriate selection of the exposure conditions but in some instances it is not possible to optimise these.
  • the particles with a coating of inorganic salt or other material, optionally in combination with a binding agent to promote adhesion of the inorganic salt to the polymer particles.
  • a coating of inorganic salt or other material optionally in combination with a binding agent to promote adhesion of the inorganic salt to the polymer particles.
  • a composition contains 0 to 5% polyethylene glycol and 5 to 90% sodium sulphate
  • JP 57162610 a composition contains 9 to 49% inorganic salt and 1 to 10% polyethylene glycol.
  • the glycol is generally applied from a solution but it is mentioned that the coating can be achieved by mixing the particles with solid granulated polyalkylene glycol in a rotating drum or blender at a temperature sufficient to melt the glycol, the blended product is then cooled while mixing, and the cooled product is discharged from the blender.
  • JP-B-4726584 JP-A-44102922
  • a foamed block is formed from a polyacrylic ester polymer, alginate polymer, aluminium sulphate, water and a foam-forming material.
  • the polyacrylic ester polymer is said to have a molecular weight of at least 10,000 and so it seems that the main water treatment chemical in this block is the aluminium sulphate.
  • blocks containing particulate polymeric flocculant For instance in EP-A- 255,283 blocks are formed of water-soluble multivalent metal coagulant and particulate polymeric flocculant, whereby the surface of the blocks is eroded by immersion in a flowing stream to form a solution of the coagulant in which the flocculant particles are entrained.
  • blocks formed from polyelectrolyte and polyethylene oxide wax In US 3,305,019 and 3,435,618 Katzer describes blocks formed from polyelectrolyte and polyethylene oxide wax. A problem with all blocks containing high molecular weight polymeric particles is that there is a tendency for these particles to form a protective layer of partially dissolved polymer gel around the blocks.
  • inorganic salt can facilitate dissolution but this tends to be rather ineffective when very high molecular weight polymers are present. This is a particular problem when the main purpose of the block is to administer the polymer into the suspension since adding sufficient salt to give a useful change in erosion rate will in practice result in the block containing, and therefore supplying to the suspension, less polymer.
  • a product which comprises particles of water-soluble or water-swellable polymeric material dispersed in a matrix of water-soluble or water-swellable bonding agent, and in this product the matrix is a foamed matrix or includes a water-activatable effervescent agent.
  • the invention is of particular value when the product is granular and the granules each comprise the polymer particles dispersed in the matrix of bonding agent and the matrix includes the water activatable effervescent agent.
  • the granules generally have a size such that at least
  • 90% by weight of the granules are below 10, and usually below 5, m and preferably below 1 mm.
  • Preferred granular products of the invention have at least 90% by weight of the granules between 200 and l,000 ⁇ m, often between 200 and 700 ⁇ m.
  • the granules can have any convenient particulate shape such as conventional powder shapes or flakes.
  • the effervescent agent in the matrix can be any material which, upon contact of the product with water, will cause effervescence.
  • the combination of the contact with water and the effervescence tends to disrupt the water-soluble or water-swellable bonding agent matrix. This will therefore tend to cause the individual polymer particles in the granular product to separate from one another and therefore promotes individual activation of the polymer particles when they are being used (for instance in iron ore pelletisation or as soil conditioner) or when they are being activated in water before use.
  • the flotation effect is selected so that in static water (or in whatever activation conditions are being used) the flotation effect is sufficient for the granules to disintegrate while the granules are floating with substantially no formation of a surface layer of granules or polymer particles.
  • weighting agent in the granular product in order to allow adjustment of the density of the granular product and thereby to allow control of the degree of flotation.
  • the amount of weighting agent (if present) and the amounts of the other components of the granules are preferably such that the granules initially sediment when added to static water but then float due to effervescence of the effervescent agent and disintegrate while floating, and preferably the disintegration is sufficiently complete that no significant layer of dissolving granules accumulates on the surface of the water.
  • the effervescent agent can be any material which, when dissolved in water, results in the suitable release of a gas. Generally it is a combination of solid materials which react in water to release a gas. Preferably it is a combination of a solid water-soluble acid with a soli d water-soluble carbonate or bicarbonate.
