US20020142020A1 - Biocidal organic acid salts of a polymeric biguanide - Google Patents

Biocidal organic acid salts of a polymeric biguanide Download PDF

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Publication number
US20020142020A1
US20020142020A1 US09/445,765 US44576599A US2002142020A1 US 20020142020 A1 US20020142020 A1 US 20020142020A1 US 44576599 A US44576599 A US 44576599A US 2002142020 A1 US2002142020 A1 US 2002142020A1
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Prior art keywords
composition
carbon atoms
organic acid
polymeric biguanide
salt
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Abandoned
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US09/445,765
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English (en)
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Peter Woollven
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Avecia Ltd
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Avecia Ltd
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Assigned to AVECIA LIMITED reassignment AVECIA LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WOOLLVEN, PETER
Publication of US20020142020A1 publication Critical patent/US20020142020A1/en
Abandoned 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof

Definitions

  • the present invention relates to organic acid salts of polymeric biguanides, to compositions thereof, and their use as an industrial biocide or in personal care applications.
  • PHMB Poly(hexamethylenebiguanide)
  • Behenic acid is an aliphatic carboxylic acid containing a C 21 -alkyl chain and falls within the group, anionic surfactants.
  • the concentrated aqueous solution of PHMB in the form of its hydrochloride salt is clearly stated to be incompatible with anionic surfactants, alkyl sulphonates and anionic caramels as disclosed in the Product Information Notes for Vantocil IB (37-8E dated Jun. 1, 1994) and Cosmocil CQ (37-26E dated Apr. 1, 1994). Both Vantocil and Cosmocil are registered trade marks of Zeneca Specialties.
  • Bisbiguanides have also been made available commercially as water-soluble salts such as chlorhexidine (1,1′-hexamethylene bis[5-(4-chlorophenyl)-biguanide]digluconate) and alexidine (1,1′-hexamethylene bis [5-(4-(2-ethylhexyl)phenyl)-biguanide]-diacetate).
  • water-soluble salts and PHMB hydrochloride are not particularly suited to provide a solution of the polymeric biguanide in organic liquids, especially non-polar organic liquids.
  • PHMB in the form of its salt of an organic acid containing from 4 to 30 carbon atoms exhibits high antimicrobial, especially antibacterial activity, and that such salts exhibit increased solubility in organic media, especially organic liquids.
  • composition comprising a carrier and a polymeric biguanide in the form of its salt with an organic acid containing from 4 to 30 carbon atoms, including mixtures thereof.
  • the polymeric biguanide contains at least one biguanide unit of Formula 1.
  • the polymeric biguanide contains at least two biguanide units of Formula 1 which are linked by a bridging group which contains at least one methylene group.
  • the bridging group may include a polymethylene chain which may optionally be interrupted by hetero atoms such as oxygen, sulphur or nitrogen.
  • the bridging group may include one or more cyclic nuclei which may be saturated or unsaturated.
  • the bridging group is such that there are at least three, and especially at least four, carbon atoms directly interposed between two adjacent biguanide units of Formula 1.
  • the polymeric biguanide may be terminated by any suitable group which may be a hydrocarbyl or substituted hydrocarbyl group or an amine or a group
  • the terminating group is a hydrocarbyl group, it may be alkyl, cycloalkyl or aralkyl.
  • the substituent may be any substituent that does not exhibit an undesirable adverse effect on the microbiological properties of the polymeric biguanide.
  • substituents or substituted hydrocarbyl groups are aryloxy, alkoxy, acyl, acyloxy, halogen and nitrile.
  • the polymeric biguanide contains two biguanide groups of Formula 1
  • the two biguanide units are preferably linked by a polymethylene group, especially a hexamethylene group.
  • the terminating groups in such polymeric biguanides are preferably 4-chlorophenyl or 2-ethylhexyl. Examples of such compounds are represented by Formulae 2 and 3 in their free base form
  • the polymeric biguanide preferably contains more than two biguanide units of Formula 1 and preferably is a linear polymeric biguanide which has a recurring polymeric unit represented by Formula 4
  • X and Y may be the same or different and represent bridging groups in which, together, the total number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by X and Y is not less than 9 and not greater than 17.
  • the bridging groups X and Y may consist of a polymethylene chain, optionally interrupted by a heteroatom such as oxygen, sulphur or nitrogen.
