WO1996028605A1 - Use of aminomethylene phosphono group-containing polymers as complexing agents - Google Patents

Use of aminomethylene phosphono group-containing polymers as complexing agents Download PDF

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Publication number
WO1996028605A1
WO1996028605A1 PCT/EP1996/000862 EP9600862W WO9628605A1 WO 1996028605 A1 WO1996028605 A1 WO 1996028605A1 EP 9600862 W EP9600862 W EP 9600862W WO 9628605 A1 WO9628605 A1 WO 9628605A1
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Prior art keywords
complexing agents
paper
bleaching
ammonium salts
aminomethylene
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PCT/EP1996/000862
Other languages
German (de)
French (fr)
Inventor
Knut Oppenländer
Wolfgang Günther
Jürgen Mohr
Friedrich Linhart
Rudolf Schuhmacher
Jaroslav Melzer
Original Assignee
Basf Aktiengesellschaft
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Publication of WO1996028605A1 publication Critical patent/WO1996028605A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • 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
    • D21H21/14—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 characterised by function or properties in or on the paper

Definitions

  • the invention relates to the use of polymers containing aminomethylenephosphono groups and their alkali metal or ammonium salts as complexing agents for alkaline earth metal and heavy metal ions in pulp bleaching, cellulose bleaching, cellulose production, paper production, textile finishing and deinking of printed waste paper.
  • complexing agents both in the oxidative and in the reductive bleaching of fibrous materials which are used for the production of paper, in particular wood pulp. Their main task is to complex interfering metal ions.
  • Complexing agents which also used in the paper industry are, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediaminetetramethylenephosphonic acid.
  • the phosphonomethylated polyvinylamines known from WO-A-91/02011 and the phosphonomethylated polyacrylamides described in DE-A-41 28 510 are used as scale inhibitors and as additives to detergents and cleaning agents.
  • EP-B-0 444 542 discloses the use of N-oxides and of alkylated phosphonomethylated polyethyleneimines as dispersants for aqueous cement compositions containing hydraulic cement.
  • the invention has for its object to provide new complexing agents for the paper industry, the pulp industry, textile finishing and deinking of printed waste paper.
  • the object is achieved according to the invention with the use of polymers containing aminomethylene phosphono groups and their alkali metal or ammonium salts and the N-oxides derived therefrom and the polyammonium salts obtainable therefrom by alkylation as complexing agents for alkaline earth metal and heavy metal ions in pulp bleaching, pulp bleaching, cellulose production, paper production, textile finishing and deinking of printed waste paper.
  • Polymers containing aminomethylene phosphono groups can be obtained by polymerizing the phosphonomethylatable
  • the phosphonomethylated polyvinylamines or copolymers containing vinylamine units described in WO-A-91/02011 are suitable for the purpose of use according to the invention.
  • the quaternary ammonium salts obtainable therefrom by alkylation and the corresponding N-oxides and the polyacrylamides known from DE-A-41 28 510 are also suitable.
  • Phosphonomethylated polyamines and N-oxides derived therefrom and ammonium salts obtainable by quaternization are also suitable for the use according to the invention.
  • Such compounds are known for example from the above-mentioned EP-B 0 444 542. They are made by phosphonomethylation of polyamines.
  • suitable polyamines are all compounds which contain at least as many basic, phosphonomethylatable nitrogen atoms in the molecule that the aminomethylene phosphonates obtainable therefrom have complexing properties.
  • the polyamines also include polyallylamines. The molar mass of the polyamines is, for example, at least 200, preferably 500 to 2 million.
  • Phosphonomethylated polyethyleneimines or their alkali metal or ammonium salts are particularly preferred as complexing agents. These products are obtained, for example, by phosphonomethylating polyethyleneimines.
  • Polyethyleneimines are known to be produced by polymerizing ethyleneimine in the presence of acids, boron trifluoride or halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, ethylene chloride or ethyl bromide as a catalyst.
  • the polyethyleneimines have molecular weights of 200 to 2 million, preferably 500 to 1.2 million, polymers of this type are commercially available. They contain structural units of the formula -CH 2 -CH 2 -N- (I),
  • Me H, alkali metal or ammonium equivalent
  • the phosphonomethylated compounds are used, for example, in amounts of 0.02 to 0.5 preferably 0.1 to 0.3% by weight, based on dry fiber material, is used as the complexing agent.
  • the polymers containing aminomethylene phosphono groups and their alkali metal and ammonium salts have e.g. an organically bound phosphorus content of 0.005 to 20, preferably 0.01 to 18,% by weight.
  • the above-described polymeric complexing agents which contain all phosphonomethyl groups, are used in wood pulp bleaching, cellulose bleaching, cellulose production, paper production, textile finishing and deinking of printed waste paper.
  • the technical raw materials and auxiliary materials used in paper production mostly contain traces of heavy metals, especially iron and manganese ions.
  • Wood chips that are difficult to bleach and other paper raw materials, such as thermomechanical material (TMP) and chemothermomechanical material (CTMP) often contain a disproportionate amount of iron ions. In contrast to iron-II ions, iron-III ions react with parts of the wood to form dark-colored compounds.
  • the use of the compounds to be used according to the invention in bleaching solutions also saves hydrogen peroxide in oxidative bleaching.
  • the compounds to be used according to the invention are therefore also suitable as complexing agents in textile finishing, in particular in pretreatment, for example prewashing and pre-cleaning, desizing, alkaline decoction and hydrogen peroxide bleaching of textile materials of all kinds, preferably textile materials containing cotton.
  • Textile materials are understood to mean, for example, yarns, woven fabrics, nonwovens or knitted fabrics.
  • hardness builders Due to the ever increasing closing of the water cycle of the paper machines, there is a constant accumulation of hardness builders. This can include lead to precipitation of carbonates and silicates, which can have a direct impact on paper properties, e.g. Strength, absorbency, dyeability and the dust behavior of the paper.
