CA1173058A - Process for obtaining a stable depressed freeze point aqueous solutions of dialdehydes - Google Patents
Process for obtaining a stable depressed freeze point aqueous solutions of dialdehydesInfo
- Publication number
- CA1173058A CA1173058A CA000391189A CA391189A CA1173058A CA 1173058 A CA1173058 A CA 1173058A CA 000391189 A CA000391189 A CA 000391189A CA 391189 A CA391189 A CA 391189A CA 1173058 A CA1173058 A CA 1173058A
- Authority
- CA
- Canada
- Prior art keywords
- percent
- weight
- glutaraldehyde
- mixture
- dialdehyde
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Described herein is a process for rapidly obtaining a stable freeze point depressed aqueous solution comprising a dialdehyde and an aliphatic alcohol and/or polyol by adding thereto a catalytic amount of a strong acid. Also included herein is a method for liberating the dialdehyde in the aqueous solution by dilution with water and the addition of a catalytic amount of a strong acid.
Described herein is a process for rapidly obtaining a stable freeze point depressed aqueous solution comprising a dialdehyde and an aliphatic alcohol and/or polyol by adding thereto a catalytic amount of a strong acid. Also included herein is a method for liberating the dialdehyde in the aqueous solution by dilution with water and the addition of a catalytic amount of a strong acid.
Description
1~730~ 13,069 This invention is directed to a process for ~apidly obtaining a stable freeze polnt depressed aqueous solution comprising a dialdehyde and an aliphatic alcohol and~or polyol by adding thereto a catalytic amount of a strong acid. Also, included herein is a method for liberating the dialdehyde in the aqueous solution by dilution with water and the addition of a catalytic amou~t of a strong acid.
Aqueou~ ~olutions of glutaraldehyde are well known commercially available materi~ls uEeful for killing or inhibiting the growth of microorgan~sms.
These squeous solutions of glutaraldehyde have been used to control the growth of bacteria in a number of different environment~. For example, glutaraldehyde ~olutions have been used to disinfect medical and surgical supplies and household ob~ects. Further, a~ described in U.S. Patent 2,801,216 glutaraldehyde 601utions have been u6ed to control bacteria in water flooding operations for the 6econdary recovery of oil and used to prevent corrosion and plugging of iron equipment due to the action of bacterin in ~torage vessel6 and as60c~ated plumbing and equipment. Thus, it can be ~een that there are occa610ns when glutaral-dehyde ~olutions are ~tored out of door~ and may be sub~ected to freezing condition6. ~he freezing point of a 25 percent aqueou6 solution of glutsraldehyde i~ ~bout 22Y~ Therefore, ~t would ~e desirsble under these conditiong to further depre~s the freezing point of the aqueou~ solution of glutaraldehyde. H~wever, ~ny additive to the ~queous glutaraldehyde ~olut~on wh~ch coula depre6~ the freeælng point of the solution
Aqueou~ ~olutions of glutaraldehyde are well known commercially available materi~ls uEeful for killing or inhibiting the growth of microorgan~sms.
These squeous solutions of glutaraldehyde have been used to control the growth of bacteria in a number of different environment~. For example, glutaraldehyde ~olutions have been used to disinfect medical and surgical supplies and household ob~ects. Further, a~ described in U.S. Patent 2,801,216 glutaraldehyde 601utions have been u6ed to control bacteria in water flooding operations for the 6econdary recovery of oil and used to prevent corrosion and plugging of iron equipment due to the action of bacterin in ~torage vessel6 and as60c~ated plumbing and equipment. Thus, it can be ~een that there are occa610ns when glutaral-dehyde ~olutions are ~tored out of door~ and may be sub~ected to freezing condition6. ~he freezing point of a 25 percent aqueou6 solution of glutsraldehyde i~ ~bout 22Y~ Therefore, ~t would ~e desirsble under these conditiong to further depre~s the freezing point of the aqueou~ solution of glutaraldehyde. H~wever, ~ny additive to the ~queous glutaraldehyde ~olut~on wh~ch coula depre6~ the freeælng point of the solution
2.
