CA1066614A - Bactericides - Google Patents
BactericidesInfo
- Publication number
- CA1066614A CA1066614A CA268,652A CA268652A CA1066614A CA 1066614 A CA1066614 A CA 1066614A CA 268652 A CA268652 A CA 268652A CA 1066614 A CA1066614 A CA 1066614A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- temperature
- components
- polyvinylpyrrolidone
- iodine
- 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
- 239000003899 bactericide agent Substances 0.000 title abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 20
- 239000011630 iodine Substances 0.000 claims abstract description 20
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 4
- 229940006461 iodide ion Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000002070 germicidal effect Effects 0.000 abstract description 4
- 241001465754 Metazoa Species 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
TITLE
IMPROVEMENTS IN OR RELATING TO BACTERICIDES
INVENTORS
VLADIMIR HACH
THOMAS HALASZ
JACQUES MEUNIER
ABSTRACT OF THE DISCLOSURE
The present invention provides an advantageous process for the preparation of a polyvinylpyrrolidone-iodine adduct exhibiting germicidal properties. The process for preparing the adduct, which is substantially nontoxic to animals and stable in aqueous media, comprises admixing elemental iodine and powdered polyvinylpyrrolidone having a moisture content of from 5-15% by weight and heating the components, during or subsequent to admixing, to a temperature of at most 70°C.
IMPROVEMENTS IN OR RELATING TO BACTERICIDES
INVENTORS
VLADIMIR HACH
THOMAS HALASZ
JACQUES MEUNIER
ABSTRACT OF THE DISCLOSURE
The present invention provides an advantageous process for the preparation of a polyvinylpyrrolidone-iodine adduct exhibiting germicidal properties. The process for preparing the adduct, which is substantially nontoxic to animals and stable in aqueous media, comprises admixing elemental iodine and powdered polyvinylpyrrolidone having a moisture content of from 5-15% by weight and heating the components, during or subsequent to admixing, to a temperature of at most 70°C.
Description
The present invention relates to germicidal and bactericidal agents and in particular a novel and advantageous process for the production thereof.
BACKGROUND OF INVENTION
Adducts of polyvinylpyrrolidone and iodine having germicidal and bactericidal properties are known. -Such compositions are preferably readily soluble in aqueous media when the iodine is in an easily available form and in a state substantially non-toxic to animals.
U.S. Patent No. 2,706,701 to Beller and Hosmer discloses a process for producing such polyvinylpyrrolidone/ -iodine (PVPI) adducts which comprises mixing dry powdered polyvinylpyrrolidone with dry elemental iodine. However, as is explained in detail in lator U.S. Patent No. 2,900,305, the product formed in the earlier patent suffers from certain disadvantages. U.S. Patent No. 2,900,305 itself teaches an improved process for producing a PVPI adduct which has the advantages of being stable in aqueous media, said process comprising thoroughly mixing elemental iodine and powdered l-vinyl-2-pyrrolidone containing from 4.9-13% water and heating the resulting composition at a temperature of ~rom 90100C. Mixing takes place in a ball mill for six hours and the subsequent heating step, effected at 95C, lasts for twenty-two hours.
STATEMENT OF INVENTION
It has now been found that a satisfactory PVPI
adduct can be prepared by a novel process comprising mixing elemental iodine and powdered PVP, the latter having a moisture content of from 5 to 1;% by weight, the components, either during, or subsequent to, mixing being heated to a temperature of at most about 70C.
It has been found that temperatures in excess of about 70C do not materially assist the production ~ ,. ~ .
BACKGROUND OF INVENTION
Adducts of polyvinylpyrrolidone and iodine having germicidal and bactericidal properties are known. -Such compositions are preferably readily soluble in aqueous media when the iodine is in an easily available form and in a state substantially non-toxic to animals.
U.S. Patent No. 2,706,701 to Beller and Hosmer discloses a process for producing such polyvinylpyrrolidone/ -iodine (PVPI) adducts which comprises mixing dry powdered polyvinylpyrrolidone with dry elemental iodine. However, as is explained in detail in lator U.S. Patent No. 2,900,305, the product formed in the earlier patent suffers from certain disadvantages. U.S. Patent No. 2,900,305 itself teaches an improved process for producing a PVPI adduct which has the advantages of being stable in aqueous media, said process comprising thoroughly mixing elemental iodine and powdered l-vinyl-2-pyrrolidone containing from 4.9-13% water and heating the resulting composition at a temperature of ~rom 90100C. Mixing takes place in a ball mill for six hours and the subsequent heating step, effected at 95C, lasts for twenty-two hours.
