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WO1994000512A1 - Procede de production de mousses au polysaccharide - Google Patents

Procede de production de mousses au polysaccharide Download PDF

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Publication number
WO1994000512A1
WO1994000512A1 PCT/US1993/005993 US9305993W WO9400512A1 WO 1994000512 A1 WO1994000512 A1 WO 1994000512A1 US 9305993 W US9305993 W US 9305993W WO 9400512 A1 WO9400512 A1 WO 9400512A1
Authority
WO
WIPO (PCT)
Prior art keywords
foam
polysaccharide
aqueous solution
solution
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1993/005993
Other languages
English (en)
Inventor
Dana Burton Eagles
George Bakis
Andrew Bruce Jeffery
Constantinos Mermingis
Thomas Henry Hagoort
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Albany International Corp
Original Assignee
Albany International Corp
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
Priority claimed from GB929212976A external-priority patent/GB9212976D0/en
Priority claimed from GB929224255A external-priority patent/GB9224255D0/en
Priority to US08/196,079 priority Critical patent/US5840777A/en
Application filed by Albany International Corp filed Critical Albany International Corp
Priority to FI940735A priority patent/FI940735A7/fi
Priority to CA002116037A priority patent/CA2116037C/fr
Priority to BR9305552A priority patent/BR9305552A/pt
Priority to AU45437/93A priority patent/AU672214B2/en
Priority to EP19930915464 priority patent/EP0612331A4/fr
Publication of WO1994000512A1 publication Critical patent/WO1994000512A1/fr
Priority to NO940546A priority patent/NO940546D0/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28—Polysaccharides or their derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00

