WO2010071925A1 - Préparation d'un antimicrobien - Google Patents

Préparation d'un antimicrobien Download PDF

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Publication number
WO2010071925A1
WO2010071925A1 PCT/AU2009/001674 AU2009001674W WO2010071925A1 WO 2010071925 A1 WO2010071925 A1 WO 2010071925A1 AU 2009001674 W AU2009001674 W AU 2009001674W WO 2010071925 A1 WO2010071925 A1 WO 2010071925A1
Authority
WO
WIPO (PCT)
Prior art keywords
propenal
poly
aqueous
propenoic acid
composition
Prior art date
Application number
PCT/AU2009/001674
Other languages
English (en)
Inventor
Robert William Dunlop
Original Assignee
Chemeq Ltd
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 Chemeq Ltd filed Critical Chemeq Ltd
Priority to CA2748074A priority Critical patent/CA2748074A1/fr
Priority to EP09833925A priority patent/EP2379604A1/fr
Priority to JP2011542626A priority patent/JP2012512955A/ja
Priority to AU2009329815A priority patent/AU2009329815A1/en
Publication of WO2010071925A1 publication Critical patent/WO2010071925A1/fr

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Classifications

    • 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
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/34—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an aldehydo radical

Definitions

  • the invention relates to a method of preparing an antimicrobial from polymers of 2-propenal such as poly-2-propenal and to a poly(2-propenal, 2- propenoic acid) polymeric antimicrobial resulting from the process.
  • the invention provides a method of preparation of poly(2-propenal, 2- propenoic acid) comprising forming an aqueous suspension of poly 2-propenal and oxidizing the suspension by mixing with a peroxide oxidant selected from the group consisting of hydrogen peroxide, peracids and mixtures thereof.
  • the invention provides a poly(2-propenal, 2-propenoic acid) composition which is colorless and preferably made according to the above process.
  • composition comprising a biologically active agent and a preservative effective amount of the above described poly(2-propenal, 2-propenoic acid).
  • the active agent may be a cosmetic, pharmaceutical, veterinary agent or the like.
  • a cosmetic composition for hair or skincare comprising an effective amount of the poly(2-propenal, 2-propenoic acid).
  • the preparation of poly(2-propenal, 2-propenoic acid) comprises forming an aqueous suspension of poly 2-propenal.
  • the aqueous suspension may be prepared by dispersing the poly 2-propenal in an aqueous liquor.
  • the poly 2- propenal may be dispersed in water to form a suspension by mixing the poly 2- propenal solid with an aqueous liquor.
  • the solid poly 2-propenal may be dry or may be a mixture containing a solvent provided addition of the composition to the aqueous liquor results in formation of a suspension of the poly 2-propenal.
  • the suspension is formed by mixing a composition of poly 2-propenal in a water miscible solvent with an aqueous liquor.
  • the poly 2- propenal may be soluble or insoluble in the solvent and when added to the aqueous liquor the composition provides a suspension of the poly 2-propenal.
  • the use of a solvent in which poly 2-propenal is soluble may facilitate storage or handling of the poly 2-propenal prior to oxidation and/or convenient handling during the mixing with the liquor but the nature and proportion of the solvent is such that when added to the aqueous liquor a suspension of the poly 2-propenal is provided.
  • the poly 2-propenal is prepared by polymerization of 2-propenal and the resulting poly 2-propenal is filtered from the reaction mixture and the filtered product used in the oxidation step optionally without further treatment.
  • the filtered material may be dried although it is preferable that the drying conditions not use a temperature exceeding 60 Q C and more preferably not exceeding 50 Q C as we have found the use of high temperature for drying results in coloration of the product possibly as a result of decomposition.
  • the poly 2-propenal be present as a suspension in an aqueous composition when the peroxide oxidant selected from the group consisting of hydrogen peroxide, peracid and mixtures thereof is mixed with the composition.
  • the peroxide oxidant selected from the group consisting of hydrogen peroxide, peracid and mixtures thereof is mixed with the composition.
  • the poly(2-propenal, 2-propenoic acid) product resulting from the process may be isolated by filtration of the aqueous liquor.