STATEMENT OF INVENTION
It has now been found that a satisfactory PVPI
adduct can be prepared by a novel process comprising mixing elemental iodine and powdered PVP, the latter having a moisture content of from 5 to 1;% by weight, the components, either during, or subsequent to, mixing being heated to a temperature of at most about 70C.
It has been found that temperatures in excess of about 70C do not materially assist the production ~ ,. ~ .
- 2 -. . ' . ' ' ,' ~ . . . -~ .
10666~4 cf the ~esired adduc and are actually detrimental in causing undesirable caking of the product. The process is generally effected at a temperature of from 30to 70C
and coveniently a temperature of from 50to 70C. It is especially preferred that the process be effected at a temperature of from 60to 70C, since the higher temperatures allow production of the desired product most economically.
As stated, the heating may be effected during mixing or subsequent thereto. Although the applicant does not wish to be bound by any specific theories, there are indications that the reaction of the PVP and iodine seems to occur in two phases - a rapid first phase and a short second phase: the first phase comprising, at most, about one-third of the total process time. It is believed that upon completion of the first phase which essentially involves mixing, the short second phase may be effected without further mixing merely by heating the mixture of reactants. It will be readily appreciated that this finding has significant economic implications in that mixing equipment, which may be expensive both to purchase and operate, need only be employed for a ;
portion of the process time and simple trays or the like may be used to contain the reaction mixture until the ;
process is completed. This offers significant reduction in processing costs.
Regarding the mixing, this may be effected by a heated rotating vessel; mechanical mixing aids such as balls or paddles generally being unnecessary, especially at the preferred temperature.
In addition to the advantages referred to above, ;
the process of the present inv~ntion has generally been
10666~4 cf the ~esired adduc and are actually detrimental in causing undesirable caking of the product. The process is generally effected at a temperature of from 30to 70C
and coveniently a temperature of from 50to 70C. It is especially preferred that the process be effected at a temperature of from 60to 70C, since the higher temperatures allow production of the desired product most economically.
As stated, the heating may be effected during mixing or subsequent thereto. Although the applicant does not wish to be bound by any specific theories, there are indications that the reaction of the PVP and iodine seems to occur in two phases - a rapid first phase and a short second phase: the first phase comprising, at most, about one-third of the total process time. It is believed that upon completion of the first phase which essentially involves mixing, the short second phase may be effected without further mixing merely by heating the mixture of reactants. It will be readily appreciated that this finding has significant economic implications in that mixing equipment, which may be expensive both to purchase and operate, need only be employed for a ;
portion of the process time and simple trays or the like may be used to contain the reaction mixture until the ;
process is completed. This offers significant reduction in processing costs.
Regarding the mixing, this may be effected by a heated rotating vessel; mechanical mixing aids such as balls or paddles generally being unnecessary, especially at the preferred temperature.
In addition to the advantages referred to above, ;
the process of the present inv~ntion has generally been
- 3 -- 10666~4 found to provide the desired product in less time than the prior art methods. This is particularly evident when the PVP starting material has a moisture content within the preferred range of from 8 to 12% by weight, --the process in such instances being completed in under twenty hours, phase one lasting at most about S to 6 hours. In general, it has been found that within the ~tated limits the lower the moisture content the longer the required reaction time although, as indicated above, -the reaction time is also dependent on the temperature involved. The novel process is completed when the desired product having an available iodine/iodide ion ratio of from 1.9 to 2.5 , preferably about 2.2 is obtained. Throughout the specification, the said available iodine/iodide ratio is determined by the method described at lines 42-63, column 1 of U.S.
Patent No. 2,900,305.
It is preferred that the polyvinylpyrrolidone polymer used in the production of the desired PVPI adduct i8 1-v~nyl-2-pyrrolidone.