Definitions

  • the present invention relates to a method of producing polysaccharide foams; in particular alginate, chitosan/starch and hyaluronate foams.
  • the invention also embraces polysaccharide foamed materials produced in accordance with the method of the invention and wound dressings, foamed cell culture replicating media, barrier media for preventing tissue adherence and other absorbent materials comprising such foams.
  • Alginates particularly calcium alginates and converted calcium alginates, have long been known for their ability to form fibres and yarns which can be knitted into fabrics or formed into nonwoven materials primarily for use as swabs or dressings for medical, surgical or other purposes.
  • British Patent Specification No. 1283399 describes and claims a method of preparing a solublized calcium-containing alginate material which comprises acidifying calcium alginate with a calculated quantity of acid sufficient to remove a desired amount of calcium, reacting the acidified calcium alginate with an excess of base selected from ammonia, amines and substituted amines and washing the solubilized calcium-containing alginate to remove the excess of base.
  • This material may be formed into a number of pieces of gauze which can then be further treated as described in the specification.
  • British Patent Specification No. 1394742 relates to a surgical dressing material comprising a layer of knitted gauze adhered to a layer of fibrous backing material, the gauze comprising alginate material and the dressing material being of lower flexibility and stretchability than the gauze itself.
  • British Patent Specification No. 1570485 relates to an absorbent material for aqueous fluids which comprises an open cell foam containing within the cells a hydrophilic gel having specific properties. Typical of the hydrophilic gels is alginates. The specification describes the incorporation of these materials in a reticulated foam; the gel being contained within the cells of the foam thus providing an absorbent material.
  • United States Patent Specification No. 4,421,583 relates to a non-woven alginate fabric useful as a wound dressing made by spreading a tow of calcium alginate filaments into a flow of water, over-feeding the spread filaments onto a water pervious support so that the filaments cross over each other, and drying the filaments so that they became bonded to each other at their points of contact where they cross over.
  • the filaments used have preferably been pre-stretched in an atmosphere of steam and wash water and not dried and are preferably subsequently dried by suction on the water pervious support.
  • Patent Specification No. 4,793,337 discloses an improved adhesive structure for adhesion of an article to a fluid emitting wound, the structure having an absorbent region comprising an absorbent fibrous fabric or foam material intermediate first and second contact regions, whereby enhanced cohesion between the first and second regions and between the second region and the article under conditions of heavy fluid emission is provided.
  • This specification discloses the use of sodium alginate in combination with a calcium powder by way of absorbent material.
  • United states patent Specification No. 4,948,575 discloses a dimensionally stable alginate hydrogel foam wound dressing that absorbs wound exudate without any appreciable swelling.
  • the wound dressing includes alkaline metal earth (except magnesium) salts and Group III metal salts of alginic acid.
  • the hydrogel foam may be formed by mixing together a first liquid component comprising (a) an aqueous suspension of particles of a water insoluble di- or trivalent metal salt and (b) an effervescent compound which effervesces upon reaction with an acid; and a second liquid component comprising an aqueous solution of biocompatible, water-soluble acid wherein at least one of the components further comprises a water-soluble alginate dissolved therein.
  • the water-insoluble metal salt reacts with the water soluble acid to form a water soluble metal salt that is subsequently ionized.
  • the polyvalent cations released from the water-soluble metal salt complex with the carboxylate groups of the water-soluble alginate causing the formation and precipitation of a water insoluble alginate hydrogel.
  • the effervescent compound is reacting with the water soluble acid; the resultant evolution of gases effects the formation of a stable hydrogel foam.
  • a method of forming a polysaccharide foam which comprises preparing an aqueous solution including a soluble polysaccharide and thereafter mechanically foaming the solution.
  • the foam may be produced by beating or otherwise mechanically agitating the material to cause the polysaccharide to foam.
  • the mechanical foaming may involve the introduction of gas into the solution, and shearing of the solution to create a mixing effect which may result in a very fine dispersion of gas bubbles in the solution.
  • the gas bubbles may be substantially spherical in shape.
  • the gas bubbles may undergo a transition from the spherical shape to a substantially polyhedral shape, with the solution distributed in thin membranes between adjacent gas bubbles and in ribs or spokes where several gas bubbles come into very close proximity to each other; the result is a foamed polymer having gas dispersed throughout the solution in a cellular structure.
  • the relative violence and/or period of agitation of mechanical action may be used to provide control over the foam pore size.
  • the foam pore size may be controlled in the range 5 - 500 ⁇ ; typically 50 - 500 ⁇ .
  • Said soluble polysaccharide may be alginic acid or hyaluronic acid.
  • said soluble polysaccharide may be a soluble polysaccharide salt such, for example, as an alginate or hyaluronate; typically, sodium alginate or sodium hyaluronate may be used.
  • the soluble polysaccharide may be carrageenans, chitosan, starch, or separately, amylose or amylopectin.
  • chitosan is soluble in acid, but is insoluble in neutral and basic solutions; on the other hand, starch is soluble in basic solutions.