  • X and Y may also incorporate a cyclic nucleus which may be saturated or unsaturated, wherein the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by X and Y is taken as including that segment of the cyclic group, or groups, which is the shortest.
  • the preferred polymeric biguanide for use in the present invention is poly(hexamethylenebiguanide), in which both X and Y in Formula 4 are the group —(CH 2 ) 6 +
  • the polymeric biguanides of Formula 4 are typically obtained as mixtures of polymers in which the polymer chains are of different lengths. Preferably, the number of individual biguanide units
  • [0018] is, together, from 3 to about 80.
  • n is from 4 to 40 and especially from 4 to 15. It is particularly preferred that the average value of n in the mixture is 12. Preferably, the average molecular weight of the polymer mixture is from 1100 to 3300.
  • the organic acid which forms the salt with the polymeric biguanide may contain a phosphonic, phosphoric, sulphonic or sulphate group but preferably contains a carboxylic acid group.
  • the organic acid may be aromatic but is preferably aliphatic, including alicyclic.
  • the aliphatic chain of the organic acid may be linear or branched, saturated or unsaturated, including mixtures thereof.
  • the aliphatic chain is linear and it is also preferred that the organic acid is an aliphatic carboxylic acid.
  • the organic acid contains not less than eight, more preferably not less than ten and especially not less than twelve carbon atoms excluding the acid group.
  • the organic acid contains not greater than 24, more preferably not greater than 20 and especially not greater than 18 carbon atoms excluding the acid group.
  • the organic acid may contain more than one acid group but it is preferred that only one such group is present.
  • the organic acid may be substituted by a halogen or particularly hydroxy group. It is, however, preferred that the organic acid is free from substituents.
  • aliphatic carboxylic acids are available commercially as mixtures such as those obtained from animal fats and vegetable oils and these contain both saturated and unsaturated aliphatic chains. These have also been found useful, especially the C 14-18 -alkyl carboxylic acids and their fully saturated or hydrogenated analogues.
  • Examples of optionally substituted carboxylic acids are valeric, hexanoic, octanoic, 2-octenoic, lauric, 5-dodecenoic, myristic, pentadecanoic, palmitic, oleic, stearic, eicosanoic, heptadecanoic, palmitoleic, ricinoleic, 1 2-hydroxystearic, 16-hydroxyhexadecanoic, 2-hydroxycaproic, 1 2-hydroxydodecanoic, 5-hydroxydodecanoic, 5-hydroxydecanoic, 4-hydroxydecanoic, dodecanedioic, undecanedioic, sebacic, benzoic, hydroxbenzoic and teraphthalic acids.
  • the carrier may be a solid but is preferably a liquid.
  • the liquid may be water whereby the composition containing the organic acid is a dispersion or emulsion.
  • the aqueous composition also contains a surfactant, particularly a non-ionic surfactant such as a polyalkylene oxide and especially an ethoxylate.
  • the aqueous composition may also contain other adjuvents which help distribute the polymeric biguanide salt uniformly throughout the composition. Examples of such adjuvants are compounds which provide structure to the water to inhibit sedimentation such as alginates and gums, particularly Xanthan gum.
  • the carrier is a liquid it is preferably a polar organic liquid, a substantially non-polar organic liquid or a halogenated hydrocarbon.
  • polar in relation to the organic liquid is meant an organic liquid or resin capable of forming moderate to strong bonds as described in the article entitled “A Three Dimensional Approach to Solubility” by Crowley et al in Journal of Paint Technology, Vol. 38, 1966, at page 269.
  • Such organic liquids generally have a hydrogen bonding number of 5 or more as defined in the abovementioned article.
  • Suitable polar organic liquids are amines, ethers, especially lower alkyl ethers, organic acids, esters, ketones, glycols, alcohols and amides. Numerous specific examples of such moderately strongly hydrogen bonding liquids are given in the book entitled “Compatibility and Solubility” by Ibert Mellan (published in 1968 by Noyes Development Corporation) in Table 2.14 on pages 3940 and these liquids all fall within the scope of the term polar organic liquid as used herein.
  • Preferred polar organic liquids are dialkyl ketones, alkyl esters of alkane carboxylic acids and alkanols, especially such liquids containing up to, and including, a total of 6 carbon atoms.
  • dialkyl and cycloalkyl ketones such as acetone, methyl ethyl ketone, diethyl ketone, di-isopropyl ketone, methyl isobutyl ketone, di-isobutyl ketone, methyl isoamyl ketone, methyl n-amyl ketone and cyclohexanone
  • alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxy propylacetate and ethyl butyrate