  • the hardening agents can also impair the effectiveness of auxiliaries and the properties of dyes. If the phosphonomethylated polyamines and their derivatives which contain units of form II, III or IV to be used according to the invention as complexing agents are added to the paper stock in the production of paper, the negative influence of the hardness forming agents in the paper production is thereby eliminated or reduced.
  • the use of the phosphonomethylated polyamines to be used according to the invention together with wetting agents has proven useful in the continuous washing of felt. Precipitations of hardness formers with resin glue or cellulose resin and precipitation products of aluminum sulfate are dissolved, so that laying of the wet felts of the paper machines is largely prevented. This keeps the felts drained for a longer period of time.
  • the reaction mixture is stirred at 110 ° C. for a further 20 h.
  • about 170 g of water are distilled off from it under vacuum and the remaining solution is dropped into a methanolic sodium hydroxide solution for precipitation.
  • the amount of sodium hydroxide used corresponds to the acid
  • Example 1 was repeated with the only exception that complexing agent II was now used.
  • the whiteness of the leaves made from the bleached wood pulp was 65.2%.
  • Example 1 was repeated with the only exception that 2% water glass was now used as the complexing agent instead of the complexing agent I.
  • the whiteness of the sheets obtained from the bleached wood pulp was 65.2%.
  • Comparative example 1 was repeated with the only exception that 0.2% diethylene triamine penta acetate in the form of the sodium salt was used instead of water glass. The whiteness of the leaves obtained from the bleached wood pulp was 65.5%.
  • Example 3
  • the bag is placed in a water bath at a temperature of 60 ° C. for 1 h.
  • the bleached wood pulp suspension is then turned into paper sheets with a weight per unit area on a Rapid Koethen sheet former
  • Example 1 35 400 g / m 2 produced and - as indicated in Example 1 - determined the whiteness of the paper sheets.
  • the paper whiteness was 64.1%. Paper sheets with a whiteness of 54.2% were obtained from the unbleached paper stock.
  • Example 3 was repeated with the only exception that complex complexing agent II was now used instead of the complexing agent used there.
  • the whiteness of sheets of paper made from 45 bleached wood chips is 63.8%. Comparative Example 3
  • Example 3 is repeated with the only exception that 0.06% diethylenetriaminepentaacetate is now used as the complexing agent.
  • the whiteness of sheets of paper made from a wood pulp bleached in this way is 62.8%.
  • the measured values given in examples and comparative examples are average values from 10 individual measurements.
  • An effect advantage for a complexing agent of at least 0.5 percentage points in the degree of whiteness can already be described as significant.
  • the adsorption behavior of the phosphonomethylated polyethyleneimines on the sewage sludge in sewage treatment plants has proven to be particularly advantageous. They can thus be largely removed from the wastewater from paper factories.
  • a static adsorption test was carried out to determine the adsorption potential of the phosphonomethylated polyethyleneimines on the activated sludge.
  • the DOC determination i.e. determination of the dissolved organic carbon
  • the complexing agent I had a DOC adsorption degree of approximately 90%, largely independent of the initial concentration, after a dwell time of 3 h.

Abstract

The use of aminomethylene phosphonic group-containing polymers and their alkaline metal or ammonium salts and the N-oxides derived therefrom and polyammonium salts obtainable by alkylisation as complexing agents for alkaline earth metal and heavy metal ions in wood-pulp bleaching, cellulose bleaching, cellulose production, papermaking, textile refinement and the de-inking of printed waste paper.

Description

Verwendung von Aminomethylenphosphonogruppen enthaltenden Polyme¬ ren als KomplexbildnerUse of aminomethylenephosphono-containing polymers as complexing agents
Beschreibungdescription
Die Erfindung betrifft die Verwendung von Aminomethylenphosphono¬ gruppen enthaltenden Polymeren und deren Alkalimetall- oder Ammoniumsalzen als Komplexbildner für Erdalkalimetall- und Schwermetallionen bei der Holzschliffbleiche, der Zellstoffblei¬ che, der Zellstoffherstellung, der Papierherstellung, der Textil¬ veredlung und dem Deinking von bedrucktem Altpapier.The invention relates to the use of polymers containing aminomethylenephosphono groups and their alkali metal or ammonium salts as complexing agents for alkaline earth metal and heavy metal ions in pulp bleaching, cellulose bleaching, cellulose production, paper production, textile finishing and deinking of printed waste paper.
Sowohl bei der oxidativen als auch bei der reduktiven Bleiche von Faserstoffen, die für die Herstellung von Papier eingesetzt wer¬ den, insbesondere von Holzschliff, ist es üblich, Komplexbildner zu verwenden. Ihre wesentliche Aufgabe besteht darin, störende Metallionen zu komplexieren. Komplexbildner, die u.a. auch in der Papierindustrie angewendet werden, sind beispielsweise Nitrilo- triessigsäure, Ethylendiamintetraessigsäure und Ethylendiamin- tetramethylenphosphonsäure.It is customary to use complexing agents both in the oxidative and in the reductive bleaching of fibrous materials which are used for the production of paper, in particular wood pulp. Their main task is to complex interfering metal ions. Complexing agents, which also used in the paper industry are, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediaminetetramethylenephosphonic acid.
Die aus der WO-A-91/02011 bekannten phosphonomethylierten Poly- vinylamine und die in der DE-A-41 28 510 beschriebenen phosphono- methylierten Polyacrylamide werden als Scaleinhibitoren und als Zusatz zu Wasch- und Reinigungsmitteln verwendet.The phosphonomethylated polyvinylamines known from WO-A-91/02011 and the phosphonomethylated polyacrylamides described in DE-A-41 28 510 are used as scale inhibitors and as additives to detergents and cleaning agents.
Aus der EP-B-0 444 542 ist die Verwendung von N-Oxiden und von alkylierten phosphonomethylierten Polyethyleniminen als Dispergiermittel für hydraulischen Zement enthaltende wäßrige Ze¬ mentzusammensetzungen bekannt.EP-B-0 444 542 discloses the use of N-oxides and of alkylated phosphonomethylated polyethyleneimines as dispersants for aqueous cement compositions containing hydraulic cement.
Der Erfindung liegt die Aufgabe zugrunde, neue Komplexbildner für die Papierindustrie, die Zellstoffindustrie, die Textilveredlung und das Deinking von bedrucktem Altpapier zur Verfügung zu stel¬ len.The invention has for its object to provide new complexing agents for the paper industry, the pulp industry, textile finishing and deinking of printed waste paper.
Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von Aminomethylenphosphonogruppen enthaltenden Polymeren und deren Alkalimetall- oder Ammoniumsalzen und der davon abgeleiteten N- Oxide und der daraus durch Alkylierung erhältlichen Polyammonium- salze als Komplexbildner für Erdalkalimetall- und Schwermetall¬ ionen bei der Holzschliffbleiche, der Zellstoffbleiche, der Zell¬ stoffherstellung, der Papierherstellung, der Textilveredlung und dem Deinking von bedrucktem Altpapier. Aminomethylenphosphonogruppen enthaltende Polymere sind dadurch erhältlich, daß man Polymerisate, die phosphonomethylierbareThe object is achieved according to the invention with the use of polymers containing aminomethylene phosphono groups and their alkali metal or ammonium salts and the N-oxides derived therefrom and the polyammonium salts obtainable therefrom by alkylation as complexing agents for alkaline earth metal and heavy metal ions in pulp bleaching, pulp bleaching, cellulose production, paper production, textile finishing and deinking of printed waste paper. Polymers containing aminomethylene phosphono groups can be obtained by polymerizing the phosphonomethylatable
Stickstoffatome in der Hauptkette oder aber auch als Seitenket- tenfunktion tragen und die z.B. in Form von primären oder sekun- dären Aminen, primären oder sekundären Amiden, bzw. Sulfonamiden oder auch als Harnstoff-Strukturen vorliegen können, einer Phos- phonomethylierung unterzieht.Nitrogen atoms in the main chain or also as a side chain function and which e.g. in the form of primary or secondary amines, primary or secondary amides, or sulfonamides or also as urea structures, is subjected to a phosphonomethylation.
Für den erfindungsgemäßen Einsatzzweck sind zum Beispiel die in der WO-A-91/02011 beschriebenen phosphonomethylierten Polyvinyl- amine bzw. Vinylamineinheiten enthaltenden Copolymere geeignet. Außerdem kommen die daraus durch Alkylierung erhältlichen quartä- ren Ammoniumsalze sowie die entsprechenden N-Oxide und die aus der DE-A-41 28 510 bekannten Polyacrylamide in Betracht.For example, the phosphonomethylated polyvinylamines or copolymers containing vinylamine units described in WO-A-91/02011 are suitable for the purpose of use according to the invention. In addition, the quaternary ammonium salts obtainable therefrom by alkylation and the corresponding N-oxides and the polyacrylamides known from DE-A-41 28 510 are also suitable.
Für die erfindungsgemäße Verwendung eignen sich auch phosphonome- thylierte Polyamine sowie davon abgeleitete N-Oxide und durch Quaternierung erhältliche Ammoniumsalze. Solche Verbindungen sind beispielsweise aus der oben genannten EP-B 0 444 542 bekannt. Sie werden durch Phosphonomethylierung von Polyaminen hergestellt. Als Polyamine kommen beispielsweise alle Verbindungen in Be¬ tracht, die mindestens so viele basische, phosphonomethylierbare Stickstoffatome im Molekül enthalten, daß die daraus erhältlichen Aminomethylenphosphonate Komplexbildnereigenschaften besitzen. Zu den Polyaminen gehören auch Polyallylamine. Die Molmasse der Po¬ lyamine beträgt beispielsweise mindestens 200, vorzugsweise 500 bis 2 Millionen.Phosphonomethylated polyamines and N-oxides derived therefrom and ammonium salts obtainable by quaternization are also suitable for the use according to the invention. Such compounds are known for example from the above-mentioned EP-B 0 444 542. They are made by phosphonomethylation of polyamines. Examples of suitable polyamines are all compounds which contain at least as many basic, phosphonomethylatable nitrogen atoms in the molecule that the aminomethylene phosphonates obtainable therefrom have complexing properties. The polyamines also include polyallylamines. The molar mass of the polyamines is, for example, at least 200, preferably 500 to 2 million.
Besonders bevorzugt man als Komplexbildner phosphonomethylierte Polyethylenimine oder deren Alkalimetall- oder Ammoniumsalze. Diese Produkte werden z.B. erhalten, indem man Polyethylenimine phosphonomethyliert. Polyethylenimine werden bekann erweise durch Polymerisieren von Ethylenimin in Gegenwart von Säuren, Bortri- fluorid oder Halogenkohlenwasserstoffen wie Tetrachlorkohlen- Stoff, Chloroform, Methylenchlorid, Ethylenchlorid oder Ethyl- bromid als Katalysator hergestellt. Die Polyethylenimine haben Molmassen von 200 bis 2 Mio, vorzugsweise 500 bis 1,2 Mio. Poly¬ merisate dieser Art sind im Handel erhältlich. Sie enthalten S ruktureinheiten der Formel -CH2-CH2-N- ( I ) ,Phosphonomethylated polyethyleneimines or their alkali metal or ammonium salts are particularly preferred as complexing agents. These products are obtained, for example, by phosphonomethylating polyethyleneimines. Polyethyleneimines are known to be produced by polymerizing ethyleneimine in the presence of acids, boron trifluoride or halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, ethylene chloride or ethyl bromide as a catalyst. The polyethyleneimines have molecular weights of 200 to 2 million, preferably 500 to 1.2 million, polymers of this type are commercially available. They contain structural units of the formula -CH 2 -CH 2 -N- (I),
H die durch Phosphonomethylierung in Einheiten der FormelH by phosphonomethylation in units of the formula
Figure imgf000005_0001
in der Me = H, Alkalimetall- oder Ammoniumäquivalent bedeuten, überführt werden.
Figure imgf000005_0001
in which Me = H, alkali metal or ammonium equivalent, are transferred.
Auch die von den Einheiten II abgeleiteten N-Oxide der FormelThe N-oxides of the formula derived from units II
Figure imgf000005_0002
Figure imgf000005_0002
in der Me die in Formel II angegebene Bedeutung hat, und die durch Alkylierung aus den Verbindungen, die Einheiten der For¬ mel II enthalten, entstehenden Polyammoniumsalze mit Einheiten der Formelin which Me has the meaning given in formula II, and the polyammonium salts formed by alkylation from the compounds which contain units of the formula II with units of the formula
Figure imgf000005_0003
Figure imgf000005_0003
in der Me die in Formel II angegebene Bedeutung hat und Alkyl = Ci- bis Cio-Alkyl oder substituiertes Alkyl wie Benzyl oder Carboxyalkyl wie Carboxymethyl und X = ein Anion wie Cl_, Br_, J-, CH3-0-S03 ~ oder C2H5-0-S03" bedeutet, kommen für den erfindungs¬ gemäßen Einsatz in Betracht. Die phosphonomethylierten Verbindungen werden beispielsweise in Mengen von 0,02 bis 0,5, vorzugsweise 0,1 bis 0,3 Gew.-%, bezogen auf trockenen Faser¬ stoff, als Komplexbildner angewendet.in which Me has the meaning given in formula II and alkyl = Ci to Cio-alkyl or substituted alkyl such as benzyl or carboxyalkyl such as carboxymethyl and X = an anion such as Cl _ , Br _ , J-, CH 3 -0-S0 3rd ~ or C 2 H 5 -0-S0 3 "means are suitable for the use according to the invention. The phosphonomethylated compounds are used, for example, in amounts of 0.02 to 0.5 preferably 0.1 to 0.3% by weight, based on dry fiber material, is used as the complexing agent.
Die Aminomethylenphosphonogruppen enthaltenden Polymeren und deren Alkalimetall- und Ammoniumsalze haben z.B. einen Gehalt an organisch gebundenem Phosphor von 0,005 bis 20, vorzugsweise 0,01 bis 18 Gew.-%.The polymers containing aminomethylene phosphono groups and their alkali metal and ammonium salts have e.g. an organically bound phosphorus content of 0.005 to 20, preferably 0.01 to 18,% by weight.
Die oben beschriebenen polymeren Komplexbildner, die alle Phos- phonomethylgruppen enthalten, werden bei der Holzschliffbleiche, der Zellstoffbleiche, der Zellstoffherstellung, der Papierher¬ stellung, der Textilveredlung und dem Deinking von bedrucktem Altpapier verwendet. Die bei der Papierherstellung eingesetzten technischen Rohstoffe und Hilfsstoffe enthalten meistens Spuren von Schwermetallen, vor allem Eisen- und Manganionen. Schwer bleichbare Holzschliffe und andere Papierrohstoffe, wie thermome- chanischer Stoff (TMP) und chemothermomechanischer Stoff (CTMP), enthalten oft sogar unverhältnismäßig viel Eisenionen. Im Gegen¬ satz zu Eisen-II-Ionen reagieren Eisen-III-Ionen mit Bestandtei- len des Holzes unter Bildung dunkel gefärbter Verbindungen. Durch den unmittelbaren Einsatz von Komplexbildnern bei der Herstellung der Papierrohstoffe, insbesondere bei der Holzschliffbleiche, kann bereits eine Aufhellung des Papierrohstoffs erzielt werden, so daß nach beendeter Bleiche der Weißgrad um etwa 2 bis 3 Punkte höher liegt als ohne Verwendung von Komplexbildnern. Durch Zusatz der erfindungsgemäß zu verwendenden polymeren Komplexbildner er¬ zielt man bei der oxidativen, reduktiven oder kombinierten Blei¬ che eine Weißgradsteigerung gegenüber solchen Stoffen, die keine Komplexbildner enthalten. Verfahren zur reduktiven Holzschliff- bleiche mit Dithionit und zur oxidativen Bleiche mit Wasserstoff¬ peroxid sind bekannt, vgl. H. Schröter, Die Holzschliffbleiche, Günter-Staib-Verlag, Biberach an der Riß, 1976.The above-described polymeric complexing agents, which contain all phosphonomethyl groups, are used in wood pulp bleaching, cellulose bleaching, cellulose production, paper production, textile finishing and deinking of printed waste paper. The technical raw materials and auxiliary materials used in paper production mostly contain traces of heavy metals, especially iron and manganese ions. Wood chips that are difficult to bleach and other paper raw materials, such as thermomechanical material (TMP) and chemothermomechanical material (CTMP), often contain a disproportionate amount of iron ions. In contrast to iron-II ions, iron-III ions react with parts of the wood to form dark-colored compounds. Through the direct use of complexing agents in the production of the paper raw materials, in particular in the pulp bleaching process, a lightening of the paper raw material can already be achieved, so that the whiteness after the bleaching is about 2 to 3 points higher than without the use of complexing agents. By adding the polymeric complexing agents to be used according to the invention, the whiteness of the oxidative, reductive or combined lead is increased compared to those substances which do not contain any complexing agents. Processes for reductive pulp bleaching with dithionite and for oxidative bleaching with hydrogen peroxide are known, cf. H. Schröter, Die Holzschliffbleiche, Günter-Staib-Verlag, Biberach an der Riß, 1976.
Auch bei der oxidativen Bleiche mit wäßrigen Peroxidlösungen wir- ken bereits Spuren von Schwermetallionen störend, weil sie die wäßrigen Peroxidlösungen zersetzen. Zur Stabilisierung der Per¬ oxidlösungen verwendet man deshalb üblicherweise beim Ansetzen der Bleichlösungen größere Mengen an Wasserglas als Stabilisator. Der Einsatz von Wasserglas führt jedoch zu einer Verschlechterung der Entwässerung des gebleichten Papierstoffs und kann darüber hinaus Ablagerungen auf dem Papier und den Filzen an der Papier¬ maschine verursachen. Das in den Bleichlösungen vorhandene Was¬ serglas kann durch die erfindungsgemäß zu verwendenden Verbindungen ersetzt werden, so daß man ein Bleichergebnis er- zielt, das dem Bleichergebnis entspricht, das mit üblichen Mengen an Wasserglas in der Bleichlösung erhalten wird. Die Verwendung der erfindungsgemäß einzusetzenden Verbindungen in Bleichlösungen führt außerdem zu einer Einsparung von Wasserstoffperoxid bei der oxidativen Bleiche. Die erfindungsgemäß zu verwendenden Verbindungen eignen sich daher ebenfalls als Komplexbildner bei der Textilveredlung, insbesondere bei der Vorbehandlung, z.B. der Vorwäsche und Vorreinigung, Entschlichtung, alkalischer Abkochung und Wasserstoffperoxidbleiche von Textilmaterial aller Art, vor¬ zugsweise von Baumwolle enthaltenden textilen Materialien. Unter textilen Materialien werden z.B. Garne, Gewebe, Vliese oder Ge¬ wirke verstanden.Even with oxidative bleaching with aqueous peroxide solutions, traces of heavy metal ions already have a disruptive effect because they decompose the aqueous peroxide solutions. To stabilize the peroxide solutions, larger amounts of water glass are therefore usually used as a stabilizer when preparing the bleaching solutions. However, the use of water glass leads to a deterioration in the dewatering of the bleached paper stock and can also cause deposits on the paper and the felts on the paper machine. The water glass present in the bleaching solutions can be replaced by the compounds to be used according to the invention, so that a bleaching result is obtained which corresponds to the bleaching result obtained with conventional amounts of waterglass in the bleaching solution. The use of the compounds to be used according to the invention in bleaching solutions also saves hydrogen peroxide in oxidative bleaching. The compounds to be used according to the invention are therefore also suitable as complexing agents in textile finishing, in particular in pretreatment, for example prewashing and pre-cleaning, desizing, alkaline decoction and hydrogen peroxide bleaching of textile materials of all kinds, preferably textile materials containing cotton. Textile materials are understood to mean, for example, yarns, woven fabrics, nonwovens or knitted fabrics.
Auch beim Deinken von bedrucktem Altpapier, das hauptsächlich mit einer Kombination aus Peroxid, Natriumhydroxid, Wasserglas, Dispergiermittel und Sammler behandelt wird, kann man je nach Rohstoffqualität bis zu 100 Gew.-% der sonst üblichen Wasserglas- menge einsparen, wenn man die erfindungsgemäß zu verwendenden Verbindungen einsetzt. Außerdem kann man einen signifikanten Anteil an Wasserstoffperoxid einsparen, ohne eine Einbuße an Weißgrad beim deinkten Altpapier hinnehmen zu müssen.Even when deinking printed waste paper, which is mainly treated with a combination of peroxide, sodium hydroxide, water glass, dispersant and collector, depending on the quality of the raw material, you can save up to 100% by weight of the usual amount of water glass if you add the amount according to the invention uses connections. You can also save a significant amount of hydrogen peroxide without sacrificing whiteness in deinked waste paper.
Aufgrund der immer stärkeren Schließung des Wasserkreislaufes der Papiermaschinen findet darin eine stetige Anreicherung von Härte- bildnern statt. Dies kann u.a. zu einer Ausfällung von Carbonaten und Silikaten führen, wodurch die Papiereigenschaften unmittelbar beeinträchtigt werden können, z.B. Festigkeit, Saugfähigkeit, Anfärbbarkeit und das Staubverhalten des Papiers. Die Härte¬ bildner können außerdem die Wirksamkeit von Hilfsmitteln und die Eigenschaften von Farbstoffen beeinträchtigen. Wenn man die erfindungsgemäß als Komplexbildner zu verwendenden phosphonome¬ thylierten Polyamine und ihre Derivate, die Einheiten der For- mein II, III oder IV enthalten, bei der Herstellung von Papier dem Papierstoff zusetzt, so wird dadurch der negative Einfluß der Härtebildner bei der Papierherstellung beseitigt bzw. vermindert. Darüber hinaus hat sich der Einsatz der erfindungsgemäß zu ver¬ wendenden phosphonomethylierten Polyamine zusammen mit Netzmit- teln bei der kontinuierlichen Filzwäsche bewährt. Ausfällungen von Härtebildnern mit Harzleim bzw. Zellstoffharz und Fällungs¬ produkten des Aluminiumsulfats werden aufgelöst, so daß ein Ver¬ legen der Naßfilze der Papiermaschinen weitgehend verhindert wird. Die Entwässerungsfähigkeit der Filze bleibt dadurch über einen längeren Zeitraum erhalten.Due to the ever increasing closing of the water cycle of the paper machines, there is a constant accumulation of hardness builders. This can include lead to precipitation of carbonates and silicates, which can have a direct impact on paper properties, e.g. Strength, absorbency, dyeability and the dust behavior of the paper. The hardening agents can also impair the effectiveness of auxiliaries and the properties of dyes. If the phosphonomethylated polyamines and their derivatives which contain units of form II, III or IV to be used according to the invention as complexing agents are added to the paper stock in the production of paper, the negative influence of the hardness forming agents in the paper production is thereby eliminated or reduced. In addition, the use of the phosphonomethylated polyamines to be used according to the invention together with wetting agents has proven useful in the continuous washing of felt. Precipitations of hardness formers with resin glue or cellulose resin and precipitation products of aluminum sulfate are dissolved, so that laying of the wet felts of the paper machines is largely prevented. This keeps the felts drained for a longer period of time.
Die Prozentangaben in den Beispielen bedeuten Gew.-%. BeispieleThe percentages in the examples mean% by weight. Examples
Herstellung von phosphonomethylierten PolyethyleniminenManufacture of phosphonomethylated polyethyleneimines
5 Koπrplexbildner I5 complexing agents I
In einem Mehrhalskolben, der mit Rührer, Rückflußkühler, Innen¬ thermometer und Tropftrichter ausgestattet ist, werden 220 g eines Polyethylenimins der Molmasse von 2000 g/mol in Form einerIn a multi-necked flask equipped with a stirrer, reflux condenser, internal thermometer and dropping funnel, 220 g of a polyethyleneimine with a molecular weight of 2000 g / mol are in the form of a
10 50 %igen wäßrigen Lösung vorgelegt und mit 380 g einer 60 %igen wäßrigen Schwefelsäure versetzt. Nach Zugabe von 205 g phosphori- ger Säure wird das Reaktionsgemisch auf ca. 100°C erhitzt. Sobald diese Temperatur erreicht ist, tropft man 205 g einer wäßrigen 36,5 %igen Formaldehydlösung langsam zu. Nach beendeter Zugabe10 50% aqueous solution presented and mixed with 380 g of a 60% aqueous sulfuric acid. After 205 g of phosphoric acid have been added, the reaction mixture is heated to about 100.degree. As soon as this temperature is reached, 205 g of an aqueous 36.5% formaldehyde solution are slowly added dropwise. After the addition is complete
15 der Formaldehydlösung wird das Reaktionsgemisch noch 20 h bei 110°C gerührt. Um das Reaktionsgemisch aufzuarbeiten, destilliert man daraus unter Vakuum ca. 170 g Wasser ab und tropft die ver¬ bleibende Lösung zur Fällung in eine methanolische Natronlauge. Die eingesetzte Menge an Natronlauge entspricht dabei dem Säure-15 of the formaldehyde solution, the reaction mixture is stirred at 110 ° C. for a further 20 h. In order to work up the reaction mixture, about 170 g of water are distilled off from it under vacuum and the remaining solution is dropped into a methanolic sodium hydroxide solution for precipitation. The amount of sodium hydroxide used corresponds to the acid
20 zahläquivalent der eingeengten Reaktionsmischung. Das in Form des Natriumsalzes ausfallende Polymere wird abfiltriert, mit Methanol gewaschen und anschließend getrocknet. Der Phosphorgehalt des Po¬ lymeren betrug 16,2 %.20 number equivalent of the concentrated reaction mixture. The polymer precipitating in the form of the sodium salt is filtered off, washed with methanol and then dried. The phosphorus content of the polymer was 16.2%.
25 Komplexbildner II25 complexing agent II
Man verfährt wie bei der Herstellung des Komplexbildners I be¬ schrieben, jedoch mit der einzigen Ausnahme, daß man ein Poly- ethylenimin mit einer mittleren Molmasse von 1,2 Millionen g/mol 30 einsetzt. Man erhält ein phosphonomethyliertes Polyethylenimin mit einem Gehalt an organisch gebundenem Phosphor von 15,9 %.The procedure is as described for the preparation of complexing agent I, but with the only exception that a polyethyleneimine with an average molar mass of 1.2 million g / mol 30 is used. A phosphonomethylated polyethyleneimine with an organically bound phosphorus content of 15.9% is obtained.
Beispiel 1example 1
35 100 g einer HolzschliffSuspension mit einer Stoffdichte von35 100 g of a wood pulp suspension with a consistency of
20 Gew.-% werden in einen Beutel aus Polyethylen gefüllt und je¬ weils, bezogen auf das Gewicht des trockenen Holzschliffs, mit 0,75 % Natronlauge, 1 % Wasserstoffperoxid und 0,2 % Komplexbild¬ ner I versetzt. Der Beutel wird dann verschlossen und der Inhalt20% by weight are filled into a polyethylene bag and, based on the weight of the dry wood pulp, 0.75% sodium hydroxide solution, 1% hydrogen peroxide and 0.2% complexing agent I are added. The bag is then closed and the contents
40 durch intensives Kneten des Beutels homogenisiert. Anschließend hängt man den Beutel 2 h in ein auf 50°C temperiertes Wasserbad. Zur Bestimmung des Bleichergebnisses bildet man aus dem gebleich¬ ten Stoff auf einem Rapid-Köthen-Blattbildner jeweils 2 Blatter mit einem Flächengewicht von 400 g/m2, trocknet die Blätter und40 homogenized by intensive kneading of the bag. The bag is then suspended in a water bath at 50 ° C. for 2 hours. To determine the bleaching result, 2 sheets each with a basis weight of 400 g / m 2 are formed from the bleached substance on a Rapid-Köthen sheet former, the sheets are dried and
45 bestimmt die Weiße der Papierblätter mit einem Elrepho-Photometer bei einer Wellenlänge von 457 nm als Prozent Remissionsgrad. Die Weiße der Papierblätter betrug bei diesem Beispiel 65,6 %. Der ungebleichte Papierstoff ergab Blätter einer Weiße von 55,2 %.45 determines the whiteness of the paper sheets with an Elrepho photometer at a wavelength of 457 nm as a percentage reflectance. The Whiteness of the paper sheets was 65.6% in this example. The unbleached paper stock gave sheets of 55.2% whiteness.
Beispiel 2 5Example 2 5
Das Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, daß man jetzt den Komplexbildner II einsetzte. Die Weiße der aus dem gebleichten Holzschliff hergestellten Blätter betrug 65,2 %.Example 1 was repeated with the only exception that complexing agent II was now used. The whiteness of the leaves made from the bleached wood pulp was 65.2%.
10 Vergleichsbeispiel 110 Comparative Example 1
Das Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, daß man jetzt als Komplexbildner 2 % Wasserglas anstelle des Komplex¬ bildners I einsetzte. Die Weiße der dabei erhaltenen Blatter aus 15 dem gebleichtem Holzschliff betrug 65,2 %.Example 1 was repeated with the only exception that 2% water glass was now used as the complexing agent instead of the complexing agent I. The whiteness of the sheets obtained from the bleached wood pulp was 65.2%.