  • the carbonate or bicarbonate is usually of sodium, but potassium or other water-soluble carbonates or bicarbonates may be used.
  • the solid water soluble acid may be, for instance, particulate citric acid, tartaric acid, benzoic acid, sulphamic acid or a polymeric carboxylic acid, generally a solid water-soluble polymer of acrylic or methacrylic acid.
  • a liquid polymeric or other acid is suitable provided that the other components of the granules are such that the acid is absorbed into a component of the granules or the granules (without reaction with the carbonate) to provide solid, substantially non- sticky, granules.
  • the preferred acid is citric acid.
  • the preferred effervescent agent is a mixture of citric acid and sodium bicarbonate.
  • the proportions of the components in the effervescent agent will be selected so as to obtain suitable effervescence and are usually within 50 to 150% of stoichiometric proportions, and preferably the proportions are stoichiometric.
  • a suitable weighting agent that can be used is barium sulphate, but any other dense, finely divided, non-toxic, particulate material can be used.
  • the polymer which forms the polymer particles is chosen according to the intended use of the product.
  • the products of the invention are suitable for use in many applications, for instance iron ore pelletisation, flocculation of mineral suspensions, flocculation of sewage sludge, soil conditioning, for instance as flocculants in field irrigation, and as agricultural anti-drift agents.
  • the polymer particles can be relatively coarse (for instance having a size up to 1 mm, when the granular size is coarse (for instance having a size up to 5 mm) .
  • the product can be a mixture of aggregates of polymer particles with non-aggregated polymer particles which are coated with the bonding agent and effervescent agent but are not aggregated with other polymer particles. Generally, however, substantially all the granules are aggregates of polymer particles and thus the polymer particle size will generally be significantly less than the granule size. Generally at least 90% by weight of the polymer particles have a size below 500 ⁇ m and preferably below 300 ⁇ m.
  • the invention is of particular value when the polymer particles are polymer fines separated during the production of coarser polymer powder.
  • the particles are below 150 ⁇ m and usually below lOO ⁇ m, often in the range 10 to 70 ⁇ m.
  • the particles are beads made by reverse phase polymerisation.
  • the polymer particles may be particles made by reverse phase emulsion polymerisation to a size below lO ⁇ m, for instance in the range 0.01 or, more usually, 0.05 or O.l ⁇ up to 5 ⁇ m.
  • the water-soluble or swellable polymer particles are generally formed from water-soluble monoethylenically unsaturated monomer or monomer blend, and the water- swellable polymer particles are generally made by cross- linking such a polymer, for instance by including a polyethylenically unsaturated cross-linking agent in the polymerisation mixture.
  • the monomers are acrylic monomers although some allyl or other vinyl monomers are suitable.
  • the monomers can be anionic or cationic or non-ionic. Blends can be amphoteric but are generally formed from anionic and non-ionic monomers or cationic and non-ionic monomers.
  • Suitable anionic monomers include (meth) acrylic acid (including alkali metal, ammonium or amine salts) and other ethylenically unsaturated carboxylic or sulphonic acid monomers.
  • Suitable cationic monomers include dialkylaminoalkyl (meth)-acrylamide and - acrylate, generally as quaternary ammonium or acid addition salts, and diallyl dimethyl ammonium chloride.
  • Suitable non-ionic monomers include acrylamide and N-vinyl formamide. The monomers and the polymerisation conditions will be chosen in conventional manner having regard to the desired end use of the product. Thus the invention provides a convenient and novel way of formulating a polymer which is otherwise of standard composition for its intended end use.
  • the polymers are usually of high molecular weight and the soluble polymers usually have intrinsic viscosity above 4 dl/g and often above 8 dl/g, for instance up to 20 or 30 dl/g. These very high intrinsic viscosity values are of particular value for polymers which are to be used as viscosifiers or bridging flocculants.