  • the substantially non-polar, organic liquids which may be used, either alone or in admixture with the aforementioned polar liquids, are aliphatic and aromatic hydrocarbons, such as toluene and xylene, and halogenated aliphatic and aromatic hydrocarbons, such as trichloro-ethylene, perchloroethylene and chlorobenzene.
  • the organic acid salt of the polymeric biguanide may be made by any method known to the art but is preferably made by precipitation of the biguanide from aqueous solution by addition of the organic acid under alkaline conditions.
  • the organic acid salts of the biguanide may be further purified by dissolution in a suitable organic liquid which is preferably immiscible with water and washing the organic phase with water to remove any residual water soluble salts.
  • the amount of polymeric biguanide in the composition may vary between wide limits depending on its end usage. Thus, where the composition is used to confer antimicrobial protection to a medium which is to be protected against microbiological spoilage the amount of polymeric biguanide may be just sufficient to provide such protection.
  • the amount of biguanide is not less than 1 ppm, more preferably not less than 10 ppm and especially not less than 20 ppm. It will be appreciated that where the composition containing the salt of the polymeric biguanide is to be transported in bulk the amount of the polymeric biguanide salt is as high as possible provided that the biguanide salt remains uniformly distributed throughout the composition.
  • the amount of polymeric biguanide salt in the composition is not greater than 30%, more preferably not greater than 25% and especially not greater than 20% based on the total weight of the composition.
  • polymeric biguanides in the form of a salt with an organic acid containing from 4 to 30 carbon atoms are novel.
  • a polymeric biguanide in the form of a salt with an aliphatic carboxylic acid containing from 4 to 20 carbon atoms, particularly from 10 to 20 carbon atoms and especially from 12 to 18 carbon atoms excluding the —COOH group, optionally substituted by hydroxy is provided.
  • the aliphatic carboxylic acid is free from substituents.
  • the aliphatic carboxylic acid may be linear or branched, saturated or unsaturated, including mixtures thereof. It is preferred that the aliphatic carboxylic acid is linear and saturated.
  • the polymeric biguanide is PHMB.
  • the organic acid salts of the polymeric biguanide exhibit antimicrobial, especially antibacterial, activity. Consequently, the polymeric biguanide salts or compositions containing the polymeric biguanide salts may be used to protect various media from microbiological growth.
  • the medium may be an industrial medium such as a cooling water tower liquid, paper mill liquor, metal working fluid, geological drilling lubricant, polymer emulsion, surface coating composition such as paint, varnish or lacquer.
  • the medium to be protected can be a solid such as wood or leather and particularly solid surfaces in the health-care or food preparation industries.
  • the solid may also be a textile material such as cellulose, including its blends with synthetic polymers and also non-woven materials such as those used in disposable items such as nappies, incontinence pads and feminine hygiene packs.
  • the polymeric biguanide salt may be applied by any method known to the art such as spraying, dipping or coating with a composition containing the polymeric biguanide salt.
  • the amount of polymeric biguanide salt which is applied to the medium to be protected from microbiological growth may be just sufficient to inhibit such growth or it may be in -excess of such amount.
  • the amount of polymeric biguanide salt which is applied to such medium is not greater than 2% and more preferably not greater than 1% by weight of the medium.
  • adequate protection is provided by from 1 ppm to 500 ppm, particularly 10 to 200 ppm and especially 10 to 100 ppm of the polymeric biguanide salt relating to the medium.
  • the product was obtained as a paste containing 11.0 Kgm PHMB stearate (50% theory).
  • the PHMB stearate salt exhibited similar microbiological activity to the hydrochloride salt when allowance is made for the different molecular weights.
  • Palmitic acid (1.35 parts ex Aldrich) were dissolved in water (15 ml) by heating to 60° C. and adjusting the pH value to between 9 and 10 by adding caustic soda.
  • PHMB hydrochloride (1 part as 20% solution, Cosmocil CQ ex Zeneca) was added and the reactants stirred at 80° C. for 2 hours. The reaction mass was then cooled to 20° C. whereupon the PHMB palmitate separated as a clear gum (1.86 parts).
  • Example 2 was repeated except replacing the palmitic acid with an equivalent amount of lauric acid and octanoic acid, respectively.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US09/445,765 1997-06-13 1998-06-05 Biocidal organic acid salts of a polymeric biguanide Abandoned US20020142020A1 (en)