The present invention will be further described with reference to, but not limited by, the following specific examples. Throughout these examples, the preferred PVP, l-vinyl-2-pyrrolidone polymer is used which had a ~K" value of 30. (By K value is meant the Fikentscher K value as defined by H. Fikentscher in Cellulosechemie 13, 58-64, 71-4 (1932), the general standard in this field. This value was evaluated using an aqueous solution of the polymer having a concentration of 1 g of anhydrous polymer per 100 ml solution in a Ubbelohde viscometer at a temperature of 25C.) .` ' ~06661g Continuous Mixing/heating of Reaction Mixture A. 18;85 Kg of powdered PVP (K-30), having a moisture content of 9.67% by weight, and 3.40 kg of elemental iodine was introduced into a rotating conically-shaped reactor provided with a heating ~acket. The reactor, known as the Pfaudler Conical Dryer-Blender (available from Pfaudler Company, 1000 West Avenue, ~ochester, New York, U.S.A., 14603) has no internal agitator or mixer devices and subjects the reactant to a gentle tumbling action or treatment.
The mixing was continued at a temperature between 64and 67C for twenty (20) hours, at the.end of which the desired product having an -avaiOdaibdee iOnine rat;io of 2.2 was obtained in a yield of 22.1 kg.
B. The process of Part A was repeated, the only di~:ference being that the processing temperature was maintained at a higher value of between 66and 69C.
It was found that the higher temperature gave the same :-:
product but in the reduced processing time of 16 hours. .. . :
Non-continuous Mixing/heating of Reaction Mixture 18.75 Kg PVP (K-30) having a moisture content .
of 9.8~ by weight and 3.4 ~g elemental iodine were maintained in a rotating polyethylene container for six hours at a temperature between 63and 66C. Upon completing that first phase of the process, the product .
had a ratio of available iodine of 3 08 ...
iodide lon :.
In a second phase the product was transferred :
to immobile drying trays and maintained at a temperature of about 65C in a drying oven for a further 13 hours.
_ 5 _ :
. : , , t,, . ~ ,~ .. .
..
- , . .
~6661~4 The resulting product obtained in a yield of 22 kg, has the desired aVaildab~ce iOnine ratio of 2.18.
The performance of the novel process may be interrupted at will with no detrimental effect to the aesired product. This result is illustrated in the following example.
18.45 Kg of PVP (K-30) having a moisture content of 9.2% by weight and 3.28 kg of elemental iodine were heated in a rotating vessel at a temperature between 5~ and 63C for 4.75 hours. The reaction mixture -~
or partially formed product, at this stage in the process, available iodine had an iodide ion ratlo of 3.21.
e reaction mixture was then maintained at room temperature (about 22C) for twelve days without mixing. The converting process, once commenced, obviously continued even at this low temperature as indicated by the reduction over that period of the aVaiodbde iiOonine ratio to 2.56.
At the end of that period, the reaction mixture was returned to the rotating vessel and heated/mixed at a temperature between 63and 68C for a further six hours. This latter treatment was sufficient to convert the reaction mixture into the desired product having an availdibde iiOonine ratio of 2.18.
The present invention therefore provides a novel process for the production of the known PVPI germicidal and bactericidal agents, which process offers the significant advantages over prior art processes of less severe, i.e. more convenient and less expensive processing, conditions as well as a possible reduction in processing time and the use of less expensive equipment.
, .
Patent No. 2,900,305.
It is preferred that the polyvinylpyrrolidone polymer used in the production of the desired PVPI adduct i8 1-v~nyl-2-pyrrolidone.
The present invention will be further described with reference to, but not limited by, the following specific examples. Throughout these examples, the preferred PVP, l-vinyl-2-pyrrolidone polymer is used which had a ~K" value of 30. (By K value is meant the Fikentscher K value as defined by H. Fikentscher in Cellulosechemie 13, 58-64, 71-4 (1932), the general standard in this field. This value was evaluated using an aqueous solution of the polymer having a concentration of 1 g of anhydrous polymer per 100 ml solution in a Ubbelohde viscometer at a temperature of 25C.) .` ' ~06661g Continuous Mixing/heating of Reaction Mixture A. 18;85 Kg of powdered PVP (K-30), having a moisture content of 9.67% by weight, and 3.40 kg of elemental iodine was introduced into a rotating conically-shaped reactor provided with a heating ~acket. The reactor, known as the Pfaudler Conical Dryer-Blender (available from Pfaudler Company, 1000 West Avenue, ~ochester, New York, U.S.A., 14603) has no internal agitator or mixer devices and subjects the reactant to a gentle tumbling action or treatment.