  • the intrinsic viscosity is usually in the range 3 to 12 dl/g and the polymer is usually anionic
  • the polymer for instance a copolymer of acrylamide and sodium acrylate
  • the intrinsic viscosity is generally in the range 0.3 to 3 dl/g, often 0.7 to 2.5 dl/g, and the polymer is usually formed from at least 50% by weight, and usually at least 80% by weight diallyldimethyl ammonium chloride or other cationic monomer.
  • the polymer may have been made from the chosen monomer or monomers by a conventional technique such as gel polymerisation followed by comminution and drying or reverse phase bead polymerisation followed by drying and separation of the beads, and optionally comminution, or reverse phase emulsion polymerisation optionally followed by distillation to render the polymer emulsion particles substantially anhydrous.
  • the water-soluble or water-swellable bonding agent can be any material which will provide a matrix which interconnects the particulate polymeric material, and thus the bonding agent should be film forming. It should normally be applied in non-aqueous form, to avoid activation of any water-soluble effervescent agent in the mixture.
  • a bonding agent which is a wax which melts at a temperature between 20 and 250°C.
  • the granular product can be made by aggregating the polymer particles and effervescent agent with molten wax and solidifying the wax.
  • the wax may be any substance or mixture of substances that is solid at normal temperatures but which can be liquid at convenient manufacturing temperatures, for instance the temperature at which molten wax is blended with the polymer particles.
  • the melting point of the wax should be above 30°C and often above 40°C. It is usually undesirable to have to heat the mixture to too high a temperature and so preferably the melting point of the wax is not above 200°C, and most preferably it is not above 120°C.
  • These are the melting points of the matrix and so may be the melting point of the single material, when the matrix is formed of a single material, or may be the melting point of the molten blend that forms the matrix.
  • the wax matrix consists of or comprises water-soluble or water dispersible wax.
  • the amount of such waxes is preferably the predominant amount (above 50% by weight of the matrix) and is preferably above 80% by weight of the matrix.
  • examples include polyethylene glycols, for example, PEG 1450, PEG 4000, PEG 8000, polyethylene glycol esters, for example, PEG 8000 distearate, fatty acids, for example stearic acid or salts for example sodium or ammonium stearate, amides of fatty acids, for example, stearic acid diethanolamide, fatty alcohols, quaternary fatty waxes such as N-hydroxyethyl ethylene diamine reacted with stearic acid and then quaternised with dimethyl sulphate, or a mixture of two or more of these compounds.
  • Oil miscible, low melting, waxy surfactants may be used as part or all of the wax matrix.
  • the preferred bonding agent is polyethylene glycol.
  • the amount of wax must be sufficient to provide enough of a matrix structure to aggregate the polymer particles into granules. Amounts as low as 3% may be usable but generally the amount is above 5% and more usually above 10% by weight of the granules. If the amount is too low it can be very difficult to achieve adequate distribution of the bonding agent through the product. Usually the amount is above 15% and preferably it is at least 20% by weight of the granules.
  • the amount of bonding agent can be high, for instance up to about 70%, but since the granular product is usually intended primarily to deliver the polymeric particles to the desired location it is usually preferred for the amount of bonding agent to be as low as is consistent with convenient manufacture and dissolution characteristics.
  • the amount of bonding agent is below 60% by weight of the granular product and preferably it is not more than 50% by weight.
  • the amount of polymer particles in the product is usually as high as is conveniently possible and is normally at least 35 or 40%, and preferably at least 50%. The use of very high amounts can lead to difficulties in manufacture and so generally the amount of polymer particles is not more than 80% and is usually below 75%.
  • the total amount of polymer particles and wax is usually at least 70%, and preferably at least 80%, by weight of the product.
  • the amount of effervescent agent will be selected so as to provide the desired degree of effervescence. Usually it is at least 3% and usually at least 5% by weight of the granules. It can be as much as, for instance, 30% by weight or even more but it is generally preferred that it is in the range 8 to 20%.
  • Minor amounts of other components may be included in the granules.
  • surfactant can be included to promote wetting of the granules with water.
  • a release aid may be included in the granules, or may be coated onto the granules, so as to improve flow properties and to minimise aggregation of the granules.
  • the granular product is made by forming a mixture of the polymer particles, molten wax and the effervescent agent and cooling and converting this mixture to form the solid granules.