7 3~ 5 8 13,069 ~ust not decrease ~he chemlcal or biological activity of the solution at time o~ use and must be one which ~aintains the freezing point at the desired tempera-ture, That is, the additive should be one which is able to main~ain the desired temperature o~er extended periods of time. For example, both alcohols and glycols, such as methanol and ethylene glyco~ are known to react with glutaraldehyde so that even though addition of methanol or ethylene glycol to an aqueous solution of glutaraldehyde initially depresses the freezing point, upon storage, the freezing point rises as ~he alcohol and glycol react with the glutaraldehyde to form a mixture containing acetal linkages. There-fore, it is dçsirable to have a stable ~ixed freezing point.
DESCRIPTION OF THE INVENTION
It has been found that the addition of a catalytic amount of a strong acid to an aqueous solu-tion comprising a dialdehyde and an aliphatic alcohol and/or polyol freeze point depressant rapidly catalyzes the formation of an equilibrium mixture of the dial-dehyde, acetal, and freeze point depressant, which equilibrium mi~ture has a stable and fixed freezing point.
It has also been found that in order to rapidly and efficiently liberate the dialdehyde for active chemical or biologi~al reactions, dilution of the equilibrium mixture with water and the further addition of a catalytic amount ~f a strong acid is necessary.
13,069 ~1~73(~51~
The allphatic alcohol~ which may be used as ~reeze point depressants herein contain from 1 to 4 carbon ato~s, such as methanol, ethanol and the like, and mixtures there~f.;~The preferred alcohol iB
methanol.
The aliphatic polyols which may be employed in this invention as freezing point depressants contain from 2 to 6 carbon atoms, and include ethylene glycol, propylene glycol, glycerol ant the like, and mixtures thereof. The preferred polyol is ethylene glycol.
It is understood that one or more aliphatic alcohols may be mixed with one sr more aliphatic polyols.
The acids which are ~uitable for use in this invention are acids capable of achieving an aqueous pH below abou~ 3.0, preferably below about 2.0, and include phosphoric acid, hydrochloric acid, sulfuric acid, trifluoromethylsulfonic acid,para-toluenesulfonic acid, as well as ~upported acid catalysts, such as Amberlyst~
which i8 a supported arylsulfonic acid (sold by Rohm & Haas Company) and Nafio~ which is a supported fluoro-sulfonic acid (sold by E. I. duPont de Nemours Co.).
In order to achieve 8 stable freeze point depresset product, the aqueous solution generally contains from about 0.1 to about 50 percent by welght o~ the di~ldehyde; from about 5 to about ~0 percent by weight of the alcohol andtor glycol.with the remainder of ehe 801ution being water such that the total solution is 100 percent by weight. A preferred ~olution contains 25 percene by weight o~ dialdehyde, _ . _ _ " .. _ . .. __ _ , ._ _ _ . , .. _ . . .. ..
1~73~5~ 13,069 30 percent by weight o~ alcohol and/or glycol and 45 percent by weight of water.
In order to rapid~y and efficiently liberate the dialdehyde for active chemical or biological reac-tions, the aqueous solution should contain from about 0.01 to about 10 percent of the dialdehyde and a cataly-tic amount of an acid, and may conta~n up to about 40 percent by weight of the alcohol and/or polyol, with the remainder of the solution being water such that the total solution is 100 percent by weight.
The solutions may contain other additives such as colorants, surfactants, chelating agents, pH buffers,and the li~e.
EXAMPLE_ The following examples serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit the scope of this invention.
CONTROL A
The freezing point of a mixture of 25 percent by weight of glutaraldehyde and 75 percent by weight of water is 22~F (as determined by the procedure as , set forth in ASTM D-1177-65).
CONTR~L B
;
The following lngredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of methanol, and 50 percent by weight of water.
- The freezing point OI the mixture was -20.5~ -and the pH was about 4Ø After storage for 55 days ., 5.
., ~173~5~ 13,069 at a~out 25C, the f~eezing point of the mixture was measured and found to be -9.5F.
