CA1119748A - Polypyrrolidone-iodine complex - Google Patents
Polypyrrolidone-iodine complexInfo
- Publication number
- CA1119748A CA1119748A CA000309628A CA309628A CA1119748A CA 1119748 A CA1119748 A CA 1119748A CA 000309628 A CA000309628 A CA 000309628A CA 309628 A CA309628 A CA 309628A CA 1119748 A CA1119748 A CA 1119748A
- Authority
- CA
- Canada
- Prior art keywords
- iodine
- polypyrrolidone
- complex
- nylon
- process according
- 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.)
- Expired
Links
Abstract
ABSTRACT OF THE DISCLOSURE
A novel complex of polypyrrolidone, also known as nylon-4, with iodine is disclosed. The complex has biocidal properties exhibiting especially the fungicidal and bactericidal properties of free iodine but not its irritating and toxic properties. The complex may be formed with polypyrrilidone having any physical form such as a powder, pulp, film, fiber or molded article.
Bandage material made from fabric woven from nylon-4 fibers and complexed with iodine is a particularly useful form. Dry powders, ointments and other compositions for topical application may also be made.
A novel complex of polypyrrolidone, also known as nylon-4, with iodine is disclosed. The complex has biocidal properties exhibiting especially the fungicidal and bactericidal properties of free iodine but not its irritating and toxic properties. The complex may be formed with polypyrrilidone having any physical form such as a powder, pulp, film, fiber or molded article.
Bandage material made from fabric woven from nylon-4 fibers and complexed with iodine is a particularly useful form. Dry powders, ointments and other compositions for topical application may also be made.
Description
11197~8 POLYPYKROLI~ONE-IODINE COMPLEX
BACKGROUND O~ THE IN~ENTI~N
The iodine complex formed by mixing polyvinylpyrrolidone (PVP) and iodine, first disclosed in U.S. Patent Number 2,739,922 issued to Herrnan A. ~helanski, has established itself as the preferred way of utilizing ~he 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 cpmplex 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.
OBJECTS OF THE INVENTION
It is a primary object of this invention to provide a water insoluble and therefore more permanent complex of iodine possess-ing medicinal properties similar to the water soluble PVP-iodine complex.
i 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 irri~ating 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.
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It is a still further object of this invention ~o provide water insoluble long lasting antiseptic ointments for topical application.
Other objects will be apparent in the detailed disclosure which fol]ows.
DESCRIPTION_OF PREFERRED EMBODIMENTS
It has been found that polypyrrolidone, also known as nylon-4, a polymer having the structure ~ (CH2)3-~
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 4-iodine complex is not soluble in water.
It is surprising and unexpected that nylon-4 should form a complex with iodine since the pyrrolidone 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 tfibrils), an extruded rod or filament, a fabric woven from a textile fiber, a film or a molded 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 ~119748 fibers and for this purpose a polymer having superior thermal ~ stability is required and the molecular weight of the resin ,`d 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 deciliter solution in hexafluoroiso-propanol 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 5':,' are also disclosed in this patent.
The complex of polypyrrolidone and iodine is formed by reacting polypyrrolidone with iodine. 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 color almost immediately and then becomes black. Upon drying the color becomes lighter. Immersion times range from a few seconds to two or three minutes. Shorter immersion times will produce a golden yellow color in the dried article while longer times will give a dark brown color in the dried material. The color of the dried complex is a measure of the amount of iodine present. Excessive amounts of iodine will tend to degrade the polymer and should be avoided if this is important as it is in a textile fiber.
~{~
~ ~ iO(~illC C(.~ `X III<Iy ~)~` t()l~ C`(I ~)y ~ r ~ ;U~}~
cxl)c;~ ?, Ihe tlylo~ rticlc to ioclirle val-or or tritur-atirlg th~
powderecl res;n ~ith ~solid iodirle crya~clls~ Al~errl~ltively t~le resin may be ball milled af-~er mixing with iodine crystals to form a powdered complex which is well suited for use as a dry powder for compounding into an ointment. Other ingredients to minimi~e cak;ng or to impart additional therapeutic properties may be added to the mixture. For compound;ng an ointment any suitable ointment base may be used such as lanolint petrolatum, 10 potassium stearate and rnany o-thers.