  • the recovery of product may in some cases be improved by modification of the pH to provide a pH of neutral or lower so that acid groups of the poly(2-propenal, 2-propenoic acid) do not solubilise the product.
  • the product may be extracted into a suitable water immiscible solvent.
  • the invention may be conducted with the poly 2-propenal in a range of concentrations in the aqueous composition provided, of course, that it is present as a suspension rather than dissolved.
  • concentration is in the range of from 0.1 % by weight to 80% by weight (preferably 1 % to 60%, more preferably from 5% to 50% and most preferably from 8% to 20%) based on the total weight of the aqueous composition.
  • the method involves oxidizing the suspension of poly 2-propenal by mixing the suspension in an aqueous liquor with a peroxide oxidant selected from the group consisting of hydrogen peroxide and peracid.
  • a peracid is an acid containing a peroxide group (-O-OH).
  • the peracid may be organic or inorganic and preferred peracids are per-carboxylic acids.
  • Percarboxylic acids may be prepared by reaction of the parent acid (RCOOH where R can be hydrogen, alkyl such as Cito C 4 alkyl optionally substituted with one or more halogen such as perfluoroacetic and aryl acetic optionally substituted with halo), with hydrogen peroxide to form a highly reactive peracid.
  • the preferred peracids are perform ic acid and peracetic acid and meta- chloroperbenzoic acid.
  • the degree of oxidation and hence proportion of acid groups in the poly(2- propenal, 2-propenoic acid) can be controlled by the ratio of peroxide to 2- propenal used in the oxidation and the period of time and conditions under which the oxidation is conducted.
  • the desired extent of oxidation can be determined by the solubility of the polymer in alkaline solution (e.g. sodium carbonate).
  • the peroxide oxidant is preferably mixed with the aqueous suspension of poly 2-propenal in a weight ratio of peroxide: poly2-propenal of 0.5:1 to 2:1 and more preferably from 0.5:1 to 1.1 :1.
  • the period of time over which the oxidation is conducted will depend on the nature and reactivity of the peroxide/peracid, the conditions used and the degree of solubility desired in the final product. In one embodiment the oxidation is conducted for a period of from 10 minutes to 10 hours, preferably from 30 minutes to 5 hours and most preferably from 30 minutes to three hours.
  • the oxidation may be conducted at elevated temperature if desired and, depending on the specific peracid and the concentration used the reaction mixture may undergo a significant exotherm during the reaction procedure.
  • the temperature of the reaction will be maintained at no more than 60 Q C and preferably no more than 50 Q C (such as no more than 45 Q C, no more than 40 Q C, no more than 35 Q C and no more than 30 Q C).
  • the reaction medium may have a temperature of at least 5 Q C and preferably at least 10 Q C. In one embodiment the temperature is maintained at about 25 Q C.
  • the poly 2-propenal used in the process of the invention is preferably formed by anionic polymerization and most preferably by base catalysed polymerisation.
  • the poly 2-propenal may be prepared in aqueous solution by base (preferably alkali metal hydroxide such as NaOH or KOH) catalysis and preferably the temperature maintained below 60 Q C preferably below 50 Q C and most preferably below 40 Q C.
  • base preferably alkali metal hydroxide such as NaOH or KOH
  • the resulting poly 2-propenal may be filtered from the aqueous mixture used in the oxidation method by resuspending it in water.
  • the poly 2-propenal formed by base catalysed polymerization will precipitate from the aqueous solution in which 2-propenal in reacted as a fine particulate solid so that it can be used in the oxidation process without particle size reduction although a process of particle size reduction such as milling may be used if desired to disrupt agglomerates or clumps of polymer.
  • the filtered polymer may be dried although as previously described the polymer is preferably not subject to temperatures over 60 Q C, preferably not temperatures over 50 Q C and more preferably not temperatures over 40 Q C.
  • the poly(2-propenal, 2-propenoic acid) may be formulated in cosmetic, pharmaceutical or veterinary products as a preservative.
  • the product may be used in the treatment of gastrointestinal disease in accordance with the disclosure of US6723336.
  • the product is also useful in formulated antiseptic, disinfectant and antifungal preparations according to the general description in US 5290894.