`CONTROL C
. The following ingredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of ethylene glycol, and 50 percent by weight of water.
The freezing point of the mixture was -14.0F
and the pH was about 4Ø After storage for 55 days at about 25C, the freezing point of the mixture was measured and found to be -7.5F.
The following ingredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of methanol, and 50 percent by weight of water.
A one percent solution of phosphoric acid ' was added to the solution until a pH of 1 to 2 was , achieved.
The freezing point of the equilibrium mixture was -9.0F.
The following ingredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of ethylene glycol, and 50 percent by weight of water.
A one pe~cent solution of phosphoric acid was added to the solution until a pH o~ 1 to 2 was achieved.
The ~reezing point of the mixture was 3F.
The aqueous equilibri~m mixtures in Examples 1 6.
~ ;30SI~
and 2 were formed in less than about 3 hours. These equilibrium mixtures are a~le to maintain the stated ~reezing point over long periods of time, even after 6 months of storage.
In contradistinction, the freezing points of the mixtures of Controls A and B varied significantly , after only 55 days and up to three months may be required for the solution to achieve equilibrium.
In these examples, the following ingredients were mlxed:
25 percent by weight of glutaraldehyde, 30 percent by weight of methanol, and 45 percent by we'ight of water.
This mixture was stored for about 6 months.
The final equilibrium of the mixture had been reached at this point in time. This mixture was diluted to 0.1% of theoretical glutaraldehyde. To separate por-tions of the mixture was added a one percent solution of phosphoric acid until the desired pH was achieved.
The percent of glutaraldehyde recovered from the mixture at various times and pH values is shown in Table I.
The glutaraldehyde levels were determined by gas chromatography.
TABLE I
Time H
'Examp'le' th'rs~ 2 3 4 5 -
7 3~ 5 8 13,069 ~ust not decrease ~he chemlcal or biological activity of the solution at time o~ use and must be one which ~aintains the freezing point at the desired tempera-ture, That is, the additive should be one which is able to main~ain the desired temperature o~er extended periods of time. For example, both alcohols and glycols, such as methanol and ethylene glyco~ are known to react with glutaraldehyde so that even though addition of methanol or ethylene glycol to an aqueous solution of glutaraldehyde initially depresses the freezing point, upon storage, the freezing point rises as ~he alcohol and glycol react with the glutaraldehyde to form a mixture containing acetal linkages. There-fore, it is dçsirable to have a stable ~ixed freezing point.
DESCRIPTION OF THE INVENTION
It has been found that the addition of a catalytic amount of a strong acid to an aqueous solu-tion comprising a dialdehyde and an aliphatic alcohol and/or polyol freeze point depressant rapidly catalyzes the formation of an equilibrium mixture of the dial-dehyde, acetal, and freeze point depressant, which equilibrium mi~ture has a stable and fixed freezing point.
It has also been found that in order to rapidly and efficiently liberate the dialdehyde for active chemical or biologi~al reactions, dilution of the equilibrium mixture with water and the further addition of a catalytic amount ~f a strong acid is necessary.
13,069 ~1~73(~51~
The allphatic alcohol~ which may be used as ~reeze point depressants herein contain from 1 to 4 carbon ato~s, such as methanol, ethanol and the like, and mixtures there~f.;~The preferred alcohol iB
methanol.
The aliphatic polyols which may be employed in this invention as freezing point depressants contain from 2 to 6 carbon atoms, and include ethylene glycol, propylene glycol, glycerol ant the like, and mixtures thereof. The preferred polyol is ethylene glycol.
It is understood that one or more aliphatic alcohols may be mixed with one sr more aliphatic polyols.
The acids which are ~uitable for use in this invention are acids capable of achieving an aqueous pH below abou~ 3.0, preferably below about 2.0, and include phosphoric acid, hydrochloric acid, sulfuric acid, trifluoromethylsulfonic acid,para-toluenesulfonic acid, as well as ~upported acid catalysts, such as Amberlyst~
which i8 a supported arylsulfonic acid (sold by Rohm & Haas Company) and Nafio~ which is a supported fluoro-sulfonic acid (sold by E. I. duPont de Nemours Co.).