  • the mechanical foaming step should be conducted in an acidic aqueous solution; where starch is used, foaming should be conducted in aqueous base.
  • a foaming agent may be included in the aqueous solution to assist in foaming the solution.
  • the fc-aming agent may be a surfactant, typically an ionic or non-ionic surfactant.
  • the ionic surfactant may be selected from sodium stearate, sodium dodecyl sulfate, alpha olefin sulfonates (commercially available under the trade name "Siponate 301-10"), sulfoalkyl amide, monocarboxyl coco imidazoline compounds, diearbc-xyl coco imidazoline compounds and sulfated fatty polyoxyethylene quatenary nitrogen compounds.
  • Said non-ionic surfactant may be selected frcm octylphenol ethoxylate (commercially available from Rohm & Haas under the trade name TRITON X-100), modified linear aliphatic polyethers and sorbitan esters.
  • a plasticizer may be included in the aqueous solution. Said plasticizer may be selected from glycerol, glucose, polyhydric alcohols, triethanolamine and stearates.
  • an oligotneric or polymeric foam modifier may be included in the aqueous solution; said foam modifier may be selected from polyethylene glycol, guar gum, albumin, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, polyoxazoline and polyethyeneimine. These foam modifiers may be used to improve the flexibility and toughness of the polysaccharide foam.
  • the foam modifier may be polyethylene glycol functionalised with vinyl groups such, for example, as acrylates.
  • the functionalised polyethylene glycol may be polymerised by irradiation (e.g. u.v. or electron) to form a polymer network within the foam; said network may improve the flexibility and toughness of the foam.
  • the aqueous solution of polysaccharide may include a foam stabiliser.
  • Said foam stabliser may be selected from ammonium stearate, dodecyl alcohol, tetradecanol, hexadecanol, tridecyloxypolyethanol and polyoxy ⁇ thylated oleylamine.
  • the resultant polysaccharide foam may be air dried after formation.
  • the foam material in an interior region of the foam may "collapse" giving the appearance of crushed foam; the cells constituting the foam may distort such that in one dimension each cell may become smaller than in another dimension substantially normal to the one dimension; this change in shape can be described as a sphere distorting to an ellipsoid.
  • the foam is referred to herein as a "collapsed" foam.
  • the foam material juxtaposed the surface of the foam may maintain its integrity preserving its mean pore size and pore size distribution.
  • the polysaccharide is chitosan which is foamed in an acidic aqueous solution it may be desirable, in some embodiments, to remove the acid after foaming while the foam is still wet since, on drying, any acid present may have an injurious effect on the chitosan foam.
  • Said acid may be removed after foaming by volatilisation or neutralisation.
  • the acid may be aqueous acetic acid which may be removed by volatilisation.
  • the foam nay be stabilized by cross-linking or coagulation thereby to provide a dimensionally stable foam.
  • the foam may be cross-linked or coagulated while wet; where a foam stabilizer is used the foam may be cross-linked or coagulated after initial drying, the foam may then be re-dried.
  • the cross-linking may be effected by reacting the foamed polysaccharide with di- or tri- valent cations.
  • Said polysaccharide foam may, in some embodiments, be immersed in or sprayed with a solution of the di- or tri- valent cations.
  • the cations may be selected from Ca2+(aq), Fe2+(aq) and Fe3+(aq).
  • an insoluble carbonate or hydrogen carbonate salt having one or more di- or tri- valent cations may be homogeneously dispersed in the foamed polysaccharide, and the foam may be subsequently treated with a strong acid to liberate carbon dioxide as gas and said cations which then cross-link with the polysaccharide to form a dimensionally stable foam structure.
  • the strong acid may have a concentration of up to 1N, typically 0.1 - 0.2N.
  • calcium carbonate may be used as an insoluble carbonate salt.
  • the cross-linked alginate or hyaluronate foam may be converted" by treatment with an aqueous solution of a reagent having solubilising mono-valent cations so that a proportion of the cross-linking di- or tri-valent cations in the foam may be replaced by the mono-valent cations, thereby imparting a degree of solubility in the foam; when contacted with water, the converted foam may form a gel.
  • the degree of conversion may be controlled; typically a small proportion of the cross linking cations may be replaced to provide a lightly gelling foam (when contacted with water).
  • substantially all the cross-linking cations n-ay be replaced to provide a substantially water soluble foam.
  • the reagent may be selected from sodium acetate and dilute hydrochloric acid.
  • the treatment may be performed at a pH in the range 4 - 7.
  • the foam may be coagulated by treatment with base.
  • said base may be sodium hydroxide solution.
  • the chitosan foam may be cross-linked by ionic or covalent bonding.
  • Ionic cxoss-linking may be obtained by treatment with an aqueous solution of polyvalent anions; typically one or more of sodium sulfate, octyl sulfate, lauryl sulfate, hexadecylsulfate, tripolyphosphate, pyrophospate and octapolyphosphate may be used as a source of polyvalent anions.
  • covalent cross-linking may be obtained by treating the chitosan foam with one or more dialdehydes e.g. glyoxal, glutaraldehye and dialdehyde starch.
  • the starch foam may be coagulated by treatment with aqueous ammonium sulfate.
  • starch foam may be cross-linked by treatment with formaldehyde; this treatment may be performed in the gaseous or liquid state. If the treatment is performed in the liquid state a solution in alcohol may typically be employed.
  • the cross-linked or coagulated polysaccharide foam may be dried in air. After drying, the dry, cross-linked or coagulated foam may be washed with water and then redried. Washing may be used to remove e.g. any foaming agent or foam stabiliser residual in the foam.
