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WO1992011074A1 - Agent antimoussant a base de derives d'acide carboxylique - Google Patents

Agent antimoussant a base de derives d'acide carboxylique Download PDF

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Publication number
WO1992011074A1
WO1992011074A1 PCT/EP1991/002360 EP9102360W WO9211074A1 WO 1992011074 A1 WO1992011074 A1 WO 1992011074A1 EP 9102360 W EP9102360 W EP 9102360W WO 9211074 A1 WO9211074 A1 WO 9211074A1
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WO
WIPO (PCT)
Prior art keywords
acid
citric acid
defoamers
alcohols
defoamer
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.)
Ceased
Application number
PCT/EP1991/002360
Other languages
German (de)
English (en)
Inventor
Brigitte Wegner
Knut Oppenlaender
Rudolf Schuhmacher
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO1992011074A1 publication Critical patent/WO1992011074A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance

Definitions

  • the invention relates to the use of at least partially esterified or at least partially amidated citric acid, tartaric acid, succinic acid, maleic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as defoamers and defoamer mixtures which contain these derivatives and an emulsifier.
  • the known defoamers for paper production are water-free or aqueous formulations.
  • the water-free formulations mostly consist of low-viscosity oils, so-called oil defoamers, which are often used in a mixture with suitable emulsifiers or around self-emulsifying fatty acid or fatty alcohol polyethers.
  • This Products have only a limited defoaming, foam-preventing and deaerating effect compared to the aqueous formulations, the so-called emulsion defoamers, which usually have a water content of over 50%.
  • DE-PS 25 32 888 describes the use of oxyalkylated, straight-chain, saturated fatty alcohols having 12 to 30 carbon atoms, which are reacted by reacting 1 mol of the alcohol with
  • the invention is based on the object of developing an oil defoamer which is still highly effective even at an elevated temperature of the circulation water of the paper machine.
  • the defoamers should form emulsions when diluted with water, which are stable for a long time and do not cream.
  • the object is achieved according to the invention by using at least partially esterified with C 12 -C 22 -alcohols or at least partially amidated with C 1 -C 6 -C 6 -alkylamines carboxylic acids from the group citric acid, tartaric acid, succinic acid, maleic acid, nitrilotriacetic acid and Ethylenediaminetetraacetic acid as a defoamer. At least 1/3 of the carboxyl groups of the carboxylic acids mentioned are preferably esterified or amidated.
  • esters and amides of citric acid, tartaric acid, succinic acid, maleic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid to be used according to the invention are prepared by known processes. Products effective as defoamers are obtained as soon as one third of the carboxyl groups of the carboxylic acids mentioned are esterified or amidated. C ⁇ ⁇ are suitable for the production of esters from the carboxylic acids mentioned
  • C 22 fatty alcohols for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol, cyclohexanol, 2-ethylcyclohexanol, n-octanol, isooctanol, nonanol, isononanol, decanol, lauryl alcohol, pal ityl alcohol, stearyl alcohol, cetyl alcohol, isotridecanol and mixtures of alcohols in any ratio.
  • alcohols which can be obtained by the oxo process by adding carbon monoxide and hydrogen to olefins in the presence of catalysts or by the Ziegler process by oxidation of aluminum alkyls and subsequent saponification.
  • These technically easily accessible alcohols are mainly alcohol mixtures from alcohols with 9 to
  • the alcohols are esterified either alone or as a mixture with one another with the abovementioned carboxylic acids in the presence of esterification catalysts.
  • carboxylic acids instead of the carboxylic acids, it is of course also possible to use carboxylic acid derivatives such as anhydrides and acid chlorides, if they can be prepared, to prepare the esters.
  • the esterification catalysts used are preferably p-toluenesulfonic acid, benzenesulfonic acid, hypophosphorous acid, potassium hydrogen sulfate or sulfuric acid.
  • the esterification reaction is generally carried out at temperatures in the range from 100 to 200 ° C. under an inert gas atmosphere in the absence of solvents. The water of reaction formed is distilled off during the esterification.
  • the esterification can be carried out under elevated pressure or under reduced pressure, for example at 100 to 800 mbar.
  • the carboxyl groups of the abovementioned carboxylic acids are esterified or amidated to at least 1/3 or completely, preferably 1/3 to 2/3.
  • Citric acid is particularly preferably subjected to the esterification of the above-mentioned carboxylic acids. 1 to 3, preferably 1 to 2, mol of an alcohol or alcohol mixture are used per 1 mol of citric acid.
  • the esterification of the citric acid is preferably carried out with 1 to 2 mol of a C ⁇ to Cig alcohol or mixtures of alcohols which can be prepared by the oxo process. Defoamers with a particularly advantageous effect are obtained by esterifying citric acid with 1 to 2 mol of saturated C ⁇ * to C 22 fatty alcohols.
  • Suitable defoamers are also amides which result from at least partial amidation of citric acid, tartaric acid, succinic acid, maleic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid with saturated C 1 -C 6 -alkylamines. At least 1/3 of the carboxyl groups of the above carbon acids is amidated.