In order to achieve 8 stable freeze point depresset product, the aqueous solution generally contains from about 0.1 to about 50 percent by welght o~ the di~ldehyde; from about 5 to about ~0 percent by weight of the alcohol andtor glycol.with the remainder of ehe 801ution being water such that the total solution is 100 percent by weight. A preferred ~olution contains 25 percene by weight o~ dialdehyde, _ . _ _ " .. _ . .. __ _ , ._ _ _ . , .. _ . . .. ..
1~73~5~ 13,069 30 percent by weight o~ alcohol and/or glycol and 45 percent by weight of water.
In order to rapid~y and efficiently liberate the dialdehyde for active chemical or biological reac-tions, the aqueous solution should contain from about 0.01 to about 10 percent of the dialdehyde and a cataly-tic amount of an acid, and may conta~n up to about 40 percent by weight of the alcohol and/or polyol, with the remainder of the solution being water such that the total solution is 100 percent by weight.
The solutions may contain other additives such as colorants, surfactants, chelating agents, pH buffers,and the li~e.
EXAMPLE_ The following examples serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit the scope of this invention.
CONTROL A
The freezing point of a mixture of 25 percent by weight of glutaraldehyde and 75 percent by weight of water is 22~F (as determined by the procedure as , set forth in ASTM D-1177-65).
CONTR~L B
;
The following lngredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of methanol, and 50 percent by weight of water.
- The freezing point OI the mixture was -20.5~ -and the pH was about 4Ø After storage for 55 days ., 5.
., ~173~5~ 13,069 at a~out 25C, the f~eezing point of the mixture was measured and found to be -9.5F.
`CONTROL C
. The following ingredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of ethylene glycol, and 50 percent by weight of water.
The freezing point of the mixture was -14.0F
and the pH was about 4Ø After storage for 55 days at about 25C, the freezing point of the mixture was measured and found to be -7.5F.
The following ingredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of methanol, and 50 percent by weight of water.
A one percent solution of phosphoric acid ' was added to the solution until a pH of 1 to 2 was , achieved.
The freezing point of the equilibrium mixture was -9.0F.
The following ingredients were mixed:
25 percent by weight of glutaraldehyde, 25 percent by weight of ethylene glycol, and 50 percent by weight of water.
A one pe~cent solution of phosphoric acid was added to the solution until a pH o~ 1 to 2 was achieved.
The ~reezing point of the mixture was 3F.
The aqueous equilibri~m mixtures in Examples 1 6.
~ ;30SI~
and 2 were formed in less than about 3 hours. These equilibrium mixtures are a~le to maintain the stated ~reezing point over long periods of time, even after 6 months of storage.
In contradistinction, the freezing points of the mixtures of Controls A and B varied significantly , after only 55 days and up to three months may be required for the solution to achieve equilibrium.
In these examples, the following ingredients were mlxed:
25 percent by weight of glutaraldehyde, 30 percent by weight of methanol, and 45 percent by we'ight of water.
This mixture was stored for about 6 months.
The final equilibrium of the mixture had been reached at this point in time. This mixture was diluted to 0.1% of theoretical glutaraldehyde. To separate por-tions of the mixture was added a one percent solution of phosphoric acid until the desired pH was achieved.
The percent of glutaraldehyde recovered from the mixture at various times and pH values is shown in Table I.
The glutaraldehyde levels were determined by gas chromatography.
TABLE I
Time H
'Examp'le' th'rs~ 2 3 4 5 -
3 1.0 90% 77Z 58% - -
4 3.0 93~/O 78lo
5.0 93% 81~/~ 58% - -
6 24.0 97V/o 93% 69% 37% 44%
7 48.0 94% 93% 73% 37% 44%
~73058 13,069 . .
In these Examples, the following ingredients were mixed:
25 percent by weight of glutaraldehyde, 30 percent by weight of ethylene glycol, and 45 percent by weight of water.
This mixture was stored for 6 months. The final equilibrium of the mixture had been reached.