The mixing was continued at a temperature between 64and 67C for twenty (20) hours, at the.end of which the desired product having an -avaiOdaibdee iOnine rat;io of 2.2 was obtained in a yield of 22.1 kg.
B. The process of Part A was repeated, the only di~:ference being that the processing temperature was maintained at a higher value of between 66and 69C.
It was found that the higher temperature gave the same :-:
product but in the reduced processing time of 16 hours. .. . :
Non-continuous Mixing/heating of Reaction Mixture 18.75 Kg PVP (K-30) having a moisture content .
of 9.8~ by weight and 3.4 ~g elemental iodine were maintained in a rotating polyethylene container for six hours at a temperature between 63and 66C. Upon completing that first phase of the process, the product .
had a ratio of available iodine of 3 08 ...
iodide lon :.
In a second phase the product was transferred :
to immobile drying trays and maintained at a temperature of about 65C in a drying oven for a further 13 hours.
_ 5 _ :
. : , , t,, . ~ ,~ .. .
..
- , . .
~6661~4 The resulting product obtained in a yield of 22 kg, has the desired aVaildab~ce iOnine ratio of 2.18.
The performance of the novel process may be interrupted at will with no detrimental effect to the aesired product. This result is illustrated in the following example.
18.45 Kg of PVP (K-30) having a moisture content of 9.2% by weight and 3.28 kg of elemental iodine were heated in a rotating vessel at a temperature between 5~ and 63C for 4.75 hours. The reaction mixture -~
or partially formed product, at this stage in the process, available iodine had an iodide ion ratlo of 3.21.
e reaction mixture was then maintained at room temperature (about 22C) for twelve days without mixing. The converting process, once commenced, obviously continued even at this low temperature as indicated by the reduction over that period of the aVaiodbde iiOonine ratio to 2.56.
At the end of that period, the reaction mixture was returned to the rotating vessel and heated/mixed at a temperature between 63and 68C for a further six hours. This latter treatment was sufficient to convert the reaction mixture into the desired product having an availdibde iiOonine ratio of 2.18.
The present invention therefore provides a novel process for the production of the known PVPI germicidal and bactericidal agents, which process offers the significant advantages over prior art processes of less severe, i.e. more convenient and less expensive processing, conditions as well as a possible reduction in processing time and the use of less expensive equipment.
, .
Claims (9)
1. A process for the preparation of a polyvinylpyrrolidone-iodine composition stable in aqueous media, which comprises admixing elemental iodine and powdered polyvinylpyrrolidone having a moisture content of from 5-15% by weight and heating the components, during or subsequent to admixing, to a temperature of from 30-70°C.
2. The process according to claim 1, wherein the powdered polyvinylpyrrolidone component has a moisture content of from 8-12% by weight.
3. The process according to claim 1, wherein the components are heated to a temperature of from 50-70°C.
4. The process according to claim 3, wherein the components are heated to a temperature of from 60-70°C.
5. The process according to claim 1, wherein the heating of the components is carried out subsequent to the admixing thereof.
6. The process according to claim 1, 2 or 3, wherein the components are admixed for a period of from 4-6 hours and the total reaction time is from 14-18 hours, whereby the-desired product has an available iodine/iodide ion ratio of from 1.9-2.5.
7. The process according to claim 4 or 5, wherein the components are admixed for a period of from 4-6 hours and the total reaction time is from 14-18 hours, whereby the desired product has an available iodine/iodide ion ratio of from 1.9-2.5.
8. The process according to claim 1, 2 or 3, wherein the polyvinylpyrrolidone component is 1-vinyl-2-pyrrolidone.
9. The process according to claim 4 or 5, wherein the polyvinylpyrrolidone component is 1-vinyl-2-pyrrolidone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5298275 | 1975-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066614A true CA1066614A (en) | 1979-11-20 |
Family
ID=10466144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA268,652A Expired CA1066614A (en) | 1975-12-29 | 1976-12-23 | Bactericides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1066614A (en) |
-
1976
- 1976-12-23 CA CA268,652A patent/CA1066614A/en not_active Expired
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