  • the fully amidated carboxylic acids mentioned above are also defoamers. Preferably 1/3 to 2/3 of the carboxyl groups of the above carboxylic acids are amidated.
  • Products which act particularly as defoamers are obtained by amidating 1 mol of citric acid with 1 to 2 mol of a primary or secondary saturated C 1 -C 6 -alkylamine or a mixture of such amines.
  • C ⁇ * to C 6 ⁇ alkylamines are preferably used for the amidation of citric acid.
  • Suitable amines are, for example, methylamine, dimethylamine, ethylamine, n-propylamine, isopropylamine, hexylamine, octyla in, decylamine, dodecylamine, tridecyla in, diisotridecylamine and coconut fatty amine.
  • the at least partially esterified or at least partially amidated carboxylic acids to be used according to the invention as defoamers are substances which are liquid at a temperature of 20 ° C. and above. When these defoamers are added to foam-forming aqueous systems, there is a strong reduction in foam formation even in the presence of very small amounts of defoamers.
  • the products to be used as defoamers according to the invention are used in such an amount that there are 0.02 to 0.5, preferably 0.05 to 0.3 part by weight of the defoamer per 100 parts by weight of a foam-forming medium.
  • the pulps that are dewatered in the manufacture of paper are regarded as the foam-forming medium.
  • Foam control in sewage treatment plants the above-described at least partially esterified or amidated esters of citric acid, tartaric acid, succinic acid, maleic acid, nitrilotetriacetic acid and ethylenediaminetetraacetic acid can be used as defoamers.
  • the defoamers are added directly to the medium to be defoamed or the products mentioned are emulsified in water and the defoamers are used in the form of an oil-in-water emulsion.
  • the average particle size of the particles emulsified in water depends on the shear forces present at the metering point, the defoamer component and the type and amount from emulsifiers, which are optionally used together with the products to be used according to the invention as defoamers.
  • the more intensive the distribution of the defoamers in an aqueous medium the better the defoaming and deaerating effect in the water cycle of the paper machine.
  • a better effect of the defoamers due to a finer distribution can be seen from the fact that the amount used for defoaming can be reduced.
  • the defoamer formulation can be used in addition to those of the invention
  • Emulsifiers with an HLB value of at least 8 are particularly suitable.
  • the mixing of the defoamers to be used according to the invention leads to an increase in activity.
  • carboxylic acids from the group citric acid, tartaric acid, succinic acid, maleic acid, nitrilotriacetic acid and ethylenediamine tetraacetic acid and at least partially esterified with C 1 -C 22 -alcohols or at least partially amidated with primary or secondary saturated C 1 -C 6 -alkylamines
  • the HLB value is understood to mean the hydrophilic-lipophilic balance of an emulsifier, cf. WC Giffin, 3rd Soc. Cosmet. Chem., 1, 311 (1950).
  • Suitable emulsifiers of this type are, for example, hydrophilic water-soluble products which can be obtained by ethoxylation of alkylphenols, fatty alcohols, fatty acids and fatty amines, and PO-EO block polymers with an ethylene oxide content of 10 to 80%.
  • the addition products of ethylene oxide or propylene oxide to fatty alcohols having 8 to 18 carbon atoms are used as emulsifiers, or ethylene oxide and then propylene oxide and, if appropriate, ethylene oxide are added to the fatty alcohols, so that block copolymers are formed.
  • the alkoxylation products can also add small amounts of butylene oxide contain.
  • the alkoxylation of the fatty alcohols can of course also be carried out using mixtures of the alkylene oxides.
  • CQ to Ci ⁇ *, in particular Cio * to Ci ß alcohols are preferably subjected to the alkoxylation, 3 to 80, preferably 10 to 30, mol of alkylene oxide being reacted per mol of alcohol.
  • alkylene oxides ethylene oxide is preferred.
  • the products are essentially characterized in that they have an HLB value of at least 8 and are water-soluble.
  • citric acid esters obtained from 1 mol of citric acid with 1 to 2 mol of a saturated C 6 -C 22 alcohol or from mixtures of such alcohols and emulsifiers based on C 6 -C 6 alcohols, preferably obtainable by the oxo process Alcohols with an ethylene oxide content of 3 to 12.
  • Products of this type can be used universally as defoamers. They act as foam dampers, foam preventers and fabric deaerators, in particular in the manufacture of paper and in paper coating colors.
  • Grid on the wall of the channel measured in units of area (cm2) and given as a so-called foam value to assess the effectiveness of a defoamer.
  • the foam value after 5 minutes is 1200 cm 2.
  • an effective defoamer a total of 10 mg solid
  • the temperature of the pulp suspension is kept constant by means of a immersion heater connected to a controller and, depending on the test, is 30, 50 or 60 ° C.
  • The% residual foam (R) is calculated as S e • 100
  • R where S e is the foam value which is after adding the defoamer and S 0 is the foam zero value, ie the value which is measured in the absence of a defoamer. In this terminology the defoamer is better the smaller R is.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)