  • the poly(2-propenal, 2-propenoic acid) is subject to further processing to improve antimicrobial activity and/ solubility in aqueous media in accordance with the methods disclosed in one or more of WO2005/044874, WO/2001 /060874, WO/2000/003723, WO2002/026211 and PCT/Au2008/001032.
  • poly(2-propenal, 2-propenoic acid) is dissolved in an alcohol solution particularly a polyalkylene glycol and/or alkaline aqueous composition such as sodium or potassium carbonate aqueous solution.
  • poly(2-propenal, 2-propenoic acid) is provided in the form of a nanoparticulate composition as described in PCT/Au2008/001032.
  • the poly(2-propenal, 2-propenoic acid) prepared in accordance with the invention has a range of uses as an antimicrobial as described in our previous patent applications.
  • the gastrointestinal disease may for example result from one or more microbes selected from the group consisting of Coliforms, Salmonella, P. aeruginosa, Helicobacter, Proteus, Enterobacteria, Yeasts, Protozoa, Clostridia, Shigella and Coccidia 14.
  • a method for the treatment or prophylaxis of diseases of the gastrointestinal tract caused by Helicobacter infection comprising the gastrointestinal administration of a therapeutic amount of a polymer comprising a derivative of poly (2-propenal, 2-propenoic acid) formed by the reaction between a poly (2-propenal, 2-propenoic acid) and an organic compound containing hydroxyl groups selected from alkanols, phenols, polyols and mixtures thereof, to form protected carbonyl groups.
  • the poly(2-propenal, 2-propenoic acid) may be administered to animals to treat gastrointestinal diseases such as collibacilosis in pigsand coccidiosis in poultry.
  • a method of treatment of gastrointestinal disease in animals comprising administering animals in need thereof an effective amount of the above described antimicrobial.
  • an antimicrobial for treating or preventing gastrointestinal disease wherein the carrier for gastrointestinal administration is selected from the group consisting of water, controlled release polymers, olive oil, peanut oil, sesame oil, sunflower oil, arachis oil, coconut oil, liquid paraffin, ethylene glycol, propylene glycol, polyethylene glycol, ethanol, propanol, isopropanol, glycerol, fatty alcohols, triglycerides, polyvinyl alcohol, partially hydrolyse polyvinylacetate and mixtures thereof.
  • an antimicrobial composition in the form of a feed additive or drinking water additive comprising from 0.1 to 70% by weight of the antimicrobial.
  • the animal of the feed composition the antimicrobial is present in an amount of from 0.001 to 25% by weight of the total feed or water composition.
  • the antimicrobial may be used in a surface cleaner antiseptic or cosmetic formulation to impart and antimicrobial effect on the surface to be treated or provide a preservative effect on the composition itself.
  • the antimicrobial will typically be present in such uses at a concentration in the range of from 0.001 to 25%by weight.
  • the white sticky residue was air dried to remove residual solvent (Yield 100%).
  • the white oxidized product was soluble in sodium carbonate solution and the FTIR consistent with a product containing carboxylic acid groups.
  • Poly 2-propenal (100 g), produced according to example 1 was suspended in deionised water (1000 g) containing sodium carbonate (100 g). Hydrogen peroxide 30% w/w (118 g) was added drop wise such that the temperature did not rise above 3O 0 C and the suspension was stirred for 2 hours after the complete addition of peroxide.
  • the white oxidized product was soluble in sodium carbonate solution and the FTIR consistent with a product containing carboxylic acid groups.
  • the white solid has the higher molecular weight polymer; the ethyl acetate extract has mid range molecular weight material and the non-extractable material is more polar lower molecular weight species.
  • the white oxidised product was soluble in sodium carbonate solution and the FTIR consistent with a product produced by hot air oxidation of poly 2- propenal as produced in example 1 b of US 6723336 (Reference sample).
  • Example 2 The procedure of Example 2 was repeated using different conditions (of contact time, amount of peroxide solution and temperature) as set out in Table 1.
  • poly 2-propenal (2 g) was suspended in water (20 ml_) containing 2 g of sodium carbonate and the indicated amount of hydrogen peroxide solution.
  • FTIR Code Compared with Poly(2-propenal, 2-propenoic acid) prepared by hot air oxidation: 1 : low carboxylic acid intensity at 1726 cm "1

