GB2031441A - Polypyrrolidone-iodine complex - Google Patents

Polypyrrolidone-iodine complex Download PDF

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Publication number
GB2031441A
GB2031441A GB7834404A GB7834404A GB2031441A GB 2031441 A GB2031441 A GB 2031441A GB 7834404 A GB7834404 A GB 7834404A GB 7834404 A GB7834404 A GB 7834404A GB 2031441 A GB2031441 A GB 2031441A
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GB
United Kingdom
Prior art keywords
iodine
polypyrrolidone
complex
composition according
nylon
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.)
Granted
Application number
GB7834404A
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GB2031441B (en
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Individual
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Individual
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 Individual filed Critical Individual
Priority to GB7834404A priority Critical patent/GB2031441B/en
Priority to DE19782837093 priority patent/DE2837093C2/en
Priority to BE190140A priority patent/BE870058A/en
Publication of GB2031441A publication Critical patent/GB2031441A/en
Application granted granted Critical
Publication of GB2031441B publication Critical patent/GB2031441B/en
Expired legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/12—Iodine, e.g. iodophors; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/785—Polymers containing nitrogen
    • A61K31/787—Polymers containing nitrogen containing heterocyclic rings having nitrogen as a ring hetero atom
    • A61K31/79—Polymers of vinyl pyrrolidone
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20—Halogens; Compounds thereof
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • 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
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/005—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters containing a biologically active substance, e.g. a medicament or a biocide
    • 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
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/0066—Medicaments; Biocides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/24—Pyrrolidones or piperidones
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/202—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with halogen atoms, e.g. triclosan, povidone-iodine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

Abstract

A novel complex of polypyrrolidone, also known as nylon-4, with iodine is disclosed. The complex has biocidal properties exhibiting expecially the fungicidal and bactericidal properties of free iodine but not its irritating and toxic properties. The complex may be formed with polypyrrolidone having any physical form such as a powder, pulp, film, fibre or moulded article. Bandage material made from fabric woven from nylon-4 fibres and complexed with iodine is a particularly useful form. Dry powders, ointments and other compositions for topical application may also be made.