The iodine is rather tightly held in the complex. By way of comparison, if cotton (another hydrophyllic fiber) is immersed in an iodine solution prepared according to the recipe given above it develops a similar dark brown color. But the iodine is only held mechanically and washes out completely with water within a minute. The dark bro~n 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 20 rapid. Thus if the complex is placed in boiling water the iodine - will be removed completely in a matter of minutes. Sirnilarly if placed in an oven at 100 C. the iodine will sublime out of the complex very rapidly leaving colorless nylon-4. Samples may be kept for several months at room temperature without appreciable loss of iodine howeverO At 40 C. no appreciable loss of iodine occurs within 24 hours. Also the complex is quite insensitive to changes in pH. No loss in iodine content (such as to iodide ion) occurs within a range of pH 5 to pll 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.
10 In this appliaction 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 ,i', the resin must be kept under dry nitrogen in the hopper f~eding ~,' 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 fiber. The size of the hole and the amount of draw ~'~ determine the diameter of the filament or filaments as well as the 20 tensile strength. For certain applications a multifilament 1 structure is preferred. In either case the suture material is ,1 then passed through an 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 ~j , 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 fiber and treated in the iodine bath in a similar manner.
~t The nylon 4-iodine complex may be utilized in many other ways, for example as an 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 vapor to provide a sterile atmosphere. Since there are many different embodiments of this invention which may be made without departing from the spirit and scope thereof, it is to be understood that the inven-tion îs not to be limited by the examples cited except as defined in the appended claims.
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.`, ' ~48 SUPPLEMENTARY DISCLOSURE
The complex of nylon-4 with iodine is best formed by immersing the nylon-4 article in a solution of iodine in an aqueous solution of an inorganic iodide. A preferred formula i s:
Potassium iodide 3.3 grams Water 100 ml Iodine 2.0 grams , .
but sodium, lithium, calcium, magnesium, etc. iodides may also be used. Any water soluble iodide which forms iodide ions in water solution is satisfactory provided the I3-ion ; is formed when iodine is added.
.
~;
~, .
BACKGROUND O~ THE IN~ENTI~N
The iodine complex formed by mixing polyvinylpyrrolidone (PVP) and iodine, first disclosed in U.S. Patent Number 2,739,922 issued to Herrnan A. ~helanski, has established itself as the preferred way of utilizing ~he 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 cpmplex 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.
OBJECTS OF THE INVENTION
It is a primary object of this invention to provide a water insoluble and therefore more permanent complex of iodine possess-ing medicinal properties similar to the water soluble PVP-iodine complex.
i 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 irri~ating 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.
~ ;~
~i~974~
It is a still further object of this invention ~o provide water insoluble long lasting antiseptic ointments for topical application.
Other objects will be apparent in the detailed disclosure which fol]ows.
DESCRIPTION_OF PREFERRED EMBODIMENTS
It has been found that polypyrrolidone, also known as nylon-4, a polymer having the structure ~ (CH2)3-~
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 4-iodine complex is not soluble in water.
It is surprising and unexpected that nylon-4 should form a complex with iodine since the pyrrolidone 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 tfibrils), an extruded rod or filament, a fabric woven from a textile fiber, a film or a molded 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 ~119748 fibers and for this purpose a polymer having superior thermal ~ stability is required and the molecular weight of the resin ,`d 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 deciliter solution in hexafluoroiso-propanol 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 5':,' are also disclosed in this patent.
The complex of polypyrrolidone and iodine is formed by reacting polypyrrolidone with iodine. 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 color almost immediately and then becomes black. Upon drying the color becomes lighter. Immersion times range from a few seconds to two or three minutes. Shorter immersion times will produce a golden yellow color in the dried article while longer times will give a dark brown color in the dried material. The color of the dried complex is a measure of the amount of iodine present. Excessive amounts of iodine will tend to degrade the polymer and should be avoided if this is important as it is in a textile fiber.
~{~
~ ~ iO(~illC C(.~ `X III<Iy ~)~` t()l~ C`(I ~)y ~ r ~ ;U~}~
cxl)c;~ ?, Ihe tlylo~ rticlc to ioclirle val-or or tritur-atirlg th~
powderecl res;n ~ith ~solid iodirle crya~clls~ Al~errl~ltively t~le resin may be ball milled af-~er mixing with iodine crystals to form a powdered complex which is well suited for use as a dry powder for compounding into an ointment. Other ingredients to minimi~e cak;ng or to impart additional therapeutic properties may be added to the mixture. For compound;ng an ointment any suitable ointment base may be used such as lanolint petrolatum, 10 potassium stearate and rnany o-thers.