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Communicable Diseases (AREA)
  • Oncology (AREA)
  • Polymers & Plastics (AREA)
  • Birds (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Dermatology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Epidemiology (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Medicinal Preparation (AREA)

Abstract

La présente invention concerne un procédé de préparation de poly(2-propénal, acide 2-propénoïque) qui consiste à former une suspension aqueuse de poly(2-propénal) et à oxyder la suspension en la mélangeant avec un oxydant peroxydique choisi parmi le peroxyde d'hydrogène, les peracides et les mélanges de ceux-ci.
PCT/AU2009/001674 2008-12-22 2009-12-21 Préparation d'un antimicrobien WO2010071925A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA2748074A CA2748074A1 (fr) 2008-12-22 2009-12-21 Preparation d'un antimicrobien
EP09833925A EP2379604A1 (fr) 2008-12-22 2009-12-21 Préparation d'un antimicrobien
JP2011542626A JP2012512955A (ja) 2008-12-22 2009-12-21 抗菌剤の製造方法
AU2009329815A AU2009329815A1 (en) 2008-12-22 2009-12-21 Preparation of antimicrobial

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19375908P 2008-12-22 2008-12-22
US61/193,759 2008-12-22

Publications (1)

Publication Number Publication Date
WO2010071925A1 true WO2010071925A1 (fr) 2010-07-01

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ID=42286787

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Application Number Title Priority Date Filing Date
PCT/AU2009/001674 WO2010071925A1 (fr) 2008-12-22 2009-12-21 Préparation d'un antimicrobien

Country Status (5)

Country Link
EP (1) EP2379604A1 (fr)
JP (1) JP2012512955A (fr)
AU (1) AU2009329815A1 (fr)
CA (1) CA2748074A1 (fr)
WO (1) WO2010071925A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011047421A1 (fr) * 2009-10-19 2011-04-28 Chemeq Ltd Composition antifongique et procédé de traitement de la dermatite
WO2011098706A1 (fr) 2010-02-15 2011-08-18 Arkema France Procede d'obtention de polymeres d'acroleine, polymeres et leurs utilisations

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3546286A (en) * 1964-07-22 1970-12-08 Dynamit Ag Oxidation of polyacroleins
US4678814A (en) * 1981-03-30 1987-07-07 California Institute Of Technology Polyacrolein microspheres
US6723336B1 (en) * 1995-05-30 2004-04-20 Chemeq Ltd. Chemotherapeutic compositions
US6803356B1 (en) * 2000-02-16 2004-10-12 Chemeq Ltd. Antimicrobial polymeric compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3546286A (en) * 1964-07-22 1970-12-08 Dynamit Ag Oxidation of polyacroleins
US4678814A (en) * 1981-03-30 1987-07-07 California Institute Of Technology Polyacrolein microspheres
US6723336B1 (en) * 1995-05-30 2004-04-20 Chemeq Ltd. Chemotherapeutic compositions
US6803356B1 (en) * 2000-02-16 2004-10-12 Chemeq Ltd. Antimicrobial polymeric compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011047421A1 (fr) * 2009-10-19 2011-04-28 Chemeq Ltd Composition antifongique et procédé de traitement de la dermatite
WO2011098706A1 (fr) 2010-02-15 2011-08-18 Arkema France Procede d'obtention de polymeres d'acroleine, polymeres et leurs utilisations
FR2956404A1 (fr) * 2010-02-15 2011-08-19 Arkema France Procede d'obtention de polymeres d'acroleine, polymeres et leurs utilisations

Also Published As

Publication number Publication date
CA2748074A1 (fr) 2010-07-01
AU2009329815A1 (en) 2011-07-21
JP2012512955A (ja) 2012-06-07
EP2379604A1 (fr) 2011-10-26

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