Description

SPECIFICATION Polypyrrolidone-iodine complex This invention relates to a water-insoluble complex of iodine and polypyrrolidone.
The iodine complex formed by mixing polyvinylpyrrolidone (PVP) and iodine, first disclosed in U.S. Patent No. 2,739,922 has established itself as the preferred way of utilizing the desirable biocidal properties of iodine while avoiding the irritating side effects. It has become the product of choice especially in surgery where it is used to coat the skin prior to incision.
PVP is a water soluble polymer and likewise the PVP-iodine complex is water soluble.
There are applications however in which this solubility in water is undesirable. For example, in topical applications the effectiveness of a water soluble antiseptic is of short duration since it is readily washed away not only by water but by perspiration. A water insoluble complex with iodine which exhibits similar "tamed iodine" properties would be much more permanent.
It is a primary object of this invention to provide a water insoluble and therefore more permanent complex of iodine possessing medicinal properties similar to the water soluble PVP-iodine complex.
It is another object of this invention to provide a water insoluble complex of iodine which slowly releases elemental iodine in small but effective amounts over a long period of time thus prolonging the microbiological activity while minimizing the irritating side effects.
It is a further object of the invention to provide a novel bandage and suture material which in itself is the bactericidal and fungicidal agent.
It is a still further object of this invention to provide water insoluble long lasting antiseptic ointments for topical application.
It has been found that polypyrrolidone, also known as nylon-4, a polymer having the structure
can be made to form a complex with elemental iodine which is very similar to the polyvinylpyrrolidone-iodine complex. Unlike the PVP-iodine complex, however, the nylon 4iodine complex is not soluble in water.
It is surprising and unexpected that nylon-4 should form a complex with iodine since the polypyrrolidone ring, which is intact in PVP, is opened and non-existent in nylon-4 which has instead a polyamide structure. Nevertheless it has been found that a complex with iodine will form and furthermore it closely resembles the PVP-iodine complex except for the lack of solubility in water.
The polypyrrolidone employed to make the iodine complex may be in any physical form such as the powdered resin, a pulp (fibrils), an extruded rod or filament, a fabric woven from a textile fibre, a film or a moulded article. For purposes of making an ointment the finely powdered resin is used and the molecular weight (i.e. the value of n in the above formula) is unimportant. But for making sutures or bandages from woven fabric it is necessary to melt extrude the resin to form the filaments or fibres and for this purpose a polymer having superior thermal stability is required and the molecular weight of the resin becomes important. A molecular weight sufficient to give an inherent viscosity of at least 2.0 deciliters per gram when measured as a 0.5 gram per diciliter solution in hexafluroisopropanol at 25"C. is needed.Most preferably resins having an inherent viscosity of from 3.0 to 4.0 or higher are used for melt spinning purposes. Methods of making polymers of 2-pyrrolidone having these characteristics are disclosed in U.S. Patent number 3,721,652. The methods of determining the inherent viscosity are also disclosed in this patent.
The complex of nylon-4 with iodine is best formed by immersing the nylon-4 article in a solution of iodine in aqueous potassium iodide. A preferred formula is Potassium iodide 3.3 grams Water 100 ml iodine 2.0 grams Upon immersion in this solution the white polypyrrolidone article turns to a dark chocolate-brown colour almost immediately and then becomes black. Upon drying the colour becomes lighter. Immersion times range from a few seconds to two or three minutes.
Shorter immersion times will produce a golden yellow colour in the dried article while longer times will give a dark brown colour in the dried material. The colour of the dried complex is a measure of the amount of iodine prlesent. Excessive amounts of iodine will tend to degrade the polymer and should be avoided if this is important as it is in a textile fibre.
The iodine complex may be formed by other methods such as exposing the nylon-4 article to iodine vapour or triturating the powered resin with solid iodine crystals. Alternatively the resin may be ball milled after mixing with iodine crystals to form a powdered complex which is well suited for use as a dry powder or for compounding into anointment.
Other ingredients to minimize caking or to impart additional therapeutic properties may be added to the mixture. For compounding an ointment any suitable ointment base may be used such a lanolin, petrolatum, potassium stearate and many others.
The iodine is rather tightly held in the complex. By way of comparison, if cotton (another hydrophilic fibre) is immersed in an iodine solution prepared according to the recipe given above it develops a similar dark brown colour. But the iodine is only held mechanically and washes out completely with water within a minute. The dark brown complex formed with nylon-4 does not readily wash out with water. Small amounts of iodine are released however at a rate which is dependent on the temperature. The rate is very slow at room temperature but at about 100"C. it is quite rapid. Thus if the complex is placed in boiling water the iodine will be removed completely in a matter of minutes. Similarly if placed in an oven at 1 00 C. the iodine will sublime out of the complex very rapidly leaving colourless nylon-4.Samples may be kept for several months at room temperature without appreciable loss of iodine however. At 40"C. no appreciable loss of iodine occurs within 24 hours. Also the complex is quite insensitve to changes in pH. No loss in iodine content (such as to iodide ion) occurs within a range of pH 5 to pH 10.
In order to be effective a slow release of iodine must occur and at body temperature this release takes place at about the proper rate. For many reasons a bandage should be changed every 24 hours but it should remain effective during this period of time. An important feature of the nylon-4 iodine complex is that, unlike its PVP-iodine counterpart, if the bandage or other dressing gets wet even from perspiration the biocidal agent is not washed away.
Another embodiment of the invention is a biocidal suture. In this application the polypyrrolidone resin is melt extruded at temperatures of about 290"C. under high pressure generated by the screw of the extruder. Care must be taken to dry the resin to not more than about 0.03% moisture content before extruding and the resin must be kept under dry nitrogen in the hopper feeding the extruder to prevent further moisture pick-up.
The molten resin is forced through a spinnerette consisting of a single hole to form a monofilament or multiple holes to form a textile fibre. The size of the hole and the amount of draw determine the diameter of the filament or filaments as well as the tensile strength. For certain applications a multifilament structure is preferred. In either case the suture material is then passed through the iodine bath made according to the recipe given earlier. The residence time in the bath may be from a-few seconds to a few minutes depending upon the amount of iodine desired in the complex. The material is then washed briefly in water then air dried.
For bandage applications a suitable fabric is woven from nylon-4 textile fibre and treated in the iodine bath in a similar manner.
The nylon-4 iodine complex may be utilized in many other ways, for example as in inner layer in packaging to serve as a biocidal barrier thus keeping the contents of the package sterile or as a source of a low concentration of iodine vapour to provide a sterile atmosphere.