  • Said aqueous solution of polysaccharide may further comprise one or more ingredients selected from particulate fillers, barium sulfate, pulp-like fibres of cellulose or other fibrous material and moisture retaining or reinforcing filler materials. Where barium sulfate is used, it will be appreciated that the resultant foam may be substantially opaque to X-rays; the foam may therefore be useful as a medical implant in radiography.
  • the foam may be bleached.
  • Bleach may be included in the aqueous solution of polysaccharide; typically, the bleach may be selected from hydrogen peroxide and sodium hypochlorite.
  • the present invention also includes a polysaccharade foam produced in accordance with the method of the invention; the foam can be controlled at various thicknesses, pore sizes and pore size distributions.
  • the foam may be cross-linked or coagulated; the foam may be a soluble foam, an insoluble foam or a "converted" foam having a desired degree of solubility in at least part of the foam.
  • the foam may be an alginate, hyaluronate, chitosan or starch foam.
  • the foam when wet, may be cast as a layer or as a shaped article.
  • Said foam may be cast inter alia in the form of buttons, beads, balls, cylinders or hemispheres , in some embodiments, the foam may be cast in the shape of a part of a human or animal body e.g. in the shape of an ear or nose.
  • the foam may be cast as a layer on a substrate.
  • Said substrate may be a woven or non-woven fibrous article, a film or a foam.
  • the substrate may comprise an assemblage of polysaccharide fibres or yarns.
  • the substrate may comprise another layer of polysaccharide foam in accordance with the invention.
  • Said other layer foam may have a different mean pore size and/or pore size distribution from the first mentioned foam.
  • the foam may be cast as a thin foam layer having a thickness up to about 1 mm.
  • the foam in accordance with the present invention may be cast as a thick foam layer having a thickness of up to about 50mm.
  • Said thick foam layer may have an interior layer of "collapsed" foam; the foam juxtaposed the surface of the foam may be not significantly collapsed, being similar in appearance and having a pore size and pore size distribution about equal to the foam when freshly formed.
  • the present invention also includes a wound dressing comprising a polysaccharide foam produced by the method in accordance with the present invention.
  • the wound dressing may comprise a layer of said polysaccharide foam.
  • the foam may be disposed on a substrate, the substrate may be a polysaccharide fabric or composed of polysaccharide yarn.
  • the present invention also includes a cell culture replicating medium comprising a polysaccharide foam produced in accordance with the present invention; the cells to be replicated can be disposed in the pores in the foam to locate the cells.
  • the cell culture replicating medium may constitute an implant, typically a bio-absorbable implant.
  • Cultured cells e.g. mammalizing cells, may be disposed in the pores of the implant which may then be implanted surgically in a human or animal body.
  • the implant containing cultured cells may encourage tissue growth in and around the implant in vivo .
  • the present invention also includes a barrier medium for preventing tissue adherence, said barrier medium comprising a polysaccharide foam in accordance with the invention.
  • the polysaccharide foam may constitute a carrier for a beneficial agent formulation.
  • Said beneficial agent formulation may be accommodated within the cells of the foam.
  • the formulation may comprise a beneficial agent and a pharmaceutically acceptable excipient therefor.
  • the beneficial agent may be a drug which can be administered to a patient transdermally.
  • the beneficial agent formulation may be included in the aqueous solution of polysaccharide prior to foaming.
  • the beneficial agent formulation may be incorporated in the foam after formation; in some embodiments the foam may be immersed in or sprayed with the formulation (which may itself be in solution); in other embodiments the formulation may be dispersed in a solid particulate form in the cellular structure of the foam,or produced by living cells (e.g. microbes) in the foam structure.
  • a foam in accordance with the present invention when wet, may be stored under pressure; typically the wet foam may be stored in a pressurised dispenser such, for example, as a conventional pressurised spray can.
  • the wet foam may be incorporated with a propellant to assist in subsequent delivery of the foam from the dispenser; said propellant may be any suitable propellant known to a person skilled in the art e.g. a gaseous lower alkane (propane, butane, pentane and the like), nitrogen and carbon dioxide.
  • a gaseous lower alkane propane, butane, pentane and the like
  • a wet foamed wound dressing in accordance with the invention may be stored under pressure in a dispenser and dispensed directly onto a patient's skin to treat e.g. abraded skin, burns and open wounds.
  • a wet foam carrying a beneficial agent in accordance with the present invention may be stored and dispensed in the same way to provide rapid therapeutic treatment of a wound or other injury when required. It will be appreciated by a person skilled in the art that a foamed wound dressing or beneficial agent formulation carrier which is stored in a pressurised dispenser may be particularly suitable for the purposes of applying first aid to a patient in an emergency.
  • Figure 1 is a scanning electron microscope (“SEM”) photograph showing a surface of a single layer foam produced in accordance with the present invention
  • Figure 2 is an SEM photograph of another surface of the single layer foam of Figure 1;
  • Figure 3 is an SEM photograph of a cross section through the thickness of the single layer foam of Figures 1 and 2;
  • Figure 4 is an SEM photograph of a surface of a two layer foam produced in accordance with the present invention.
  • Figure 5 is an SEM photograph of another surface of the two layer foam of Figure 4.