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GB9712317.8 1997-06-13
GBGB9712317.8A GB9712317D0 (en) 1997-06-13 1997-06-13 Composition, compound and use

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US09/094,324 Expired - Lifetime US6509022B2 (en) 1997-06-13 1998-06-09 Composition for use in personal care comprising organic acid salts of polymeric biguanidines

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AT (1) ATE227932T1 (en)van)
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CA (2) CA2295012A1 (en)van)
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WO2011131773A1 (en) 2010-04-23 2011-10-27 Centre National De La Recherche Scientifique (C.N.R.S) Novel antimicrobial composition, use and preparation thereof

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FR2827507B1 (fr) * 2001-07-18 2005-07-01 Oreal Compose derive de polyguanidine et utilisation d'un tel compose pour la protection et/ou le soin des fibres keratiniques
JP2005505660A (ja) 2001-10-09 2005-02-24 ザ プロクター アンド ギャンブル カンパニー ポリマービグアニドを含む表面処理用予備湿潤拭き取り用品
FR2830442B1 (fr) * 2001-10-09 2004-02-06 Oreal Utilisation d'un compose de polyguanidine pour le traitement ou la mise en forme des cheveux, notamment le defrisage ou la permanente
FR2841778B1 (fr) * 2002-07-05 2004-10-01 Oreal Utilisation d'un compose derive de polyguanidine dans un traitement de coloration
US8795638B1 (en) * 2003-08-26 2014-08-05 Nevada Naturals Inc. Compositions for dental care
FR2860158A1 (fr) * 2003-09-30 2005-04-01 Oreal Composition moussante contenant un derive de polyguanidine, et ses utilisations notamment cosmetiques
RU2256439C1 (ru) * 2004-04-08 2005-07-20 Генкин Дмитрий Дмитриевич Композиция для умывания кожи лица
DE102004037598A1 (de) * 2004-08-03 2006-02-23 Prontomed Gmbh Mundspüllösung
US20060269498A1 (en) * 2005-05-17 2006-11-30 Gerard Malle Hair shaping composition comprising at least one polyguanidine other than hydroxide
US20060272107A1 (en) * 2005-05-17 2006-12-07 Gerard Malle Hair relaxing composition comprising at least one non-hydroxide polyguanidine
FR2885902B1 (fr) * 2005-05-17 2008-05-09 Oreal Composition de defrisage des cheveux comprenant au moins une multiguanidine hors hydroxyde
FR2885800B1 (fr) * 2005-05-17 2008-05-09 Oreal Composition de mise en forme des cheveux comprenant au moins une multiguanidine hors hydroxyde
DE502005009924D1 (de) * 2005-09-15 2010-08-26 Aesculap Ag Bioverträgliches antimikrobielles nahtmaterial
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US8685379B2 (en) * 2008-01-29 2014-04-01 International Art And Science Group, Inc. Functional material and delivery gel composition and method for manufacturing