  • polymer powder may be blended with the wax which can be melted before or during the blending. Often the proportions are such that a melt dispersion i ⁇ formed of the polymer particles and effervescent agent in the molten wax.
  • melt dispersion Another way of forming such a melt dispersion is by forming a reverse phase dispersion or emul ⁇ ion of ⁇ ubstantially anhydrous polymer particles in a volatile organic liquid, dissolving wax into this liquid at a temperature at which the wax is molten, and evaporating the volatile liquid, as described in PCT/GB95/00283.
  • the mixing conditions may be such that the particles are formed while mixing is continuing, for instance by use of a mixer which resembles a domestic food blender, in which event cooling and solidification of the wax may be conducted during the mixing or during or immediately after discharge from the mixer. For instance the particles may be cooled while entrained in an air stream which carries them out of the mixer.
  • Other ways of forming the desired granular product include spraying or otherwise distributing the molten mixture as droplets, for instance onto a release coating or by spray chilling, or by extrusion into the desired granular form or by comminution of larger granules, blocks sheets which have been formed from the molten product.
  • the matrix of the granules can additionally have a foamed structure, for instance as a result of thermal decomposition of effervescent agent during the melt mixing.
  • the invention also includes block products, ie products which are larger than granules and which normally have a minimum dimension of at least 10 mm.
  • the product can be in the form of one or more blocks having a minimum dimension of at least 20mm and often 30mm or 50mm or more and having a maximum dimension of up to 50mm, 100mm, 500mm or more.
  • Typical blocks can have a weight of 0.02 to 10kg, often 0.05 to 5kg. For instance where prolonged relatively slow release i ⁇ required it may be appropriate to provide blocks of 1 to 5kg for immersion in a flowing stream but where faster relea ⁇ e is required it may be more appropriate to ⁇ upply blocks of 0.05 to 0.5kg.
  • Block products according to the invention can be made from the same materials and by the same general techniques as described above with respect to granular products, with appropriate modification of the molding or other shaping technique by which the molten mix is converted into the final solid block form.
  • the blocks should have a foamed matrix.
  • the foaming is preferably provided by thermal dissociation of a gas-forming compound during the manufacture of the block.
  • the block is preferably made by shaping a melt dispersion of the polymer particles and gas-forming compound in the wax while it is molten and allowing thermal decomposition to occur, and solidifying the foamed melt dispersion. Thu ⁇ the gas-forming compound liberates gas in the melt and the re ⁇ ultant foam is trapped upon solidification of the dispersion.
  • the gas-forming compound can be part of an effervescent agent combination, in which event the block will have a foamed ⁇ tructure and will effervesce upon contact with water. Often, however, the block does not ⁇ ubstantially efferve ⁇ ce on contact with water and the gas forming compound may be included primarily or only to cause foaming of the matrix.
  • the preferred gas-forming compounds are heat- decomposable carbonates and bicarbonates, preferably the sodium salts.
  • the amount of gas forming compound is typically in the range 3 to 20% by weight of the molten mixture. However the use of the higher amounts tend ⁇ to make handling of the mixture more difficult and ⁇ o generally the amount i ⁇ not more than about 10 or 15% by weight of the molten mixture.
  • the resulting agglomerated mix had a particle size between 200 ⁇ m and 5 mm and was chilled at 4 ⁇ C for 30 minutes and was then ground to a particle size of between 200 and 700 ⁇ m.
  • the granular product On addition to water, the granular product initially settled to the bottom of the vessel but then started to effervesce whereupon the granules slowly rose and disintegrated, allowing the individual polymer particles to activate and dissolve independently into the water.
  • the resultant solution can be used as a flocculant solution for a mineral suspension.
  • Example 2 60 pbw of a particulate homopolymer of diallyl dimethylammonium chloride IV 2 dl/g particle size 90% below 425 ⁇ m were blended in the general manner of Example 1 with 10 pbw citric acid, 10 pbw sodium bicarbonate and 20 pbw polyethyleneglycol. Upon addition to water, the granule ⁇ effervesced and disintegrated and the polymer dissolved quickly into the water.