The iodine is rather tightly held in the complex. By way of comparison, if cotton (another hydrophyllic fiber) is immersed in an iodine solution prepared according to the recipe given above it develops a similar dark brown color. But the iodine is only held mechanically and washes out completely with water within a minute. The dark bro~n 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 20 rapid. Thus if the complex is placed in boiling water the iodine - will be removed completely in a matter of minutes. Sirnilarly if placed in an oven at 100 C. the iodine will sublime out of the complex very rapidly leaving colorless nylon-4. Samples may be kept for several months at room temperature without appreciable loss of iodine howeverO At 40 C. no appreciable loss of iodine occurs within 24 hours. Also the complex is quite insensitive to changes in pH. No loss in iodine content (such as to iodide ion) occurs within a range of pH 5 to pll 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.
10 In this appliaction 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 ,i', the resin must be kept under dry nitrogen in the hopper f~eding ~,' 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 fiber. The size of the hole and the amount of draw ~'~ determine the diameter of the filament or filaments as well as the 20 tensile strength. For certain applications a multifilament 1 structure is preferred. In either case the suture material is ,1 then passed through an 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 ~j , 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 fiber and treated in the iodine bath in a similar manner.
~t The nylon 4-iodine complex may be utilized in many other ways, for example as an 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 vapor to provide a sterile atmosphere. Since there are many different embodiments of this invention which may be made without departing from the spirit and scope thereof, it is to be understood that the inven-tion îs not to be limited by the examples cited except as defined in the appended claims.
. .
.,.~
, .
" ~
f ~
., .
;, .
..~
.`, ' ~48 SUPPLEMENTARY DISCLOSURE
The complex of nylon-4 with iodine is best formed by immersing the nylon-4 article in a solution of iodine in an aqueous solution of an inorganic iodide. A preferred formula i s:
Potassium iodide 3.3 grams Water 100 ml Iodine 2.0 grams , .
but sodium, lithium, calcium, magnesium, etc. iodides may also be used. Any water soluble iodide which forms iodide ions in water solution is satisfactory provided the I3-ion ; is formed when iodine is added.
.
~;
~, .
Claims (10)
1. A process of forming a complex of polypyrrolidone and iodine which comprises reacting polypyrrolidone with iodine.
2. A process according to claim 1 which comprises immersing polypyrrolidone in a solution of iodine in aqueous potassium iodide.
3. A process according to claim 1, which comprises exposing polypyrrolidone to iodine vapor.
4. A process according to claim 1, which comprises triturating powdered polypyrrolidone with iodine crystals.
5. A process according to claim 1, which comprises forming a mixture of polypyrrolidone and iodine crystals followed by ball milling said mixture.
6. A complex of polypyrrolidone and iodine whenever produced by the process of claims 1, 2 or 3 or its obvious chemical equivalents.
7. A complex of polypyrrolidone and iodine whenever produced by the process of claims 4 or 5, or by its obvious chemical equivalents.
CLAIMS SUPPORTED BY SUPPLEMENTAL DISCLOSURE
CLAIMS SUPPORTED BY SUPPLEMENTAL DISCLOSURE
8. A method according to claim 1 which comprises immersing polypyrrolidone in a solution of iodine in an aqueous solution of an inorganic iodide.
9. A method of preparing a water-insoluble complex of iodine and polypyrrolidone which comprises contacting the polypyrrolidone with an aqueous solution containing I3- ions.
10. A complex of polypyrrolidone and iodine whenever formed by the method of claims 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000309628A CA1119748A (en) | 1978-08-18 | 1978-08-18 | Polypyrrolidone-iodine complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000309628A CA1119748A (en) | 1978-08-18 | 1978-08-18 | Polypyrrolidone-iodine complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119748A true CA1119748A (en) | 1982-03-09 |
Family
ID=4112150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000309628A Expired CA1119748A (en) | 1978-08-18 | 1978-08-18 | Polypyrrolidone-iodine complex |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1119748A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4888118A (en) * | 1988-04-18 | 1989-12-19 | Nyodine Products, Inc. | Water purification process and apparatus employing nylon 4 |
-
1978
- 1978-08-18 CA CA000309628A patent/CA1119748A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4888118A (en) * | 1988-04-18 | 1989-12-19 | Nyodine Products, Inc. | Water purification process and apparatus employing nylon 4 |
| EP0412227A1 (en) * | 1988-04-18 | 1991-02-13 | Barson Corporation | Water purification process and apparatus employing polypyrrolidone |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |