WO1995034718A1 - Anti-foaming agent for use in the paper industry - Google Patents

Anti-foaming agent for use in the paper industry Download PDF

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Publication number
WO1995034718A1
WO1995034718A1 PCT/EP1995/002026 EP9502026W WO9534718A1 WO 1995034718 A1 WO1995034718 A1 WO 1995034718A1 EP 9502026 W EP9502026 W EP 9502026W WO 9534718 A1 WO9534718 A1 WO 9534718A1
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WIPO (PCT)
Prior art keywords
ethylene oxide
propylene oxide
alkoxylated
paper
foam
Prior art date
Application number
PCT/EP1995/002026
Other languages
German (de)
French (fr)
Inventor
Knut Oppenländer
Gabriele Dralle-Voss
Rudolf Schuhmacher
Horst Trapp
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU26712/95A priority Critical patent/AU2671295A/en
Publication of WO1995034718A1 publication Critical patent/WO1995034718A1/en

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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
    • B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/12—Defoamers

Definitions

  • the invention relates to the use of alkoxylated amines and of alkoxylated polyamines as defoamers in the paper industry, and also defoamer mixtures which contain these compounds and an emulsifier.
  • the known defoamers for paper production are water-free or aqueous formulations.
  • the water-free formulations mostly consist of thinly liquid oils, so-called oil defoamers, which are often used in a mixture with suitable emulsifiers or self-emulsifying agents. yawning fatty acid or fatty alcohol polyether.
  • 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
  • CH-B-610 210 discloses foam suppressants which contain an anionic surfactant, water and reaction products of propylene oxide with alcohols, monoamines, diamines and / or carboxylic acids.
  • the foam damping agents are used, for example, in paper production, the surface sizing of paper or as an additive to paper coating slips for the coating of paper. The effectiveness of such foam damping agents is also dependent on the temperature of the foam-forming medium.
  • the invention is based on the object of developing oil defoamers which are still highly effective even at elevated temperature of the circulating 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.
  • alkoxylated amines or alkoxylated polyamines each of which contains ethylene oxide and propylene oxide blocks or ethylene oxide and propylene oxide units in statistical distribution, and the molar ratio of ethylene oxide units to propylene oxide units in each case 1: 4 to 1: Is 20, as a defoamer for the paper industry.
  • the invention also relates to defoamers for the paper industry with a content of
  • the alkoxylated amines and polyamines to be used according to the invention are known substances. They are produced by the addition of propylene oxide and ethylene oxide to amines or polyamines, it being possible, if appropriate, to first add part of the ethylene oxide to the amines or polyamines and then propylene oxide and finally ethylene oxide, so that structures are formed which contain ethylene oxide. , Propylene oxide and ethylene oxide blocks included.
  • a mixed gas of ethylene oxide and propylene oxide can be used in the alkoxylation, so that alkoxylated amines or alkoxylated polyamines are obtained in which the ethylene oxide and propylene oxide units are present in statistical distribution.
  • alkylamines which have 1 to 22 carbon atoms in the alkyl chain.
  • the carbon chain can optionally be branched or can also contain a double bond.
  • Individual amines of this type are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, cyclohexylamine, laurylamine, oleylamine and stearylamine.
  • the alkoxylation of these amines gives rise to compounds of the structure
  • R Ci to C 22 alkyl
  • Alkoxylated polyamines can be characterized using formula II, for example:
  • R 1 and R 2 are identical or different and represent C 2 - to C ⁇ -alkyl or A stand, in which A has the meaning indicated in formula I,
  • R 3 C 2 to C 6 alkylene
  • R 1 , R 2 and R 3 stand for straight-chain and for branched alkyl or alkylene radicals.
  • Alkoxylated diamines of the formula are preferably used
  • R 4 represents C 2 to C 6 alkylene
  • Suitable diamines and polyamines are, for example, ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, 1,3-diaminopropane, diethylenetriamine, dipropylenetriamine, bishexamethylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and polyethyleneimines, which contain 10 to 50 ethyleneimine units and a unpolymerized unit Polyvinylamines that contain 5 to 50 vinylamine units copolymerized.
  • the alkoxylated amines or alkoxylated polyamines described above have an alkylene oxide content of 95 to 99.5% by weight, the molar ratio of ethylene oxide units to propylene oxide units in each case being 1: 4 to 1:20, preferably 1: 4 to 1:10.
  • the alkoxylated compounds are used as defoamers in the paper industry. puts. They act as foam dampers, foam preventers and fabric deaerators, in particular in the production of paper and cellulose, and as an additive in paper coating colors.
  • the alkoxylated amines and polyamines to be used according to the invention are liquid at room temperature.
  • the alkoxylated products to be used as defoamers according to the invention are used, for example, in such an amount that from 100 parts by weight of dry paper fibers in a paper stock suspension as a foam-forming medium 0.02 to 0.5, preferably 0.05 to 0.3 parts by weight of the defoamer come.
  • Pulps which are dewatered in the manufacture of paper are regarded as foam-forming medium, for example.
  • strongly foaming media are present in sulfite pulp cooking.
  • the alkoxylated amines and alkoxylated polyamines are also used in the foam control of waste water from paper mills.
  • the defoamers are usually added directly to the foaming medium or the defoamers mentioned are emulsified in water and 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 of emulsifiers, which may be combined can be used with the alkoxylated products to be used according to the invention.
  • the more intensive the distribution of the defoamers in an aqueous medium the better their defoaming and deaerating effect in the water cycle of the paper machine. A better effectiveness of the defoamers due to a finer distribution can be seen, for example, from the fact that the amount used for defoaming can be reduced.
  • Mixtures are therefore frequently produced for industrial purposes which, in addition to an alkoxylated amine or alkoxylated polyamine to be used according to the invention, contain 1 to 10, preferably 3 to 8% by weight of at least one emulsifier with an HLB value of at least 8 and up to Contain 90 wt .-% water.
  • the HLB value is known to mean the hydrophilic-lipophilic balance of an emulsifier, cf. WC Giffin, J. Soc. Cosmet. Chem., Vol. 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 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 first, so that block copolymers are formed.
  • the alkoxylation products can also contain small amounts of butylene oxide.
  • the alkoxylation of the fatty alcohols can of course also be carried out using mixtures of the alkylene oxides. In the latter case, you get statistically structured addition products.
  • 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.
  • a particularly preferred defoamer is an alkoxylated ethylenediamine which can be obtained by reacting 1 mol of ethylenediamine with 50 to 70 mol of propylene oxide and 5 to 20 mol of ethylene oxide.
  • the defoamers are preferably used in the manufacture of paper by dewatering a pulp suspension.
  • a block copolymer is again prepared by first adding 4.5 moles of ethylene oxide to one mole of ethylenediamine, then reacting the reaction product with 53 moles of propylene oxide and adding 11.5 moles of ethylene oxide to the reaction product obtained.
  • a block copolymer is prepared by adding 52 mol of propylene oxide to 1 mol of ethylenediamine and then adding 7.1 mol of ethylene oxide to this reaction product.
  • a 30% aqueous formulation of the defoamer 1 is prepared, to which 8% by weight, based on the entire formulation, of an addition product of 11 mol ethylene oxide and 1 mol of a co-oxo alcohol is added as a solubilizer.
  • a foam-developing pulp suspension which contains 0.1% wood pulp and 0.01% casein, are pumped around for 5 minutes in a channel made of a transparent plastic.
  • the amount of foam formed on the surface of the stock suspension is then measured with the aid of a grid on the wall of the trough in surface units (cm 2 ) and is given as a so-called foam value for assessing the effectiveness of a defoamer.
  • the foam value after 5 minutes is 1220 cm 2 .
  • an effective defoamer a total of 10 mg solid
  • the temperature of the pulp suspension is kept constant by means of an immersion heater connected to a controller and is 5 ° C. During the test, the temperature of the substance suspension is 50 ⁇ 1 ° C. The effectiveness of the defoamers is shown as% residual foam.
  • The% residual foam (R) is calculated as 0
  • S e is the foam value which is measured after the addition of the defoamer and S 0 is the foam zero value, ie the value which is measured in the absence of a defoamer.
  • S 0 is the foam zero value, ie the value which is measured in the absence of a defoamer.
  • the defoamer is better the smaller R is.

Abstract

The invention concerns the use, as anti-foaming agents in the paper industry, of alkoxylated amines or alkoxylated polyamines which each contain random ethylene oxide and propylene oxide blocks or ethylene oxide and propylene oxide units, the molar ratio of the ethylene oxide to the propylene oxide units being 1:4 to 1:20. The invention also concerns anti-foaming agents containing such alkoxylated amines and/or alkoxylated polyamines, at least one emulsifier with an HLB value of at least 8 and, optionally, up to 90 % by wt. of water.

Description

Entschäumer für die PapierindustrieDefoamers for the paper industry
Beschreibungdescription
Die Erfindung betrifft die Verwendung von alkoxylierten Aminen und von alkoxylierten Polyaminen als Entschäumer in der Papierin¬ dustrie sowie Entschäumermischungen- die diese Verbindungen und einen Emulgator enthalten.The invention relates to the use of alkoxylated amines and of alkoxylated polyamines as defoamers in the paper industry, and also defoamer mixtures which contain these compounds and an emulsifier.
Aufgrund eines hohen Luftgehaltes im Wasserkreislauf von Papier¬ maschinen sowie infolge von Schaumbildung können bei der Papier¬ fabrikation mannigfache Störungen auftreten. Wenn dabei der Schaum mit flotiertem Schmutz während der Blattbildung auf die Papierbahn gelangt, entstehen auf dem Papier Schaumflecken. Der Schaum, der sich bei der Papierherstellung bildet, ist in der Re¬ gel stabil und hält sich daher lange an strömungsarmen Stellen im Papiermaschinenkreis auf, an denen er eintrocknen und in dieser Form vom Stoff weggetragen werden kann. Bei der Blattbildung ent- stehen dann ebenfalls Flecken im Papier. Man verwendet daher Ent¬ schäumer, die die Neigung haben, sich an der Phasengrenze Luft/ Wasser anzureichern und somit einer Schaumbildung entgegenwirken. Die Luftblasen stören beispielsweise den Entwässerungsvorgang des Papierstoffs auf der Papiermaschine, verursachen eine poröse Struktur des Blatts und können sogar Löcher in der Papierbahn bilden. Da bei der Papierherstellung aus Rationalisierungsgründen immer höhere Arbeitsgeschwindigkeiten auf den Maschinen angewen¬ det werden, steigt naturgemäß die Gefahr der Untermischung von Luft in die Fasersuspension.Due to a high air content in the water cycle of paper machines and due to foam formation, various faults can occur in paper production. If the foam with floated dirt gets onto the paper web during sheet formation, foam spots will appear on the paper. The foam that forms during paper production is generally stable and therefore remains in low-flow locations in the paper machine circuit for a long time, where it can dry up and can be carried away by the material in this form. Stains also appear in the paper during sheet formation. Defoamers are therefore used which have the tendency to accumulate at the air / water phase boundary and thus counteract foam formation. The air bubbles, for example, interfere with the dewatering process of the paper stock on the paper machine, cause a porous structure of the sheet and can even form holes in the paper web. Since ever higher working speeds are used on the machines for reasons of rationalization in paper production, the risk of air being mixed into the fiber suspension naturally increases.
Da die Wasserkreisläufe der Papiermaschinen immer stärker ge¬ schlossen werden, reichern sich darin wasserlösliche Stoffe an, die den Schaum stabilisieren und teilweise sogar auch die Schaum¬ bildung fördern. Außerdem erhöht sich dadurch die Temperatur des im Kreise geführten Wassers der Papiermaschine. Diese Temperatur¬ erhöhung hat einen starken Einfluß auf die Wirkung von Ent¬ schäumern. Bei den bekannten Entschäumern für die Papierherstel¬ lung handelt es sich um wasserfreie oder um wäßrige Formulierun¬ gen. Die wasserfreien Formulierungen bestehen meistens aus dünn- flüssigen Ölen, sogenannten Öl-Entschäumern, die oft im Gemisch mit geeigneten Emulgatoren eingesetzt werden oder um selbstemul- gierende Fettsäure- bzw. Fettalkoholpolyether. Diese Produkte be¬ sitzen nur eine begrenzte entschäumende, schaumverhütende und entlüftende Wirkung im Vergleich zu den wäßrigen Formulierungen, den sogenannten Emulsionsentschäumern, die meist einen Wasseran¬ teil von über 50 % aufweisen. Aus der DE-PS 25 32 888 ist die Verwendung von oxalkylierten, geradkettigen, gesättigten Fettalkoholen mit 12 bis 30 Kohlen¬ stoffatomen, die durch Umsetzung von 1 Mol des Alkohols mitSince the water cycles of the paper machines are closed more and more, water-soluble substances accumulate therein, which stabilize the foam and in some cases even promote foam formation. This also increases the temperature of the circulating water of the paper machine. This increase in temperature has a strong influence on the action of defoamers. The known defoamers for paper production are water-free or aqueous formulations. The water-free formulations mostly consist of thinly liquid oils, so-called oil defoamers, which are often used in a mixture with suitable emulsifiers or self-emulsifying agents. yawning fatty acid or fatty alcohol polyether. These products have only a limited defoaming, antifoam 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
(a) 5 bis 60 Mol Propylenoxid und anschließend mit(a) 5 to 60 moles of propylene oxide and then with
(b) 0,5 bis 20 Mol Ethylenoxid(b) 0.5 to 20 moles of ethylene oxide
erhältlich sind, als Stoffentlüfter bei der Papierfabrikation be- kannt. Bei höherer Temperatur des Kreislaufwassers der Papierma¬ schine geht jedoch die Wirksamkeit dieser Entschäumer zurück.are available, known as fabric deaerators in paper manufacturing. At a higher temperature of the circulation water of the paper machine, however, the effectiveness of these defoamers decreases.
Aus der CH-B-610 210 sind Schaumdämpfungsmittel bekannt, die ein anionisches Tensid, Wasser und Umsetzungsprodukte von Propylen- oxid mit Alkoholen, Monoaminen, Diaminen und/oder Carbonsäuren enthalten. Die Schaumdämpfungsmittel werden beispielsweise bei der Papierherstellung, der Oberflächenleimung von Papier oder als Zusatz zu Papierstreichmassen für die Beschichtung von Papier verwendet. Die Wirksamkeit solcher Schaumdämpfungsmittel ist ebenfalls von der Temperatur des schaumbildenden Mediums abhän¬ gig.CH-B-610 210 discloses foam suppressants which contain an anionic surfactant, water and reaction products of propylene oxide with alcohols, monoamines, diamines and / or carboxylic acids. The foam damping agents are used, for example, in paper production, the surface sizing of paper or as an additive to paper coating slips for the coating of paper. The effectiveness of such foam damping agents is also dependent on the temperature of the foam-forming medium.
Der Erfindung liegt die Aufgabe zugrunde, Öl-Entschäumer zu ent¬ wickeln, die auch bei erhöhter Temperatur des Kreislaufwassers der Papiermaschine noch gut wirksam sind. Außerdem sollen die Entschäumer beim Verdünnen mit Wasser Emulsionen bilden, die lange Zeit stabil sind und nicht aufrahmen.The invention is based on the object of developing oil defoamers which are still highly effective even at elevated temperature of the circulating water of the paper machine. In addition, the defoamers should form emulsions when diluted with water, which are stable for a long time and do not cream.
Die Aufgabe wird erfindungsgemäß gelöst durch Verwendung von alkoxylierten Aminen oder von alkoxylierten Polyaminen, die je¬ weils Ethylenoxid- und Propylenoxidblöcke oder Ethylenoxid- und Propylenoxideinheiten in statistischer Verteilung enthalten, und wobei das Molverhältnis von Ethylenoxideinheiten zu Propylenoxid¬ einheiten jeweils 1:4 bis 1:20 beträgt, als Entschäumer für die Papierindustrie.The object is achieved according to the invention by using alkoxylated amines or alkoxylated polyamines, each of which contains ethylene oxide and propylene oxide blocks or ethylene oxide and propylene oxide units in statistical distribution, and the molar ratio of ethylene oxide units to propylene oxide units in each case 1: 4 to 1: Is 20, as a defoamer for the paper industry.
Gegenstand der Erfindung sind außerdem Entschäumer für die Pa¬ pierindustrie mit einem Gehalt vonThe invention also relates to defoamers for the paper industry with a content of
(a) 10 bis 99 Gew.-% an alkoxylierten Aminen und/oder alkoxy¬ lierten Polyaminen, die jeweils Ethylenoxid- und Propylen¬ oxidblöcke oder Ethylenoxid- und Propylenoxideinheiten in statistischer Verteilung enthalten, und wobei das Mol¬ verhältnis Ethylenoxideinheiten zu Propylenoxideinheiten je- weils 1:4 bis 1:20 beträgt, (b) 1 bis 10 Gew.-% mindestens eines Emulgators mit einem HLB- Wert von mindestens 8 und(a) 10 to 99% by weight of alkoxylated amines and / or alkoxylated polyamines, each of which contains ethylene oxide and propylene oxide blocks or ethylene oxide and propylene oxide units in statistical distribution, and the molar ratio of ethylene oxide units to propylene oxide units in each case because it is 1: 4 to 1:20, (b) 1 to 10% by weight of at least one emulsifier with an HLB value of at least 8 and
(c) 0 bis 90 Gew.-% Wasser.(c) 0 to 90 wt% water.
Die erfindungsgemäß zu verwendenden alkoxylierten Amine und Poly¬ amine sind bekannte Stoffe. Sie werden durch Anlagerung von Propylenoxid und Ethylenoxid an Amine oder Polyamine hergestellt, wobei man gegebenenfalls auch zunächst einen Teil des Ethylen- oxids an die Amine oder Polyamine und anschließend Propylenoxid und zum Schluß Ethylenoxid anlagern kann, so daß Strukturen ent¬ stehen, die Ethylenoxid-, Propylenoxid- und Ethylenoxid-Blöcke enthalten. Außerdem kann man bei der Alkoxylierung ein Mischgas aus Ethylenoxid und Propylenoxid einsetzen, so daß man alkoxy- lierte Amine bzw. alkoxylierte Polyamine erhält, in denen die Ethylenoxid- und Propylenoxideinheiten in statistischer Vertei¬ lung vorliegen.The alkoxylated amines and polyamines to be used according to the invention are known substances. They are produced by the addition of propylene oxide and ethylene oxide to amines or polyamines, it being possible, if appropriate, to first add part of the ethylene oxide to the amines or polyamines and then propylene oxide and finally ethylene oxide, so that structures are formed which contain ethylene oxide. , Propylene oxide and ethylene oxide blocks included. In addition, a mixed gas of ethylene oxide and propylene oxide can be used in the alkoxylation, so that alkoxylated amines or alkoxylated polyamines are obtained in which the ethylene oxide and propylene oxide units are present in statistical distribution.
Zur Herstellung der erfindungsgemäß zu verwendenden Verbindungen kann man beispielsweise von Alkylaminen ausgehen, die 1 bis 22 C- Atome in der Alkylkette haben. Die Kohlenstoffkette kann gegebe¬ nenfalls verzweigt sein oder auch eine Doppelbindung enthalten. Einzelne Amine dieser Art sind beispielsweise Methylamin, Ethyl- a in, n-Propylamin, iso-Propyla in, n-Butylamin, tert.-Butylamin, Cyclohexylamin, Laurylamin, Oleylamin und Stearylamin. Bei der Alkoxylierung dieser Amine entstehen Verbindungen der StrukturTo prepare the compounds to be used according to the invention, it is possible, for example, to start from alkylamines which have 1 to 22 carbon atoms in the alkyl chain. The carbon chain can optionally be branched or can also contain a double bond. Individual amines of this type are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, cyclohexylamine, laurylamine, oleylamine and stearylamine. The alkoxylation of these amines gives rise to compounds of the structure
R-N ( I) .R-N (I).
in derin the
R = Ci- bis C22-Alkyl,R = Ci to C 22 alkyl,
A = - [EO. x- .PO. y- .EO. z-HA = - [EO. x- .PO. y- .EO. z-H
EO = EthylenoxideinheitEO = ethylene oxide unit
PO = PropylenoxideinheitPO = propylene oxide unit
x = 0-3x = 0-3
y = 10-25, vorzugsweise 12-20 undy = 10-25, preferably 12-20 and
z = 0,75-4, vorzugsweise 2-3 bedeuten. Alkoxylierte Polyamine können beispielsweise mit Hilfe der Formel II charakterisiert werden:z = 0.75-4, preferably 2-3 mean. Alkoxylated polyamines can be characterized using formula II, for example:
Figure imgf000006_0001
Figure imgf000006_0001
in derin the
R1 und R2 gleich oder verschieden sind und für C2- bis Cδ-Alkyl oder A stehen, wobei A die in Formel I angegebene Bedeutung hat,R 1 and R 2 are identical or different and represent C 2 - to C δ -alkyl or A stand, in which A has the meaning indicated in formula I,
R3 = C2- bis C6-Alkylen undR 3 = C 2 to C 6 alkylene and
1- 61- 6
bedeuten. Die Substituenten R1, R2 und R3 stehen für geradkettige und für verzweigte Alkyl- bzw. Alkylenreste. Vorzugsweise ver¬ wendet man alkoxylierte Diamine der Formelmean. The substituents R 1 , R 2 and R 3 stand for straight-chain and for branched alkyl or alkylene radicals. Alkoxylated diamines of the formula are preferably used
Figure imgf000006_0002
Figure imgf000006_0002
in derin the
R4 für C2- bis C6-Alkylen steht undR 4 represents C 2 to C 6 alkylene and
die in Formel I angegebene Bedeutung hathas the meaning given in formula I.
Geeignete Diamine und Polyamine sind beispielsweise Ethylen- diamin, 1, 4-Diaminobutan, Hexamethylendiamin, 1, 3-Diaminopropan, Diethylentriamin, Dipropylentriamin, Bishexamethylentriamin, Tri- ethylentetramin, Tripropylentetramin, Tetraethylenpentamin und Polyethylenimine, die 10 bis 50 Ethylenimineinheiten einpolymeri- siert enthalten sowie Polyvinylamine, die 5 bis 50 Vinylamin- einheiten einpolymerisiert enthalten. Die oben beschriebenen alkoxylierten Amine oder alkoxylierten Polyamine haben einen Al- kylenoxidgehalt von 95 bis 99,5 Gew.-%, wobei das Molverhältnis von Ethylenoxideinheiten zu Propylenoxideinheiten jeweils 1:4 bis 1:20, vorzugsweise 1:4 bis 1:10 beträgt. Die alkoxylierten Verbindungen werden als Entschäumer in der Papierindustrie einge- setzt. Sie wirken als Schaumdämpfer, Schaumverhüter und Stoffent- lüfter, insbesondere bei der Herstellung von Papier, und Zell¬ stoff sowie als Additiv in Papierstreichfarben. Die erfindungs¬ gemäß zu verwendenden alkoxylierten Amine und Polyamine sind bei Raumtemperatur flüssig. Bei Zugabe dieser Verbindungen zu einem schaumbildenden wäßrigen System tritt bereits in Gegenwart sehr geringer Mengen an Entschäumern eine starke Verminderung der Schaumbildung ein. Die erfindungsgemäß als Entschäumer zu verwen¬ denden alkoxylierten Produkte werden beispielsweise in einer sol- chen Menge eingesetzt, daß auf 100 Gew.-Teile trockener Papierfa¬ sern in einer PapierstoffSuspension als schaumbildendes Medium 0,02 bis 0,5, vorzugsweise 0,05 bis 0,3 Gew.-Teile des Ent¬ schäumers kommen. Als schaumbildendes Medium werden beispiels¬ weise Pulpen angesehen, die bei der Herstellung von Papier ent- wässert werden. Außerdem liegen bei der Sulfitzellstoffkochung stark schaumbildende Medien vor. Die alkoxylierten Amine und alkoxylierten Polyamine werden auch bei der Schaumbekämpfung von Abwässern aus Papierfabriken verwendet.Suitable diamines and polyamines are, for example, ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, 1,3-diaminopropane, diethylenetriamine, dipropylenetriamine, bishexamethylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and polyethyleneimines, which contain 10 to 50 ethyleneimine units and a unpolymerized unit Polyvinylamines that contain 5 to 50 vinylamine units copolymerized. The alkoxylated amines or alkoxylated polyamines described above have an alkylene oxide content of 95 to 99.5% by weight, the molar ratio of ethylene oxide units to propylene oxide units in each case being 1: 4 to 1:20, preferably 1: 4 to 1:10. The alkoxylated compounds are used as defoamers in the paper industry. puts. They act as foam dampers, foam preventers and fabric deaerators, in particular in the production of paper and cellulose, and as an additive in paper coating colors. The alkoxylated amines and polyamines to be used according to the invention are liquid at room temperature. When these compounds are added to a foam-forming aqueous system, a considerable reduction in foam formation occurs even in the presence of very small amounts of defoamers. The alkoxylated products to be used as defoamers according to the invention are used, for example, in such an amount that from 100 parts by weight of dry paper fibers in a paper stock suspension as a foam-forming medium 0.02 to 0.5, preferably 0.05 to 0.3 parts by weight of the defoamer come. Pulps which are dewatered in the manufacture of paper are regarded as foam-forming medium, for example. In addition, strongly foaming media are present in sulfite pulp cooking. The alkoxylated amines and alkoxylated polyamines are also used in the foam control of waste water from paper mills.
Die Entschäumer werden üblicherweise direkt dem schäumenden Me¬ dium zugesetzt oder man emulgiert die genannten Entschäumer in Wasser und verwendet sie in Form einer Öl-in-Wasser-Emulsion. Bei der direkten Dosierung der flüssigen Entschäumer in das zu ent¬ schäumende wäßrige Medium hängt die mittlere Teilchengröße der in Wasser emulgierten Teilchen von den unmittelbar an der Dosier¬ stelle vorhandenen Scherkräften, der Entschäumerkomponente und der Art«und Menge an Emulgatoren ab, die gegebenenfalls zusammen mit den erfindungsgemäß zu verwendenden alkoxylierten Produkten eingesetzt werden. Je intensiver die Verteilung der Entschäumer in einem wäßrigen Medium ist, desto besser ist auch ihre ent¬ schäumende und entlüftende Wirkung im Wasserkreislauf der Papier¬ maschine. Eine bessere Wirksamkeit der Entschäumer aufgrund einer feineren Verteilung ist beispielsweise daran erkenntlich, daß die zur Entschäumung eingesetzte Menge erniedrigt werden kann.The defoamers are usually added directly to the foaming medium or the defoamers mentioned are emulsified in water and used in the form of an oil-in-water emulsion. When the liquid defoamers are metered directly into the aqueous medium to be defoamed, 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 of emulsifiers, which may be combined can be used with the alkoxylated products to be used according to the invention. The more intensive the distribution of the defoamers in an aqueous medium, the better their defoaming and deaerating effect in the water cycle of the paper machine. A better effectiveness of the defoamers due to a finer distribution can be seen, for example, from the fact that the amount used for defoaming can be reduced.
Für technische Einsatzzwecke werden daher häufig Mischungen her¬ gestellt, die außer einem erfindungsgemäß zu verwendenden alkoxy¬ lierten Amin oder alkoxylierten Polyamin 1 bis 10, vorzugsweise 3 bis 8 Gew.-% mindestens eines Emulgators mit einem HLB-Wert von mindestens 8 und bis zu 90 Gew.-% Wasser enthalten.Mixtures are therefore frequently produced for industrial purposes which, in addition to an alkoxylated amine or alkoxylated polyamine to be used according to the invention, contain 1 to 10, preferably 3 to 8% by weight of at least one emulsifier with an HLB value of at least 8 and up to Contain 90 wt .-% water.
Unter HLB-Wert wird bekanntlich die hydrophile-lipophile Balance eines Emulgators verstanden, vgl. W.C. Giffin, J. Soc. Cosmet. Chem., Band 1, 311 (1950) . Geeignete Emulgatoren dieser Art sind beispielsweise hydrophile wasserlösliche Produkte, die durch Ethoxylierung von Alkylphenolen, Fettalkoholen, Fettsäuren und Fettaminen erhältlich sind, sowie PO-EO-Blockpolymerisate mit einem Ethylenoxid-Anteil von 10 bis 80 %. Insbesondere verwendet man als Emulgator die Additionsprodukte von Ethylenoxid oder Propylenoxid an Fettalkohole mit 8 bis 18 C-Atomen oder man la¬ gert an die Fettalkohole zunächst Ethylenoxid und dann Propylen- oxid und gegebenenfalls wieder Ethylenoxid an, so daß Block- copolymerisate entstehen. Die Alkoxylierungsprodukte können au¬ ßerdem noch geringe Mengen an Butylenoxid angelagert enthalten. Ebenso sind auch Additionsprodukte geeignet, die durch Anlagerung von Propylenoxid und danach Ethylenoxid an Fettalkohole entstehen oder bei denen zunächst Butylenoxid und danach Ethylenoxid an einen Fettalkohol oder ein Fettalkoholgemisch angelagert wird. Selbstverständlich kann die Alkoxylierung der Fettalkohole auch mit Mischungen der Alkylenoxide durchgeführt werden. Im zuletzt genannten Fall erhält man statistisch aufgebaute Anlagerungspro- dukte. Vorzugsweise werden Cß- bis C-.8-, insbesondere Cio- bis Cχ6-Alkohole der Alkoxylierung unterworfen, wobei man pro Mol Alkohol 3 bis 80, vorzugsweise 10 bis 30 Mol Alkylenoxid zur Reaktion bringt. Von den Alkylenoxiden wird Ethylenoxid bevor¬ zugt. Die Produkte sind im wesentlichen dadurch charakterisiert, daß sie einen HLB-Wert von mindestens 8 haben und wasserlöslich sind.The HLB value is known to mean the hydrophilic-lipophilic balance of an emulsifier, cf. WC Giffin, J. Soc. Cosmet. Chem., Vol. 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 an ethylene oxide content of 10 to 80%. In particular, 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 first, so that block copolymers are formed. The alkoxylation products can also contain small amounts of butylene oxide. Also suitable are addition products which are formed by the addition of propylene oxide and then ethylene oxide to fatty alcohols or in which butylene oxide and then ethylene oxide are added to a fatty alcohol or a fatty alcohol mixture. The alkoxylation of the fatty alcohols can of course also be carried out using mixtures of the alkylene oxides. In the latter case, you get statistically structured addition products. Preferably C ß - to C .8 -, in particular CIO to Cχ subjected to the alkoxylation 6 alcohols, wherein one to 80, preferably 10 to 30 moles of alkylene oxide per mole of alcohol brings 3 for the reaction. Of the 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.
Besonders bevorzugt als Entschäumer ist ein alkoxyliertes Ethylendiamin, das durch Umsetzung von 1 Mol Ethylendiamin mit 50 bis 70 Mol Propylenoxid und 5 bis 20 Mol Ethylenoxid erhältlich ist. Die Entschäumer werden vorzugsweise bei der Herstellung von Papier durch Entwässern einer PapierstoffSuspension verwendet.A particularly preferred defoamer is an alkoxylated ethylenediamine which can be obtained by reacting 1 mol of ethylenediamine with 50 to 70 mol of propylene oxide and 5 to 20 mol of ethylene oxide. The defoamers are preferably used in the manufacture of paper by dewatering a pulp suspension.
BeispieleExamples
Entschäumer 1Defoamer 1
An 1 Mol Ethylendiamin werden zunächst 4,5 Mol Ethylenoxid ange¬ lagert . Das dabei erhaltene Reaktionsprodukt wird anschließend mit 63 Mol Propylenoxid umgesetzt. Sobald die Umsetzung beendet ist, lagert man an das Umsetzungsprodukt 12,8 Mol Ethylenoxid an.4.5 mol of ethylene oxide are initially added to 1 mol of ethylenediamine. The reaction product obtained is then reacted with 63 moles of propylene oxide. As soon as the reaction has ended, 12.8 mol of ethylene oxide are added to the reaction product.
Entschäumer 2Defoamer 2
Man stellt wiederum ein Blockcopolymerisat her, indem man zu¬ nächst 4,5 Mol Ethylenoxid an ein Mol Ethylendiamin anlagert, dann das Reaktionsprodukt mit 53 Mol Propylenoxid zur Reaktion bringt und an das dabei erhaltene Umsetzungsprodukt 11,5 Mol Ethylenoxid anlagert. Entschäumer 3A block copolymer is again prepared by first adding 4.5 moles of ethylene oxide to one mole of ethylenediamine, then reacting the reaction product with 53 moles of propylene oxide and adding 11.5 moles of ethylene oxide to the reaction product obtained. Defoamer 3
Man stellt ein Blockcopolymerisat her, indem man an 1 Mol Ethy- ' lendiamin 52 Mol Propylenoxid anlagert und an dieses Reaktions- produkt anschließend 7,1 Mol Ethylenoxid addiert.A block copolymer is prepared by adding 52 mol of propylene oxide to 1 mol of ethylenediamine and then adding 7.1 mol of ethylene oxide to this reaction product.
Entschäumer 4Defoamer 4
Man stellt eine 30 %ige wäßrige Formulierung des Entschäumers 1 her, zu der man als Lösungsvermittler 8 Gew.-%, bezogen auf die gesamte Formulierung, eines Additionsprodukts von 11 Mol Ethylen¬ oxid an 1 Mol eines Cχo-Oxoalkohols zusetzt.A 30% aqueous formulation of the defoamer 1 is prepared, to which 8% by weight, based on the entire formulation, of an addition product of 11 mol ethylene oxide and 1 mol of a co-oxo alcohol is added as a solubilizer.
Entschäumer 5 (Vergleich)Defoamer 5 (comparison)
Man stellt ein Additionsprodukt von 43 Mol Propylenoxid an 1 Mol Ethylendiamin her.An addition product of 43 moles of propylene oxide with 1 mole of ethylenediamine is prepared.
Entschäumer 6 (Vergleich)Defoamer 6 (comparison)
Hierbei handelt es sich um ein Additionsprodukt von 76 Mol Propylenoxid an 1 Mol Ethylendiamin.This is an addition product of 76 moles of propylene oxide with 1 mole of ethylenediamine.
Die oben beschriebenen Entschäumer wurden folgendermaßen geprüft:The defoamers described above were tested as follows:
Bestimmung des Schaumwertes:Determination of the foam value:
In einer Rinne aus einem durchsichtigen Kunststoff werden jeweils 5 1 einer schaumentwickelnden PapierstoffSuspension, die 0,1 % Holzschliff und 0,01 % Casein enthält, 5 Minuten umgepumpt. Die an der Oberfläche der StoffSuspension gebildete Schaummenge wird dann mit Hilfe eines Rasters an der Wand der Rinne in Flächenein¬ heiten (cm2) gemessen und als sogenannter Schaumwert zur Beurtei¬ lung der Wirksamkeit eines Entschäumers angegeben.5 l of a foam-developing pulp suspension, which contains 0.1% wood pulp and 0.01% casein, are pumped around for 5 minutes in a channel made of a transparent plastic. The amount of foam formed on the surface of the stock suspension is then measured with the aid of a grid on the wall of the trough in surface units (cm 2 ) and is given as a so-called foam value for assessing the effectiveness of a defoamer.
Pumpt man die PapierstoffSuspension in Abwesenheit eines Ent¬ schäumers um, so beträgt der Schaumwert nach 5 Minuten 1220 cm2. Durch Zugabe von jeweils 2 mg/1 eines wirksamen Entschäumers (insgesamt 10 mg fest) zu der HolzschliffSuspension wird dieser Schaumwert deutlich reduziert, so daß er ein Maß für die Wirksam¬ keit eines Entschäumers darstellt. Prüfung der Entschäumer:If the pulp suspension is pumped around in the absence of a defoamer, the foam value after 5 minutes is 1220 cm 2 . By adding 2 mg / 1 of an effective defoamer (a total of 10 mg solid) to the wood pulp suspension, this foam value is significantly reduced, so that it represents a measure of the effectiveness of a defoamer. Checking the defoamers:
Die Temperatur der PapierstoffSuspension wird mittels eines, mit einem Regler verbundenen Tauchsieders konstant gehalten und be- 5 trägt 50°C. Während der Prüfung beträgt die Temperatur der Stoff- Suspension 50 ± 1°C. Die Wirksamkeit der Entschäumer wird als % Restschaum dargestellt.The temperature of the pulp suspension is kept constant by means of an immersion heater connected to a controller and is 5 ° C. During the test, the temperature of the substance suspension is 50 ± 1 ° C. The effectiveness of the defoamers is shown as% residual foam.
Der % Restschaum (R) wird berechnet als 0The% residual foam (R) is calculated as 0
100100
R =R =
wobei Se der Schaumwert ist, der nach Zugabe des Entschäumers ge¬ messen wird und S0 der Schaumnullwert ist, d.h. der Wert, der in Abwesenheit eines Entschäumers gemessen wird. In dieser Termino¬ logie ist der Entschäumer um so besser, je kleiner R ist.where S e is the foam value which is measured after the addition of 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.
Für die oben beschriebenen Entschäumer wurden die in der folgen¬ den Tabelle angegebenen Werte für den Restschaum R erhalten.The values for the residual foam R given in the table below were obtained for the defoamers described above.
Beispiel Nr. Entschäumer Nr. RExample No. Defoamer No. R
1 1 361 1 36
2 2 372 2 37
3 3 293 3 29
4 4 464 4 46
VergleichsbeispielComparative example
1 5 591 5 59
2 6 522 6 52
z:ozo/s6-ia/X3-ϊ 8Uf ε/S6 OAV z: ozo / s6-ia / X3-ϊ 8Uf ε / S6 OAV

Claims

Patentansprüche Claims
1. Verwendung von alkoxylierten Aminen und von alkoxylierten Polyaminen, die jeweils Ethylenoxid- und Propylenoxidblöcke oder Ethylenoxid- und Propylenoxideinheiten in statistischer Verteilung enthalten, und wobei das Molverhältnis von Ethylenoxideinheiten zu Propylenoxideinheiten jeweils 1:4 bis 1:20 beträgt, als Entschäumer für die Papierindustrie.1. Use of alkoxylated amines and of alkoxylated polyamines, each of which contains ethylene oxide and propylene oxide blocks or ethylene oxide and propylene oxide units in statistical distribution, and the molar ratio of ethylene oxide units to propylene oxide units in each case being 1: 4 to 1:20, as defoamers for the paper industry .
Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man als Entschäumer ein alkoxyliertes Ethylendiamin einsetzt, das durch Umsetzung von 1 Mol Ethylendiamin mit 50 bis 70 Mol Propylenoxid und 5 bis 25 Mol Ethylenoxid erhältlich ist.Use according to claim 1, characterized in that the defoamer used is an alkoxylated ethylenediamine which can be obtained by reacting 1 mol of ethylenediamine with 50 to 70 mol of propylene oxide and 5 to 25 mol of ethylene oxide.
Entschäumer für die Papierindustrie mit einem Gehalt vonDefoamer for the paper industry containing
(a) 10 bis 99 Gew.-% an alkoxylierten Aminen und/oder alkoxy¬ lierten Polyaminen, die jeweils Ethylenoxid- und Propyle- noxidblöcke oder Ethylenoxid- und Propylenoxideinheiten in statistischer Verteilung enthalten, und wobei das Mol¬ verhältnis von Ethylenoxideinheiten zu Propylenoxidein¬ heiten jeweils 1:4 bis 1:20 beträgt,(a) 10 to 99% by weight of alkoxylated amines and / or alkoxylated polyamines, each of which contains ethylene oxide and propylene oxide blocks or ethylene oxide and propylene oxide units in statistical distribution, and the molar ratio of ethylene oxide units to propylene oxide units units is 1: 4 to 1:20,
(b) 1 bis 10 Gew.-% mindestens eines Emulgators mit einem HLB-Wert von mindestens 8 und(b) 1 to 10% by weight of at least one emulsifier with an HLB value of at least 8 and
(c) 0 bis 90 Gew.-% Wasser. (c) 0 to 90 wt% water.
PCT/EP1995/002026 1994-06-13 1995-05-27 Anti-foaming agent for use in the paper industry WO1995034718A1 (en)

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CN115105867A (en) * 2022-06-21 2022-09-27 杭州撒拉弗科技有限公司 Emulsion type defoaming agent for papermaking and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US6524435B1 (en) * 2000-05-08 2003-02-25 Ondeo Nalco Company Method and composition for dispersing hydrophobic particles in aqueous suspensions

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DE2553994A1 (en) * 1974-12-11 1976-06-24 Sandoz Ag IMPROVEMENTS IN ORGANIC PRODUCTS
US4871483A (en) * 1987-04-16 1989-10-03 Gaf Corporation Novel non-depositing defoaming compositions
US4960540A (en) * 1989-08-24 1990-10-02 Friel Jr Thomas C Alkoxylated bis-amide defoaming compounds

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
DE2553994A1 (en) * 1974-12-11 1976-06-24 Sandoz Ag IMPROVEMENTS IN ORGANIC PRODUCTS
US4871483A (en) * 1987-04-16 1989-10-03 Gaf Corporation Novel non-depositing defoaming compositions
US4960540A (en) * 1989-08-24 1990-10-02 Friel Jr Thomas C Alkoxylated bis-amide defoaming compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115105867A (en) * 2022-06-21 2022-09-27 杭州撒拉弗科技有限公司 Emulsion type defoaming agent for papermaking and preparation method thereof

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