Vergleichsbeispiel 2Comparative Example 2
Das Vergleichsbeispiel 1 wurde mit der einzigen Ausnahme wieder- 20 holt, daß man anstelle von Wasserglas 0,2 % Diethylentriaminpen- taacetat in Form des Natriumsalzes einsetzte. Die Weiße der aus dem gebleichten Holzschliff erhaltenen Blätter betrug 65,5 %. Beispiel 3Comparative example 1 was repeated with the only exception that 0.2% diethylene triamine penta acetate in the form of the sodium salt was used instead of water glass. The whiteness of the leaves obtained from the bleached wood pulp was 65.5%. Example 3
25 100 g einer HolzschliffSuspension mit einer Stoffdichte von25 100 g of a wood pulp suspension with a consistency of
4 Gew.-% werden in einen Beutel aus Polyethylen gefüllt und mit, jeweils bezogen auf trockenen Holzschliff, 1 Gew.-% Natriumdi- thionit und 0,06 % Komplexbildner I versetzt. Der pH-Wert der Holzschliffaufschlä mung beträgt 6. Der Beutel wird dann ver-4% by weight are filled into a polyethylene bag and mixed with 1% by weight sodium di-thionite and 0.06% complexing agent I, based on dry wood pulp. The pH value of the wood pulp slurry is 6. The bag is then sealed
30 schlössen und der Inhalt durch intensives Kneten homogenisiert. Der Beutel wird nach dem Durchmischen des Inhalts für 1 h in ein Wasserbad eingebracht, das eine Temperatur von 60°C hat. Danach werden aus der gebleichten Holzschliffsuspension auf einem Rapid- Köthen-Blatt-Bildner Papierblatter mit einem Flächengewicht von30 locks and the contents homogenized by intensive kneading. After the contents have been mixed, the bag is placed in a water bath at a temperature of 60 ° C. for 1 h. The bleached wood pulp suspension is then turned into paper sheets with a weight per unit area on a Rapid Koethen sheet former
35 400 g/m2 hergestellt und - wie in Beispiel 1 angegeben - die Weiße der Papierblätter bestimmt. Die Papierweiße betrug 64,1 %. Aus dem ungebleichten Papierstoff erhielt man Papierblätter mit einer Weiße von 54,2 %.35 400 g / m 2 produced and - as indicated in Example 1 - determined the whiteness of the paper sheets. The paper whiteness was 64.1%. Paper sheets with a whiteness of 54.2% were obtained from the unbleached paper stock.
40 Beispiel 440 Example 4
Das Beispiel 3 wurde mit der einzigen Ausnahme wiederholt, daß man anstelle des dort verwendeten Komplexbildners jetzt den Kom¬ plexbildner II einsetzte. Die Weiße von Papierblattern, die aus 45 dem gebleichten Holzschliff hergestellt werden, beträgt 63,8 %. Vergleichsbeispiel 3Example 3 was repeated with the only exception that complex complexing agent II was now used instead of the complexing agent used there. The whiteness of sheets of paper made from 45 bleached wood chips is 63.8%. Comparative Example 3
Das Beispiel 3 wird mit der einzigen Ausnahme wiederholt, daß man jetzt 0,06 % Diethylentriaminpentaacetat als Komplexbildner verwendet. Die Weiße von Papierblättern, die aus einem in dieser Weise gebleichten Holzschliff hergestellt werden, beträgt 62,8 %.Example 3 is repeated with the only exception that 0.06% diethylenetriaminepentaacetate is now used as the complexing agent. The whiteness of sheets of paper made from a wood pulp bleached in this way is 62.8%.
Die Ergebnisse der Beispiele zeigen, daß phosphonomethylierte Polyethylenimine sowohl bei der oxidativen als auch bei der re- duktiven Bleiche wirksame Komplexbildner sind. Bei den in denThe results of the examples show that phosphonomethylated polyethyleneimines are effective complexing agents in both oxidative and reductive bleaching. In the in the
Beispielen und Vergleichsbeispielen angegebenen Meßwerten handelt es sich jeweils um Mittelwerte aus 10 Einzelmessungen. Ein Wir¬ kungsvorteil für einen Komplexbildner von mindestens 0,5 Prozent¬ punkten im Weißegrad ist bereits als signifikant zu bezeichnen.The measured values given in examples and comparative examples are average values from 10 individual measurements. An effect advantage for a complexing agent of at least 0.5 percentage points in the degree of whiteness can already be described as significant.
Als besonders vorteilhaft hat sich das Adsorptionsverhalten der phosphonomethylierten Polyethylenimine am Klärschlamm in Kläran¬ lagen erwiesen. Sie können somit aus dem Abwasser von Papierfa¬ briken weitestgehend entfernt werden. Um das Adsorptionspotential der phosphonomethylierten Polyethylenimine am Belebtschlamm zu ermitteln, wurde ein statischer Adsorptionstest durchgeführt. Die DOC-Bestimmung (d.h. Bestimmung des gelösten organischen Kohlen¬ stoffs) erfolgte dabei nach DIN 38409, Teil 3 (1983). Nach diesem Test ergab sich zum Beispiel für den Komplexbildner I nach einer Verweilzeit von 3 h ein von der Ausgangskonzentration weitgehend unabhängiger DOC-Adsorptionsgrad von ca. 90 %. The adsorption behavior of the phosphonomethylated polyethyleneimines on the sewage sludge in sewage treatment plants has proven to be particularly advantageous. They can thus be largely removed from the wastewater from paper factories. A static adsorption test was carried out to determine the adsorption potential of the phosphonomethylated polyethyleneimines on the activated sludge. The DOC determination (i.e. determination of the dissolved organic carbon) was carried out in accordance with DIN 38409, Part 3 (1983). According to this test, for example, the complexing agent I had a DOC adsorption degree of approximately 90%, largely independent of the initial concentration, after a dwell time of 3 h.