  • the re ⁇ ultant polymer solution can be used as a coagulant ⁇ olution for the treatment of a suspension.
  • Example 1 The process of Example 1 is repeated using 60 pbw of a cationic copolymer of acrylamide and dimethylaminoethyl acrylate quaternised with methyl chloride, IV 7 dl/g, 1 0 pbw citric acid, 10 pbw sodium bicarbonate and 20 pbw polyethylene glycol.
  • the resultant solution can be used for flocculating sewage sludge.
  • a bonding agent for pelletising iron ore comprises a blend of 45 pbw lightly cros ⁇ -linked, partially soluble, fines (below 200 ⁇ m) copolymer of acrylamide and sodium acrylate and 20 pbw sodium carbonate. This mixture was blended with 9 pbw citric acid and 26 pbw polyethylene glycol in the same general manner as in Example 1.
  • Example 5 A blend was formed of 50 pbw bead fines of a copolymer of acrylamide and sodium acrylate having IV 18 dl/g (sieved from a bead product made by reverse phase bead polymerisation) and 50 pwb polyethylene glycol 4,000 by mixing the materials at a temperature at which the polyethylene glycol is molten. The resultant melt dispersion was cast into blocks and allowed to cool.
  • melt disper ⁇ ion became increasingly difficult to handle and cast as the amount of sodium bicarbonate increased, especially above 10 pbw.
  • a product for use as an agricultural anti-drift agent comprises a blend of 64.9 pbw of a water-soluble copolymer of acrylamide and sodium acrylate, IV 10 dl/g, 28 pbw PEG 4000, 2 pbw citric acid and 5.1 pbw sodium bicarbonate.
  • Granules are prepared in the same general manner as in Example 1.
  • Example 7 When added to water, the granules effervesce and disintegrate so that the polymer can dissolve quickly into the water.
  • This example demonstrates the provision of soil conditioners in the form of the products of the invention.
  • Soil trays measuring 16 x 20 cm were filled with a sandy silt loam, which had been dried and sieved tc produce aggregates between 710 and 8,000 ⁇ m.
  • the soil (containing 2.6% organic matter and with pH 7.45) was known to be extremely poorly ⁇ tructured.
  • Two row ⁇ of onion seeds were sown per tray, at a rate of six seeds per row, to a depth of 1 cm. The following treatments were applied dry to the soil surface above the seed row.
  • Example 2 Composition of Example 1 0.033g/row (67% active) (Effervescent Granule)
  • the granular polymer had the same chemical composition as the fine granules used to form the effervescent granule.
  • the particle size of the granular polymer was similar to that of the effervescent granule.
  • a soil 'cap' was created by spraying water onto the surface of the soils, via a Lurmark Flat Fan nozzle 015 F80°.
  • a compressed air cylinder was used to deliver the water at a pre ⁇ sure of 3 bar.
  • the trays were periodically watered with identical amounts of tap water, taking care not to disturb the soil 'cap'. All trays were placed below UV lights for 9 hours per day. Germination counts (expressed as percentage of total seeds) were taken at regular periods and were as shown in Table l below. Table 1

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Abstract

L'invention concerne un produit composé de particules d'un matériau polymère soluble dans l'eau ou gonflant dans l'eau, dispersées dans une matrice d'agent liant soluble dans l'eau ou gonflant dans l'eau, ladite matrice comprenant un agent effervescent pouvant être activé par l'eau et/ou étant mise à l'état moussant. Ces produits permettent d'obtenir un matériau polymère sous une forme capable de se disperser et de se dissoudre facilement.