Claims (11)

1. A composition having microbiological activity comprising a complex of polypyrrolidone and iodine.
2. A composition according to claim 1 wherein the polypyrrolidone is in the form of a bandage or wound dressing material.
3. A composition according to claim 1 wherein the polypyrrolidone is in the form of a suture.
4. A composition according to claim 1 wherein the polypyrrolidone is in the form of a finely divided powder.
5. A composition according to claim 1 wherein the polypyrrolidone is in the form of a film.
6. A composition according to claim 1 wherein the polypyrrolidone is in the form of fibrils.
7. A composition according to claim 1 wherein the polypyrrolidone is in the form of a woven fabric.
8. A composition according to claim 1 wherein the polypyrrolidone is in the form of a non-woven fabric.
9. An ointment comprising a composition according to claim 1 and a suitable pharmaceutically acceptable vehicle.
10. A biocidal powder comprising a composition according to claim 1 and a pharmaceutically acceptable solid carrier.
11. A composition according to claim 1 wherein the polypyrrolidone is in the form of a moulded article.
1 2. A method of preparing a water-insoluble complex of iodine and nylon-4 which comprises contacting the nylon-4 with a solution of an iodide.
GB7834404A 1978-08-24 1978-08-24 Polypyrrolidone iodine complex Expired GB2031441B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB7834404A GB2031441B (en) 1978-08-24 1978-08-24 Polypyrrolidone iodine complex
DE19782837093 DE2837093C2 (en) 1978-08-24 1978-08-24 Microbiologically active substance
BE190140A BE870058A (en) 1978-08-24 1978-08-29 COMPOSITION WITH MICROBIOLOGICAL ACTIVITY

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7834404A GB2031441B (en) 1978-08-24 1978-08-24 Polypyrrolidone iodine complex

Publications (2)

Publication Number Publication Date
GB2031441A true GB2031441A (en) 1980-04-23
GB2031441B GB2031441B (en) 1982-11-17

Family

ID=10499244

Family Applications (1)

Application Number Title Priority Date Filing Date
GB7834404A Expired GB2031441B (en) 1978-08-24 1978-08-24 Polypyrrolidone iodine complex

Country Status (3)

Country Link
BE (1) BE870058A (en)
DE (1) DE2837093C2 (en)
GB (1) GB2031441B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128125A (en) * 1988-02-16 1992-07-07 Barnes Arthur C Method for preparing finely divided nylon-4 complex with iodine and antiseptic preparation made therefrom
US7217417B2 (en) * 2002-05-20 2007-05-15 Dermacia, Inc. Gel-based cosmetic and wound-healing formulation and method
WO2016042406A1 (en) * 2014-09-19 2016-03-24 Galia Textil Impregnated dry substrates for a dressing material, method and system for manufacturing the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6425870A (en) * 1987-04-30 1989-01-27 Ajinomoto Kk Support for anastomosis or bonding of living body
US5232692A (en) * 1989-04-28 1993-08-03 Research And Education Institute, Inc. Povidone-iodine neonatal ophthalmic antimicrobial prophylactic agent

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739922A (en) * 1952-03-13 1956-03-27 Herman A Shelanski Mixtures of polymeric n-vinyl pyrrolidone and halogens

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128125A (en) * 1988-02-16 1992-07-07 Barnes Arthur C Method for preparing finely divided nylon-4 complex with iodine and antiseptic preparation made therefrom
US7217417B2 (en) * 2002-05-20 2007-05-15 Dermacia, Inc. Gel-based cosmetic and wound-healing formulation and method
WO2016042406A1 (en) * 2014-09-19 2016-03-24 Galia Textil Impregnated dry substrates for a dressing material, method and system for manufacturing the same

Also Published As

Publication number Publication date
BE870058A (en) 1978-12-18
DE2837093C2 (en) 1986-07-31
DE2837093A1 (en) 1980-03-06
GB2031441B (en) 1982-11-17

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19920824