Abstract

On utilise comme agents antimoussants des esters et des amides d'acide citrique, d'acide tartrique, d'acide succinique, d'acide maléique, d'acide nitrilotriacétique et d'acide diamintétraacétique d'éthylène. L'invention concerne également des mélanges antimoussants qui contiennent en outre jusqu'à 40 % en poids d'un émulsifiant ayant une valeur HLB d'au moins 8.
PCT/EP1991/002360 1990-12-21 1991-12-10 Agent antimoussant a base de derives d'acide carboxylique Ceased WO1992011074A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904041184 DE4041184A1 (de) 1990-12-21 1990-12-21 Entschaeumer auf basis von carbonssaeurederivaten
DEP4041184.2 1990-12-21

Publications (1)

Publication Number Publication Date
WO1992011074A1 true WO1992011074A1 (fr) 1992-07-09

Family

ID=6421034

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/002360 Ceased WO1992011074A1 (fr) 1990-12-21 1991-12-10 Agent antimoussant a base de derives d'acide carboxylique

Country Status (3)

Country Link
EP (1) EP0563090A1 (fr)
DE (1) DE4041184A1 (fr)
WO (1) WO1992011074A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5725815A (en) * 1993-03-15 1998-03-10 Henkel Kommanditgesellschaft Auf Aktien Foam control agents for the food, paint and paper industries

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6423376B1 (en) 2000-04-06 2002-07-23 Air Products And Chemicals, Inc. Tartaric acid diesters as biodegradable surfactants
US6306463B1 (en) * 2000-07-20 2001-10-23 Air Products And Chemicals, Inc. Citric acid tri-alkylamide surfactants
US6399543B1 (en) 2001-03-29 2002-06-04 Air Products And Chemicals, Inc. Low foam N,N′-dialkyltartaramide wetting agents
DE10122145A1 (de) * 2001-05-08 2002-11-28 Celanese Chem Europe Gmbh Zitronensäureester und ein Verfahren zu ihrer Herstellung
JP4725742B2 (ja) 2007-02-19 2011-07-13 信越化学工業株式会社 水硬性組成物
WO2023052542A1 (fr) 2021-10-01 2023-04-06 Clariant International Ltd Agents tensioactifs biologiques faiblement moussants, bloqués par des groupes terminaux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035702A2 (fr) * 1980-03-08 1981-09-16 Bayer Ag Produit antimousse, sa fabrication et son utilisation dans des systèmes aqueux
EP0335173A2 (fr) * 1988-03-26 1989-10-04 Bayer Ag Additif antimousse
EP0378049A2 (fr) * 1989-01-09 1990-07-18 Ciba-Geigy Ag Produit antimousse exempt d'huile silicone et résistant aux alcalis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035702A2 (fr) * 1980-03-08 1981-09-16 Bayer Ag Produit antimousse, sa fabrication et son utilisation dans des systèmes aqueux
EP0335173A2 (fr) * 1988-03-26 1989-10-04 Bayer Ag Additif antimousse
EP0378049A2 (fr) * 1989-01-09 1990-07-18 Ciba-Geigy Ag Produit antimousse exempt d'huile silicone et résistant aux alcalis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5725815A (en) * 1993-03-15 1998-03-10 Henkel Kommanditgesellschaft Auf Aktien Foam control agents for the food, paint and paper industries

Also Published As

Publication number Publication date
DE4041184A1 (de) 1992-06-25
EP0563090A1 (fr) 1993-10-06

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