  • Figure 6 is an SEM photogoraph of a cross section through the thickness of the two layer foam of Figures 4 and 5.
  • a solution containing 3 wt % of sodium alginate having a viscosity of 1500 centipoise was prepared and to 100 grams of this solution was added 0.1 grams of sodium dodecyl sulfate as a foaming agent.
  • the resultant solution was beaten with a Kitchenaid mixer to form a foam.
  • the foam was spread on a metal tray and cross-linked with an aqueous solution containing 5% by weight calcium chloride. The foam was then dried and after drying was found to be 0.05 mm thick and weighing 7 grams per square meter.
  • a scanning electron microscope photograph of the cross-linked foam revealed an open pore structure which was found to have an air permeability of 110 m/min measured at 12.7 mm H 2 O pressure.
  • a portion of the foam produced in the manner described above was converted by placing it in an aqueous solution of hydrogen chloride with a pH of 5 for 30 minutes.
  • the conversion did not affect the gauge weight or pore size, but did change the solubility characteristics.
  • Contact of the non-converted foam with a 1% sodium citrate solution did not affect the structure, whereas the contact of the converted foam with the same 1% sodium citrate solution resulted in a gelation of the foam. This latter action suggested the solubility characteristics were modified by the conversion process.
  • a 3" ⁇ 3" gauze pad comprising a 12-ply 20 ⁇ 12 mesh fabric was used as a substrate for a layer of alginate foam as described in Example 1.
  • the foam was spread on the fabric and cross-linked with a 5% aqueous solution of calcium chloride. The material was then dried and it was found that the cross-linked foam had adhered to the gauze pad to form a coating.
  • a photomicrograph of the resultant structure reveals a thin, 0.05 ram thick foam coating on the gauze pad which had a similar structure as the foam without the substrate described in Example 1.
  • the coated pad When the coated pad was placed in an aqueous solution of hydrogen chloride at a pH of 5 for 30 minutes, the calcium structure was converted to a soluble form. Contact of the converted naterial with sodium citrate once again resulted in gelation of the alginate coating.
  • aqueous solution containing 2 wt % sodium alginate was prepared. To this solution was added 0.2 wt % ammonium stearate as a foam stabiliser and 2 wt % calcium carbonate. The mixture was then well mixed in a kitchenaid mixer to produce a foam having the calcium carbonate dispersed therethrough. The foam was drawn in a plastic tray, and 200ml of 0.1K hydrochloric acid was then added in the tray. As a result of the addition of strong acid, the foam cross-linked. After drying, the foam was found to have a final thickness of
  • the foam was found to be coagulated uniformly through its thickness.
  • a 3% wt aqueous solution of sodium alginate was prepared. To the solution was added 0.85 grams of sodium dodecyl sulphate per 100 grams of alginate solution as a foaming agent. In addition, 2.3 grams of ammonium stearate per 100 grams of alginate solution was added as a foam stabilizer. The resultant solution was beaten with a Kitchenaid mixer to form a foam. The foam was spread on a polyester sheet and allowed to air dry. The surface of the dried foam maintained a similar appearance to the wet foam and did not collapse; the foam material in the interior of the foam was found to have "collapsed" and had the appearance of crushed foam. The dried foam was immersed in a 5% wt calcium chloride solution and then allowed to air dry.
  • the dried foam maintained the appearance of the original drawn material. Inspection under an optical microscope revealed the foam was an open-cell structure with fairly uniform pore sizes.
  • the foam had a final thickness of 2.8 mm, a density of 0.05 g/cm, and a permeability of 90 ro/min at 12.7 mm H 2 O.
  • Example 6 To a solution of similar composition to Example 1 was added 1 gram of anhydrous glycerol per gram of alginate material. The solution was foamed mechanically, drawn into a desired thickness and allowed to air dry. The dried foam was cross-linked using a 5% wt calcium chloride solution and air dried. The resultant foam had a final thickness of 0.25 mm, a density of 0.14 g/cm and an air permeability of 100 m/min at 12.7 mm H 2 O pressure. After 3 months under ambient conditions, the foam had a similar handling ability as a newly formed foam. EXAMPLE 6
  • FIGS. 1 to 3 are Scanning Electron Microscope photographs of the resultant dried foam (10). It will be noted that an interior region (12) of the foam is “collapsed” giving the appearance of "crushed” foam, while the surfaces (14, 16) of the foam substantially maintain their pore size and pore size distributions.
  • FIGS. 4 to 6 are Scanning Electron Microscope photographs of the resultant two-layer foam (20). It will be noted that an interior (22) of the foam is "collapsed", while the surfaces (24, 26) substantially maintain their controlled pore sizes and pore size distributions.
  • Example 8
  • aqueous solution containing 5 wt% sodium hyaluronate was prepared. To this solution was added 2.7 grams of sodium dodecyl sulphate and 5.3 grams of a ⁇ inonium stearate per 100 grams of solution. The mixture was well beaten with a KitchenAid mixer to form a foam. The foam was spread onto a polyester sheet and air dried. Inspection under an optical microscope revealed the foam was an open-cell structure with fairly uniform pore size.
  • a solution was prepared with 10 grams of 37.5 w/w HCl and 490 grams water. Fifteen grams of chitosan were added and dissolved in the acid. To the solution were added 1.5 grams of sodium dodecyl sulfate and 15 grams of ammonium stearate. The mixture was beaten in a KitchenAid mixer to form a foam which was subsequently drawn to 25 mils thickness and air dried. Inspection under an optical microscope revealed the foam was open-celled and fairly uniform in pore size.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Hematology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Materials For Medical Uses (AREA)
  • Medicinal Preparation (AREA)