PCT/GB1996/001638 1995-07-13 1996-07-08 Produits polymeres solides et leur utilisation WO1997003111A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63660/96A AU6366096A (en) 1995-07-13 1996-07-08 Solid polymeric products and their use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9514283.2 1995-07-13
GBGB9514283.2A GB9514283D0 (en) 1995-07-13 1995-07-13 Solid polymeric products and their use

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WO1997003111A2 true WO1997003111A2 (fr) 1997-01-30
WO1997003111A3 WO1997003111A3 (fr) 1997-03-20

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6300302B1 (en) * 1997-04-14 2001-10-09 The Procter & Gamble Detergent particle
US6440926B1 (en) * 1997-04-14 2002-08-27 The Procter & Gamble Company Effervescent compositions and dry effervescent granules
EP1771531A2 (fr) * 2004-06-22 2007-04-11 Biocentral Laboratories Limited Concentrat de retention d'eau polymere biodegradable
WO2012117211A1 (fr) * 2011-03-03 2012-09-07 S.P.C.M. Sa Produit destine a etre additionne a l'eau d'irrigation de cultures
WO2014040120A1 (fr) * 2012-09-11 2014-03-20 Vitel Australia Pty Ltd Comprimé effervescent pour une réduction de dérive de pulvérisation et procédé d'utilisation

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Publication number Priority date Publication date Assignee Title
US4389506A (en) * 1981-06-29 1983-06-21 E. I. Du Pont De Nemours And Company Polyvinyl alcohol dust suppression by admixing polyglycol
WO1989005326A1 (fr) * 1987-12-04 1989-06-15 Chemische Fabrik Stockhausen Gmbh Procede d'agglomeration par frittage de polymeres gonflables dans l'eau
WO1992013912A1 (fr) * 1991-02-09 1992-08-20 Basf Aktiengesellschaft Particules agglomerees en polymeres finement pulverises solubles ou gonflables dans l'eau
WO1995021797A1 (fr) * 1994-02-11 1995-08-17 Allied Colloids Limited Produits polymeres solides et leur utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4389506A (en) * 1981-06-29 1983-06-21 E. I. Du Pont De Nemours And Company Polyvinyl alcohol dust suppression by admixing polyglycol
WO1989005326A1 (fr) * 1987-12-04 1989-06-15 Chemische Fabrik Stockhausen Gmbh Procede d'agglomeration par frittage de polymeres gonflables dans l'eau
WO1992013912A1 (fr) * 1991-02-09 1992-08-20 Basf Aktiengesellschaft Particules agglomerees en polymeres finement pulverises solubles ou gonflables dans l'eau
WO1995021797A1 (fr) * 1994-02-11 1995-08-17 Allied Colloids Limited Produits polymeres solides et leur utilisation

Cited By (10)

* Cited by examiner, † Cited by third party
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US6300302B1 (en) * 1997-04-14 2001-10-09 The Procter & Gamble Detergent particle
US6440926B1 (en) * 1997-04-14 2002-08-27 The Procter & Gamble Company Effervescent compositions and dry effervescent granules
EP1771531A2 (fr) * 2004-06-22 2007-04-11 Biocentral Laboratories Limited Concentrat de retention d'eau polymere biodegradable
EP1771531B1 (fr) * 2004-06-22 2014-05-21 Biocentral Laboratories Limited Concentrat de polymere biodegradable pour retention d'eau
WO2012117211A1 (fr) * 2011-03-03 2012-09-07 S.P.C.M. Sa Produit destine a etre additionne a l'eau d'irrigation de cultures
FR2972197A1 (fr) * 2011-03-03 2012-09-07 Snf Sas Produit destine a etre additionne a l'eau d'irrigation de cultures
US20130340333A1 (en) * 2011-03-03 2013-12-26 S.P.C.M. Sa Product intended to be added to crop irrigation water
WO2014040120A1 (fr) * 2012-09-11 2014-03-20 Vitel Australia Pty Ltd Comprimé effervescent pour une réduction de dérive de pulvérisation et procédé d'utilisation
CN104684386A (zh) * 2012-09-11 2015-06-03 维泰尔澳大利亚有限公司 用于喷雾漂移减少的泡腾片剂及使用方法
EP2894977A4 (fr) * 2012-09-11 2016-05-11 Vitel Australia Pty Ltd Comprimé effervescent pour une réduction de dérive de pulvérisation et procédé d'utilisation

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GB9514283D0 (en) 1995-09-13
WO1997003111A3 (fr) 1997-03-20
ZA965952B (en) 1997-07-14
AU6366096A (en) 1997-02-10

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