TW201138843A (en) * 2009-12-18 2011-11-16 Colgate Palmolive Co Biguanide preservation of precipitated calcium carbonate
PL2524705T3 (pl) * 2011-05-19 2014-12-31 Lohmann & Rauscher Gmbh & Co Kg Sterylne opatrunki ran zawierające syntetyczny elastomer trój-blokowy i hydrofobowy polimer biguanidyny
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CN105315459B (zh) * 2014-10-29 2017-09-26 吉林云飞医药有限公司 一种聚己二酸基胍盐酸盐的制备方法
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Publication number Priority date Publication date Assignee Title
US20100075560A1 (en) * 2008-09-19 2010-03-25 Kannan Seshadri Ligand Graft Functionalized Substrates
US20100075131A1 (en) * 2008-09-19 2010-03-25 Etzel Mark R Ligand Graft Functionalized Substrates
US8551894B2 (en) * 2008-09-19 2013-10-08 3M Innovative Properties Company Ligand graft functionalized substrates
US9302208B2 (en) 2008-09-19 2016-04-05 3M Innovative Properties Company Ligand graft functionalized substrates
US9492771B2 (en) 2008-09-19 2016-11-15 3M Innovative Properties Company Ligand graft functionalized substrates
WO2011131773A1 (en) 2010-04-23 2011-10-27 Centre National De La Recherche Scientifique (C.N.R.S) Novel antimicrobial composition, use and preparation thereof
EP2386589A1 (en) * 2010-04-23 2011-11-16 Centre National de la Recherche Scientifique (C.N.R.S) Novel antimicrobial composition, use and preparation thereof

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ZA985096B (en) 1999-01-12
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DE69809548T2 (de) 2003-09-25
RU2209620C2 (ru) 2003-08-10
JP2002505695A (ja) 2002-02-19
GB9712317D0 (en) 1997-08-13
HUP0003065A3 (en) 2001-05-28
DE69809548D1 (de) 2003-01-02
ATE227932T1 (de) 2002-12-15
EP0987946B1 (en) 2002-11-20
CN1266350A (zh) 2000-09-13
KR20010013704A (ko) 2001-02-26
BR9810435A (pt) 2000-09-19
CN100577142C (zh) 2010-01-06
PL188771B1 (pl) 2005-04-29
DE69817564D1 (de) 2003-10-02
US20010006647A1 (en) 2001-07-05
EP0987947A1 (en) 2000-03-29
NO996042L (no) 1999-12-08
CN1259846A (zh) 2000-07-12
JP4308331B2 (ja) 2009-08-05
WO1998056253A1 (en) 1998-12-17
AR012965A1 (es) 2000-11-22
HUP0003065A2 (hu) 2001-02-28
DE69817564T2 (de) 2004-03-18
ID24652A (id) 2000-07-27
CA2293558A1 (en) 1998-12-17
IN190655B (en)van) 2003-08-16
JP2002510298A (ja) 2002-04-02
US6509022B2 (en) 2003-01-21
NZ501740A (en) 2002-02-01
AR015884A1 (es) 2001-05-30
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ES2205509T3 (es) 2004-05-01
AU7919298A (en) 1998-12-30
NO996042D0 (no) 1999-12-08
ZA985030B (en) 1999-12-10
BR9810251A (pt) 2000-09-19
CA2295012A1 (en) 1998-12-17
AU7782598A (en) 1998-12-30
AU742600B2 (en) 2002-01-10
PL337277A1 (en) 2000-08-14

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