This mixture was diluted to 0.1% of theoretical glu-taraldehyde. To separate portions of the mixtùre was added a one percent solution of phosphoric acid until the desired pH was achieved. The percent of glutar-aldehyde recovered from the mixture at variQus times and pH values is shown in Table II. The glutaraldehyde levels were determined by gas chromatography.
TABLE II
Time pH
Exam~
~73058 13,069 . .
In these Examples, the following ingredients were mixed:
25 percent by weight of glutaraldehyde, 30 percent by weight of ethylene glycol, and 45 percent by weight of water.
This mixture was stored for 6 months. The final equilibrium of the mixture had been reached.
This mixture was diluted to 0.1% of theoretical glu-taraldehyde. To separate portions of the mixtùre was added a one percent solution of phosphoric acid until the desired pH was achieved. The percent of glutar-aldehyde recovered from the mixture at variQus times and pH values is shown in Table II. The glutaraldehyde levels were determined by gas chromatography.
TABLE II
Time pH
Exam~
8 1~0 - - 50%
9 1.67 77% 54%
2.17 81% 66% - - -11 3.0 - - - 59% 57%
12 24.0 99% 76% 54%
13 72.0 - - - 61% 52%
2.17 81% 66% - - -11 3.0 - - - 59% 57%
12 24.0 99% 76% 54%
13 72.0 - - - 61% 52%
Claims (4)
1. A process for rapidly obtaining a stable freeze point depressed aqueous solution comprising a dialdehyde and an aliphatic alcohol and/or polyol by adding thereto a catalytic amount of a strong acid.
2. A process as defined in claim 1 wherein the dialdehyde is glutaraldehyde.
3. A process as defined in claim 1 wherein the aliphatic alcohol is methanol.
4. A process as defined in claim 1 wherein the aliphatic polyol is ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000437505A CA1175861A (en) | 1981-11-30 | 1983-09-23 | Process for liberating dialdehyde from an aqueous solution |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22150680A | 1980-12-30 | 1980-12-30 | |
| US221,506 | 1980-12-30 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000437505A Division CA1175861A (en) | 1981-11-30 | 1983-09-23 | Process for liberating dialdehyde from an aqueous solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1173058A true CA1173058A (en) | 1984-08-21 |
Family
ID=22828108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000391189A Expired CA1173058A (en) | 1980-12-30 | 1981-11-30 | Process for obtaining a stable depressed freeze point aqueous solutions of dialdehydes |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1173058A (en) |
| DE (1) | DE3151694C2 (en) |
| GB (1) | GB2090140B (en) |
| NO (1) | NO156784C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60500014A (en) * | 1982-11-12 | 1985-01-10 | バツクスター トラベノル ラボラトリーズ インコーポレーテツド | Chemical sterilization of biological tissue ready for transplantation |
| GB2171307A (en) * | 1985-02-27 | 1986-08-28 | White S S Ltd | Sterilising composition containing a dialdehyde |
| BR8907663A (en) * | 1988-09-19 | 1991-07-30 | Henkel Kgaa | PROCESS FOR THE DISINFECTION OF MEDICAL MOLDING MASSES |
| BR112019021913A2 (en) * | 2017-04-27 | 2020-05-26 | Dow Global Technologies Llc | STABLE BIOCIDAL COMPOSITION AND METHOD FOR USING A STABLE BIOCIDAL COMPOSITION |
-
1981
- 1981-11-30 CA CA000391189A patent/CA1173058A/en not_active Expired
- 1981-12-22 NO NO814404A patent/NO156784C/en unknown
- 1981-12-24 GB GB8138888A patent/GB2090140B/en not_active Expired
- 1981-12-29 DE DE3151694A patent/DE3151694C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO814404L (en) | 1982-07-01 |
| DE3151694C2 (en) | 1983-12-08 |
| NO156784B (en) | 1987-08-17 |
| GB2090140B (en) | 1984-04-11 |
| GB2090140A (en) | 1982-07-07 |
| NO156784C (en) | 1987-11-25 |
| DE3151694A1 (en) | 1982-07-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |