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CA1175861A - Process for liberating dialdehyde from an aqueous solution - Google Patents

Process for liberating dialdehyde from an aqueous solution

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Publication number
CA1175861A
CA1175861A CA000437505A CA437505A CA1175861A CA 1175861 A CA1175861 A CA 1175861A CA 000437505 A CA000437505 A CA 000437505A CA 437505 A CA437505 A CA 437505A CA 1175861 A CA1175861 A CA 1175861A
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CA
Canada
Prior art keywords
percent
dialdehyde
weight
aqueous solution
mixture
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
Application number
CA000437505A
Other languages
French (fr)
Inventor
Gerald J. Murphy
Robert G. Eagar, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
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
Priority claimed from CA000391189A external-priority patent/CA1173058A/en
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Priority to CA000437505A priority Critical patent/CA1175861A/en
Application granted granted Critical
Publication of CA1175861A publication Critical patent/CA1175861A/en
Expired legal-status Critical Current

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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.

Description

This invention is di~ected to a process for sapidly obtaining a stable ~reeze point depressed aqueous solution comp~ising a dialdehyde and an .. alip~atic alcoho} ~n~/or polyol by adding ~here~o a catalytic amount o~ a strong acid. Also, included herein is a method for liberating the d:ialdehyde ~n the aqueous solution by dilution with water and the addition o a catalytic a~unt of a strong acid.
Aqueous ~olution~ of ~lutaraldehyde ~re well kno~n commerei~lly ~v~lable materi81~ u~eful for k~ll$ng or lnhibiting lche gsowth ~f micrs:)org8.n~6ms.
~e8e aqueou~ ~olutions of glutaraldehyde have been u~ed to ~ontrol the grawth o: bacteri~ in ~ nun~er s:~f different env~ronment3d For ex~ , glu~ar~Lldehyde 801utions have been used to di~infeet ~edical and ~urgic~l s~pplies and househo~d ob,3eces. Fur~herg a~ de~cribed in U.S. Pate~ 2~801~16 ~lu~r~ldehyde ~vlut~ons have be~n u~ed to control bac~er~a in w~er .. flooding operations ~or ~he ~econdary recovery ~f oil and u~ed ~o prevent corrosion and plugg~ng of iron equipment due to ~he action of bacteri~ or~ge vessels and as~oclated plumbing and equ~pme~t~ Thu~, ~t can be seen that there a~e o~C~610~S ~hen glu~ar~l-dehyde ~o$utions ~re ~ored out of door~ a~d may ~e ~ub~ected to ~reezing condieio~. The freezi~g poi~t of ~ 25 percent aqueou~ ~olution of glut~raldehyte ~ ou~ 22~. ~herefore, lt ~ould be des~able ~nder these cond~tio~ to ~urthes d~pre3s ~he ~reezing pol~t o ~he aqueou~ ~olutisn of g~utassld~h~d~. ~owever9 ~y ~ddi~lve ~o ~he ~queous glutaraldehyt~ ~olu~o~
~ch c~uld depre~ ~he free~B po~e o~ ~h~ ~olu~a .

must not dec~ease t~e che~ical or biolog:lcal activity o~ ~e solution At time o~ use and n~tst be one which ~a~ntains the freezing polnt at the desired tempera-eure. ~ha~ is, the.addi~ive ~hould be one which i9 able to maintain the desired temperature over extendad periods of time. For example, bot~ alcohvls ~nd I

glycols, such as meth~nol and ethylenle glyco~ are known to react with glutaraldehyde so tha~ even though addition of methanol or e~ylene glycol to an aqueous solution of glutaraldehyde initially depr~sses the freezlng point, upon storage) ~he free~ing point ri.se~
as the alcohol and glycol react with ~he glutaraldehyde to fo~m a mixture containing acetal linkages. There-~ore, it i~ ~çsirablé to have a 3table ~ixed reezing point.
DESCRIPTION OF THE INVENTION
I~ has been found ~hat the addition of a cataly~ic amount of a strong acid ~o an aqueou~ æolu-tion compris~ng a dialdehyde and an aliphatic alcohol and/or polyol free~e point depre~sant rapidly catalyzes the formation of an equilibrium mix~ure of the dial-dehyde, acetal, and freeze point depress~n~, which equilibrium mixture has a stable and fixed freezing point.
I~ has also been found that in order to rapldly and efficien~ly llberate the dialdehyde for acti~e chemic~l or b~.o~ogical reactions, dilution o~ ~e equllibrium mixture with water and the ~urt~er ~dd~.t~on o~ a c~taly~ic ~mount o~ a strong acld i~
necessary, 5~6~

The aliphatic alcohols which may ~e used as ~ree~e point depressants herein contain from 1 to 4 ca~bon ato~s, such as methano~, ethémol and the llke, and ~ixtur~s there.of~ T~e pre~erred alcohol i~
methanol.
The aliphatic polyols which may be employed ~n this in~ention as ~reezing point depressants contain from 2 to 6 carbon atoms, and include ethylene glycol, propylene glycol, glycerol and the like, and mixtures thereof. The preferred polyol ls ethyl~ne glycol.
It is understood that one or more aliphatic alco~ols may be mixed wlth one or more aliphatic polyo~s.
The acids which are suitable for use in this invention are acids capable of achieving ~n aqueous pH below abou~ 3.0, preferably below about 2.0, and include pho~phorir acid, hydrochloric acid, sulfuric acid, trifluoromethylsulfonic acid,para- oluenesulfonic acid, ' as well as supported acid catalyst~, ~uch as ~mberlyst~
whlch ~s a supported arylsulfonic acid (sold by Ro~
& Haas Company~ and Nafion which ~s a supported fluoro-~ulfonic acid (sold by E. I. duPont de Nemours Co.),.
In order to achieve a ~table freeze point depressed produc~, ~he aqueous solution generally contaln~ from about 0.1 ~o about 50 percent by weight.
o~ the dialde~yde; from about 5 to about ~0 percent by weigh~ of the aleohol and~os glycol,with the ~emainder of ~he ~olutio~ belng water 3UC~ that the total ~olutioR i~ 100 percent by weighe. A preferred ~olution contain~ ~ percene by weight of dialdehyd~, R ~ R ~ ~ -7~

30 percent by weight o~ alcohol and/or glycol and 45 percent ~y weight o water.
In order to rapidly and efficiently liberate the dlaldehyde for ac~lve chem~cal or biolo~7ical reac-~tions, the aqueous ~olu~ion should contain from about O. 01 to about 10 percent o the d~aldehyde and a cataly-tic amount of an acid, and may contain up to about 40 percent by w ight o the alcohol and/or polyol, with the remainder of ~he solution being water such that the total 301u~ion i8 100 percent by welg,ht.
The solul:ions may contain o~her additi~Te~
8UC~ as coloran~s, sur~actants, chelating agents, p~ bu~er~,and the l~ke.
EXAMPLES
The ~ollowing exa~ples ~erve to give specific ~llustratlons of the practice of this invention but they are not intended în any way to limit the ~cope o~ this invention.
CONTROL A
The freezing point of a mixture of ~5 percent by weight of glutaraldehyde and 75 pe~cent by welght of water ls 22~F (as determined by the procedure as ~et forth in ASTM D-1177-65).
CONTR~L B
, The following ingredient w2re mixed:
25 percent by ~eight of glutaraldehyde, ~5 percent by weight of methanolJ a~d -50 percen~ by weight of water.
- - The ~eez~ng poi~t o~ the m~xture w~ -20.15~F
and ~he pH was ab9ut 4Ø A~ter ~torage for 55 da~y~

.. . . .. ..... . .. .. . .. . .. . ... . .... ... . .. ..

t~5~ L

at a~out ~5C, the ~reezing point of the mixture was measured and found to be -9.5F.
CO~lTROL G
The f~llowing lngredients were mixed: . . . .
25 percent by weight o glut~raldehyde, 25 percent by weight of ethylene glycol, and 50 percent by weight of water.
The freezing point o~ the mixture was -14.0F
and the pH was about 4Ø After storage or 55 days at about 25C, the freezing point of the mixture was measured ~nd ound to be -7. 5~F, EXA~LE 1 The following ingredients were mixed:
25 percent by welght of glutaraldehyde, 25 percent by weight of methanol, and 50 perrent by weight of water.
A one percent solution of phosphoric acid was added ~o the solutio~ un~il a pH of 1 to 2 was achie~ed.
The freezing point of the equilibrium mixture was -9.0~F.