Claims

Patentansprüche claims
1. Verwendung von Aminomethylenphosphonogruppen enthaltenden Po- lymeren und deren Alkalimetall- oder A moniumsalzen und der davon abgeleiteten N-Oxide und der daraus durch Alkylierung erhältlichen Polyammoniumsalze als Komplexbildner für Erd¬ alkalimetall- und Schwermetallionen bei der Holzschliff¬ bleiche, der Zellstoffbleiche, der Zellstoffherstellung, der Papierherstellung, der Textilveredlung und dem Deinking von bedrucktem Altpapier.1. Use of polymers containing aminomethylene phosphono groups and their alkali metal or ammonium salts and the N-oxides derived therefrom and the polyammonium salts obtainable therefrom by alkylation as complexing agents for alkaline earth metal and heavy metal ions in pulp bleaching, pulp bleaching and pulp production , paper production, textile finishing and deinking of printed waste paper.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man als Komplexbildner phosphonomethylierte Polyethylenimine oder deren Alkalimetall- oder Ammoniumsalze einsetzt.2. Use according to claim 1, characterized in that phosphonomethylated polyethyleneimines or their alkali metal or ammonium salts are used as complexing agents.
3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man phosphonomethylierte Polyethylenimine oder deren Alkali¬ metall- oder Ammoniumsalze als Komplexbildner bei der Holz- schliffbleiche einsetzt.3. Use according to claim 1, characterized in that one uses phosphonomethylated polyethyleneimines or their alkali metal or ammonium salts as complexing agents in wood pulp bleaching.
4. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man phosphonomethylierte Polyethylenimine oder deren Alkali¬ metall- oder Ammoniumsalze als Komplexbildner bei der Textil- Veredlung einsetzt. 4. Use according to claim 1, characterized in that one uses phosphonomethylated polyethyleneimines or their alkali metal or ammonium salts as complexing agents in textile finishing.
PCT/EP1996/000862 1995-03-13 1996-03-01 Use of aminomethylene phosphono group-containing polymers as complexing agents WO1996028605A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103328455A (en) * 2010-12-13 2013-09-25 巴斯夫欧洲公司 Bleach catalysts

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000059965A1 (en) * 1999-04-06 2000-10-12 Minerals Technologies Inc. Bifunctional polymers
US7169257B2 (en) 2003-11-12 2007-01-30 Kemira Chemicals, Inc. Method of deinking waste paper using a reduced alkali system

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885069A (en) * 1972-08-11 1975-05-20 Us Agriculture Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine
US4035412A (en) * 1971-05-28 1977-07-12 Petrolite Corporation Methylene phosphonates of poly-diepoxidized polyalkylene polyamines
US4064044A (en) * 1971-07-06 1977-12-20 Petrolite Corporation Process for chelating and inhibiting scale in aqueous systems
US4080375A (en) * 1971-02-05 1978-03-21 Petrolite Corporation Methylene phosphonates of amino-terminated oxyalkylates and uses therefor
DE3101939A1 (en) * 1981-01-22 1982-07-29 Benckiser-Knapsack Gmbh, 6802 Ladenburg Polymeric aminophosphonocarboxylic acids, alkali metal salts thereof, and the use thereof
WO1991002011A1 (en) * 1989-08-07 1991-02-21 Basf Aktiengesellschaft Phosphonomethylated polyvinyl amines, process for preparing them and their use
EP0444542A1 (en) * 1990-03-02 1991-09-04 BASF Corporation Cementing compositions containing polyethyleneimine phosphonate derivatives as dispersants
DE4128510A1 (en) * 1991-08-28 1993-03-04 Basf Ag New N-phosphono-methyl-polyacrylamide derivs. - useful as detergent additives and water treatment agents, with builder, complexing, bleach stabilising and scale inhibiting activities
WO1995002086A2 (en) * 1993-07-09 1995-01-19 The Dow Chemical Company Process for removing metal ions from liquids

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080375A (en) * 1971-02-05 1978-03-21 Petrolite Corporation Methylene phosphonates of amino-terminated oxyalkylates and uses therefor
US4035412A (en) * 1971-05-28 1977-07-12 Petrolite Corporation Methylene phosphonates of poly-diepoxidized polyalkylene polyamines
US4064044A (en) * 1971-07-06 1977-12-20 Petrolite Corporation Process for chelating and inhibiting scale in aqueous systems
US3885069A (en) * 1972-08-11 1975-05-20 Us Agriculture Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine
DE3101939A1 (en) * 1981-01-22 1982-07-29 Benckiser-Knapsack Gmbh, 6802 Ladenburg Polymeric aminophosphonocarboxylic acids, alkali metal salts thereof, and the use thereof
WO1991002011A1 (en) * 1989-08-07 1991-02-21 Basf Aktiengesellschaft Phosphonomethylated polyvinyl amines, process for preparing them and their use
EP0444542A1 (en) * 1990-03-02 1991-09-04 BASF Corporation Cementing compositions containing polyethyleneimine phosphonate derivatives as dispersants
DE4128510A1 (en) * 1991-08-28 1993-03-04 Basf Ag New N-phosphono-methyl-polyacrylamide derivs. - useful as detergent additives and water treatment agents, with builder, complexing, bleach stabilising and scale inhibiting activities
WO1995002086A2 (en) * 1993-07-09 1995-01-19 The Dow Chemical Company Process for removing metal ions from liquids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARK, H.F. ET AL: "Encyclopedia of polymer science and engineering - 2. Auflage, Band 3", 1985, JOHN WILEY & SONS, INC., NEW YORK, XP002005075 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103328455A (en) * 2010-12-13 2013-09-25 巴斯夫欧洲公司 Bleach catalysts
CN103328455B (en) * 2010-12-13 2016-02-24 巴斯夫欧洲公司 Bleaching catalyst

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