Abstract

Procédé de production d'une mousse au polysaccharide selon lequel on fait mousser mécaniquement une solution aqueuse d'un polysaccharide soluble puis on fait réagir la mousse pour obtenir une mousse stable. Plus spécifiquement le polysaccharide soluble est un alginate, un hyaluronate, des carraghénanes, du chitosane, ou de l'amidon.
PCT/US1993/005993 1992-06-19 1993-06-18 Procede de production de mousses au polysaccharide Ceased WO1994000512A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP19930915464 EP0612331A4 (fr) 1992-06-19 1993-06-18 Procede de production de mousses au polysaccharide.
AU45437/93A AU672214B2 (en) 1992-06-19 1993-06-18 Method of producing polysaccharide foams
US08/196,079 US5840777A (en) 1992-06-19 1993-06-18 Method of producing polysaccharide foams
FI940735A FI940735A7 (fi) 1992-06-19 1993-06-18 Menetelmä polysakkaridivaahtojen valmistamiseksi
CA002116037A CA2116037C (fr) 1992-06-19 1993-06-18 Methode de production de mousses de polysaccharides
BR9305552A BR9305552A (pt) 1992-06-19 1993-06-18 Processo para produzir espumas de polissacarídeos
NO940546A NO940546D0 (no) 1992-06-19 1994-02-17 Fremgangsmåte for fremstilling av et polysakkaridskum og anvendelse av dette

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9212976.6 1992-06-19
GB929212976A GB9212976D0 (en) 1992-06-19 1992-06-19 Wound dressings
GB9224255.1 1992-11-19
GB929224255A GB9224255D0 (en) 1992-11-19 1992-11-19 Alginate wound dressings

Publications (1)

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WO1994000512A1 true WO1994000512A1 (fr) 1994-01-06

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PCT/US1993/005993 Ceased WO1994000512A1 (fr) 1992-06-19 1993-06-18 Procede de production de mousses au polysaccharide

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EP (1) EP0612331A4 (fr)
JP (1) JP2644626B2 (fr)
AU (1) AU672214B2 (fr)
BR (1) BR9305552A (fr)
CA (1) CA2116037C (fr)
FI (1) FI940735A7 (fr)
WO (1) WO1994000512A1 (fr)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994017137A1 (fr) * 1993-01-19 1994-08-04 Rapaport, Erich Eponges d'hydrocolloides
EP0747420A1 (fr) * 1995-06-07 1996-12-11 Albany International Research Company Procédé de production de mousses de polysaccharide
DE19729273A1 (de) * 1997-07-09 1999-01-14 Hoechst Ag Thermoplastische Mischung auf 1,4-alpha-D-Polyglucanbasis, Verfahren zu deren Herstellung und Verwendung
WO2000019979A1 (fr) * 1998-10-07 2000-04-13 Giltech Limited Formulation moussante et mousse
EP1033141A1 (fr) * 1999-03-02 2000-09-06 Bristol-Myers Squibb Company Hydrocolloide adhésif
EP1072636A1 (fr) * 1999-07-28 2001-01-31 ZIMMERMANN, Ulrich Réticulation de gels ionotropiques
US6187290B1 (en) 1994-12-06 2001-02-13 Giltech Limited Physiologically acceptable foamable formulation and foam
WO2001016220A1 (fr) * 1999-08-30 2001-03-08 Sca Hygiene Products Ab Procede de production d'un materiau de mousse absorbant
GB2357765A (en) * 1999-04-29 2001-07-04 George H Scherr Water-insoluble alginate sponge material
WO2005023323A1 (fr) * 2003-09-08 2005-03-17 Fmc Biopolymer As Mousse gelifiee a base de biopolymere
US7408057B2 (en) 2000-07-03 2008-08-05 Marine Bioproducts Intenational Clarified hydrocolloids of undiminished properties and method of producing same
WO2007103208A3 (fr) * 2006-03-01 2008-12-24 Fmc Biopolymer As Mousse biodégradable
FR2925316A1 (fr) * 2007-12-21 2009-06-26 Oreal Kit comprenant un alginate et un agent de complexation sous forme de sel insoluble dans l'eau
FR2925315A1 (fr) * 2007-12-21 2009-06-26 Oreal Kit comprenant un alginate et un agent de complexation sous forme de sel hydrosoluble
EP2270082A1 (fr) 2004-05-21 2011-01-05 Dr. Suwelack Skin & Health Care AG Procédé pour fabriquer des éléments moulés poreux à base d'alginate
US8143472B1 (en) 1999-08-30 2012-03-27 Sca Hygiene Products Ab Absorbent structure in an absorbent article and a method of producing it
WO2016030279A1 (fr) 2014-08-26 2016-03-03 Renfortech Mousses epoxy derivees de formulations reactives biosourcees
US10017621B2 (en) 2014-05-19 2018-07-10 Basf Se Process for producing porous alginate-based aerogels
WO2018234680A1 (fr) 2017-06-22 2018-12-27 Jellynov Composition auto-moussante en milieu acide et procédé de préparation
FR3089224A1 (fr) 2018-12-04 2020-06-05 Jellynov Composition auto-moussante en milieu acide et procédé de préparation
FR3102364A1 (fr) 2019-10-28 2021-04-30 Urgo Recherche Innovation Et Developpement Mousse gélifiée à base de polysaccharide
EP3848409A1 (fr) 2020-01-13 2021-07-14 Basf Se Aérogels d'alginate réticulés de polyurée/polyuréthane
WO2023170134A1 (fr) 2022-03-08 2023-09-14 Aerogel-It Gmbh Procédé de production de matériaux poreux
US11771122B2 (en) 2020-09-29 2023-10-03 Nitto Denko Corporation Foam body and method for manufacturing the same