_ _ The following ingredients were mLxed:
- 25 percent by weight of gl~taraldPhyde, ~5 percent by weight of eehylene glycol, and 50 percent by weight of water.
A one pe~een~ ~olution o~ phosphor~c acid was ~ddet to ehe ~olution until ~ p~ o~ 1 ~o ~ was a~hievQd.
~he ~reezing point o~ t~e mixture was 3~F.
The aqueous equilibrium m~xtures ~n Exampl2s 1 . . . . .. . .... . . .. .. . . . .

5~

and ~ were ~onmed ~n less than about 3 hours. These e~u~librium mixtures are able to mantain the stated ~reezing point over long per~ods of time, even after G months of storage.
~n contradistinct~on, the ~ree2ing points of the mixtures of Controls ~ and B varied~ significantly a~ter only 55 ~ays and up t~ three m~nths may be required for the solu~ion ~o achieve e~uil:Lbrium.
~x~n~ 6 3 10 7 In these examples, the follo~ing ingredients were mixed:
25 perce~t by weight of glutaraldehyde, 30 perc~nt by weight of methanol, ~nd 45 percent by weight of water.
Thi8 mixture was stored for about 6 months.
The ~inal equilibrium of the mix~ure had been reached ~t this point in time. Thls mlxture was diluted to 0.1% of theoretical glutaraldehyde. T~ ~Farate por-tion~ of the mixture was added a one p~rcent ~olution o~ phosphoric acid until the desired pH was achieved.
The percent of glu~araldehyde recovered from the mixlture at various times and pH values is shown in Table I.
The glutaralde~yde le~els were determinet by gas ehromatography.
~ TABLE I

Time P~ -~x~ple ~ ) : 2 3 4 5 I~
3 l,0 ~0% 77% 5~%
4 3.0 ~3Z 7~
i.0 g37O 81% ~%
24~ ~7~ 93% ~9% 37% 44Z
7 48.0 9~ ~3% 73Z 37% 44%

,P~`~

In these Examples, the followlng ingredients were mixed:
~5 percent by weight of glutaraldehyd~J
. 30 percent by weight of ethylene glycol, and 45 percent by weight o~ water.
This mixture was stored for 6 months. The ~inal equilibrium of ~he mixture had been reached.
This mixture was diluted to 0.1% of theoretical glu-taraldehyde. To separate portions of the mixture was added a one percent 801ution o phosphoric acid until the desired pH was achieved. The percent of glutar-~ldehyde recovered from the mixture a~ var~us times and pH values is shown in Table X~. The glutaraldehyde levels were determ med ~y gas chromatography.
TABLE II
T~me H
Example ~ ) Z 3 ~~
8 1.0 - - 50% -
2~ 9 1.67 77% 54% - - -1~ 2.17 81% 66% - ~ ~
11 3.0 - _ _ 59% ~7%
12 24.0 99% 76% 54% - ~
13 72.0 ~ 1% 5270 ~.

Claims (4)

WHAT IS CLAIMED:
1. A process for liberating a dialdehyde from an aqueous equilibrium mixture comprising a dialdehyde, acetal, and an aliphatic alcohol and/or polyol by first diluting the mixture with water and then adding 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.
CA000437505A 1981-11-30 1983-09-23 Process for liberating dialdehyde from an aqueous solution Expired CA1175861A (en)

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
CA000391189A CA1173058A (en) 1980-12-30 1981-11-30 Process for obtaining a stable depressed freeze point aqueous solutions of dialdehydes
CA000437505A CA1175861A (en) 1981-11-30 1983-09-23 Process for liberating dialdehyde from an aqueous solution

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA000391189A Division CA1173058A (en) 1980-12-30 1981-11-30 Process for obtaining a stable depressed freeze point aqueous solutions of dialdehydes

Publications (1)

Publication Number Publication Date
CA1175861A true CA1175861A (en) 1984-10-09

Family

ID=25669496

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000437505A Expired CA1175861A (en) 1981-11-30 1983-09-23 Process for liberating dialdehyde from an aqueous solution

Country Status (1)

Country Link
CA (1) CA1175861A (en)

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