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EP1169378A4 (fr) * 1999-04-09 2004-06-02 Univ Michigan Preparation de produits a base d'hydrogel
AU2002327507A1 (en) * 2001-09-04 2003-03-18 Dow Global Technologies Inc. Aqueous air foam
JP4869066B2 (ja) * 2003-04-25 2012-02-01 ケイオウエス ライフ サイエンスイズ，インコーポレイテッド 丈夫な超多孔性ヒドロゲルの形成技術
US8999377B2 (en) * 2007-09-19 2015-04-07 Surmodics, Inc. System for forming a biocompatible foam using polymerizable alpha(1-4)glucopyranose polymers and gas-producing component
JP2012506478A (ja) * 2008-10-22 2012-03-15 サーモディクス，インコーポレイティド 膨潤性および生分解性を有するポリマーマトリクス並びにその製造方法
JP4358895B1 (ja) * 2009-01-06 2009-11-04 昭和高分子株式会社 発泡性樹脂組成物及び発泡体
JP5805847B2 (ja) * 2011-04-07 2015-11-10 ザ プロクター アンド ギャンブルカンパニー 使用時に溶解して界面活性剤を送達する物品を作製する連続式プロセス
JP6206089B2 (ja) * 2013-04-23 2017-10-04 Jnc株式会社 多糖類モノリス構造体及びその製造方法
JP2019037608A (ja) * 2017-08-28 2019-03-14 大日精化工業株式会社 柔軟性成形体の製造方法及び柔軟性成形体
CN110433321A (zh) * 2019-07-06 2019-11-12 张明 一种具有缓释抗菌的医用泡沫敷料的制备方法

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US4002178A (en) * 1973-12-27 1977-01-11 Amf Incorporated Foams and sponge sheet for cigar manufacture
US4139699A (en) * 1976-03-25 1979-02-13 National Starch And Chemical Corporation Water insensitive starch fibers and a process for the production thereof

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CA2080035A1 (fr) * 1991-10-15 1993-04-16 George Colegrove Gels-mousses

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US3868355A (en) * 1972-12-26 1975-02-25 Pillsbury Co Foam separation of gluten and starch
US4002178A (en) * 1973-12-27 1977-01-11 Amf Incorporated Foams and sponge sheet for cigar manufacture
US4139699A (en) * 1976-03-25 1979-02-13 National Starch And Chemical Corporation Water insensitive starch fibers and a process for the production thereof

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Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994017137A1 (fr) * 1993-01-19 1994-08-04 Rapaport, Erich Eponges d'hydrocolloides
US6187290B1 (en) 1994-12-06 2001-02-13 Giltech Limited Physiologically acceptable foamable formulation and foam
EP0747420A1 (fr) * 1995-06-07 1996-12-11 Albany International Research Company Procédé de production de mousses de polysaccharide
AU708720B2 (en) * 1995-06-07 1999-08-12 Albany International Research Co. Method of producing polysaccharide foams
DE19729273A1 (de) * 1997-07-09 1999-01-14 Hoechst Ag Thermoplastische Mischung auf 1,4-alpha-D-Polyglucanbasis, Verfahren zu deren Herstellung und Verwendung
DE19729273C2 (de) * 1997-07-09 2000-08-17 Aventis Res & Tech Gmbh & Co Thermoplastische Mischung auf 1,4-alpha-D-Polyglucanbasis, Verfahren zu deren Herstellung und Verwendung
US7070722B1 (en) 1998-10-07 2006-07-04 Giltech Limited Foamable formulation and foam
WO2000019979A1 (fr) * 1998-10-07 2000-04-13 Giltech Limited Formulation moussante et mousse
EP1033141A1 (fr) * 1999-03-02 2000-09-06 Bristol-Myers Squibb Company Hydrocolloide adhésif
GB2357765A (en) * 1999-04-29 2001-07-04 George H Scherr Water-insoluble alginate sponge material
GB2357765B (en) * 1999-04-29 2004-04-21 George H Scherr Alginate foam compositions
EP1072636A1 (fr) * 1999-07-28 2001-01-31 ZIMMERMANN, Ulrich Réticulation de gels ionotropiques
AU778418B2 (en) * 1999-08-30 2004-12-02 Sca Hygiene Products Ab Absorbent foam material and an absorbent structure containing said foam material
US6774151B2 (en) 1999-08-30 2004-08-10 Sca Hygiene Products Ab Method of producing an absorbent foam material
US8143472B1 (en) 1999-08-30 2012-03-27 Sca Hygiene Products Ab Absorbent structure in an absorbent article and a method of producing it
WO2001016220A1 (fr) * 1999-08-30 2001-03-08 Sca Hygiene Products Ab Procede de production d'un materiau de mousse absorbant
US7408057B2 (en) 2000-07-03 2008-08-05 Marine Bioproducts Intenational Clarified hydrocolloids of undiminished properties and method of producing same
WO2005023323A1 (fr) * 2003-09-08 2005-03-17 Fmc Biopolymer As Mousse gelifiee a base de biopolymere
EP2270082A1 (fr) 2004-05-21 2011-01-05 Dr. Suwelack Skin & Health Care AG Procédé pour fabriquer des éléments moulés poreux à base d'alginate
US7998379B2 (en) 2004-05-21 2011-08-16 Dr. Suwelack Skin & Health Care Ag Process for the production of porous moulded articles containing alginate
WO2007103208A3 (fr) * 2006-03-01 2008-12-24 Fmc Biopolymer As Mousse biodégradable
WO2009080627A3 (fr) * 2007-12-21 2010-07-01 L'oreal Kit comprenant un alginate et un agent complexant sous forme d'un sel soluble dans l'eau
FR2925315A1 (fr) * 2007-12-21 2009-06-26 Oreal Kit comprenant un alginate et un agent de complexation sous forme de sel hydrosoluble
FR2925316A1 (fr) * 2007-12-21 2009-06-26 Oreal Kit comprenant un alginate et un agent de complexation sous forme de sel insoluble dans l'eau
WO2009080628A3 (fr) * 2007-12-21 2010-07-01 L'oreal Kit comprenant un alginate et un agent complexant sous forme d'un sel soluble dans l'eau
US11028247B2 (en) 2014-05-19 2021-06-08 Basf Se Process for producing porous alginate-based aerogels
US10017621B2 (en) 2014-05-19 2018-07-10 Basf Se Process for producing porous alginate-based aerogels
WO2016030279A1 (fr) 2014-08-26 2016-03-03 Renfortech Mousses epoxy derivees de formulations reactives biosourcees
WO2018234680A1 (fr) 2017-06-22 2018-12-27 Jellynov Composition auto-moussante en milieu acide et procédé de préparation
FR3068039A1 (fr) * 2017-06-22 2018-12-28 Jellynov Composition auto-moussante en milieu acide et procede de preparation
US12178906B2 (en) 2017-06-22 2024-12-31 Jellynov Method of administering a self-foaming composition
US11471407B2 (en) 2017-06-22 2022-10-18 Jellynov Composition that is self-foaming in an acid medium, and method for preparing same
WO2020114966A1 (fr) 2018-12-04 2020-06-11 Jellynov Composition auto-moussante en milieu acide et procede de preparation
FR3089224A1 (fr) 2018-12-04 2020-06-05 Jellynov Composition auto-moussante en milieu acide et procédé de préparation
WO2021084200A1 (fr) 2019-10-28 2021-05-06 Urgo Recherche Innovation Et Developpement Mousse gélifiée à base de polysaccharide
FR3102364A1 (fr) 2019-10-28 2021-04-30 Urgo Recherche Innovation Et Developpement Mousse gélifiée à base de polysaccharide
US12414909B2 (en) 2019-10-28 2025-09-16 Urgo Recherche Innovation Et Developpement Polysaccharide-based gelled foam
EP3848409A1 (fr) 2020-01-13 2021-07-14 Basf Se Aérogels d'alginate réticulés de polyurée/polyuréthane
US11771122B2 (en) 2020-09-29 2023-10-03 Nitto Denko Corporation Foam body and method for manufacturing the same
WO2023170134A1 (fr) 2022-03-08 2023-09-14 Aerogel-It Gmbh Procédé de production de matériaux poreux

Also Published As

Publication number Publication date
FI940735L (fi) 1994-02-16
EP0612331A4 (fr) 1994-11-23
AU672214B2 (en) 1996-09-26
FI940735A0 (fi) 1994-02-16
AU4543793A (en) 1994-01-24
FI940735A7 (fi) 1994-02-16
BR9305552A (pt) 1994-12-20
CA2116037C (fr) 2000-01-04
JP2644626B2 (ja) 1997-08-25
CA2116037A1 (fr) 1994-01-06
EP0612331A1 (fr) 1994-08-31
JPH06510330A (ja) 1994-11-17

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