+

WO1996028605A1 - Utilisation de polymeres contenant des groupes aminomethylenephosphono en tant qu'agents complexants - Google Patents

Utilisation de polymeres contenant des groupes aminomethylenephosphono en tant qu'agents complexants Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
complexing agents
paper
bleaching
ammonium salts
aminomethylene
Prior art date
Application number
PCT/EP1996/000862
Other languages
German (de)
English (en)
Inventor
Knut Oppenländer
Wolfgang Günther
Jürgen Mohr
Friedrich Linhart
Rudolf Schuhmacher
Jaroslav Melzer
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
Publication of WO1996028605A1 publication Critical patent/WO1996028605A1/fr

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

Des polymères, contenant des groupes aminométhylènephosphono, leurs sels de métaux alcalins ou d'ammonium ainsi que des oxydes d'azotes dérivés de ces composés, et des sels de polyammonium obtenus par alkylation, sont utilisés en tant qu'agents complexants destinés à des ions de métaux alcalinoterreux et de métaux lourds pour le blanchiment de pâte mécanique et de cellulose, la fabrication de la cellulose et du papier, l'ennoblissement de textiles et le désencrage de vieux papiers imprimés.
PCT/EP1996/000862 1995-03-13 1996-03-01 Utilisation de polymeres contenant des groupes aminomethylenephosphono en tant qu'agents complexants WO1996028605A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995108936 DE19508936A1 (de) 1995-03-13 1995-03-13 Komplexbildner für Papierindustrie
DE19508936.7 1995-03-13

Publications (1)

Publication Number Publication Date
WO1996028605A1 true WO1996028605A1 (fr) 1996-09-19

Family

ID=7756487

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/000862 WO1996028605A1 (fr) 1995-03-13 1996-03-01 Utilisation de polymeres contenant des groupes aminomethylenephosphono en tant qu'agents complexants

Country Status (2)

Country Link
DE (1) DE19508936A1 (fr)
WO (1) WO1996028605A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103328455A (zh) * 2010-12-13 2013-09-25 巴斯夫欧洲公司 漂白催化剂

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2455300A (en) * 1999-04-06 2000-10-23 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 (de) * 1981-01-22 1982-07-29 Benckiser-Knapsack Gmbh, 6802 Ladenburg Polymere amino-phosphono-carbonsaeuren, deren alkalisalze und ihre verwendung
WO1991002011A1 (fr) * 1989-08-07 1991-02-21 Basf Aktiengesellschaft Amines polyvinyliques phosphonomethylees, leur procede de fabrication et leur utilisation
EP0444542A1 (fr) * 1990-03-02 1991-09-04 BASF Corporation Compositions de ciments contenant des dérivés de polyethylèneiminephosphonate comme agent dispersant
DE4128510A1 (de) * 1991-08-28 1993-03-04 Basf Ag Phosphonomethylierte polyacrylamide, verfahren zu ihrer herstellung und ihre verwendung
WO1995002086A2 (fr) * 1993-07-09 1995-01-19 The Dow Chemical Company Procede d'elimination des ions metal presents dans des liquides

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 (de) * 1981-01-22 1982-07-29 Benckiser-Knapsack Gmbh, 6802 Ladenburg Polymere amino-phosphono-carbonsaeuren, deren alkalisalze und ihre verwendung
WO1991002011A1 (fr) * 1989-08-07 1991-02-21 Basf Aktiengesellschaft Amines polyvinyliques phosphonomethylees, leur procede de fabrication et leur utilisation
EP0444542A1 (fr) * 1990-03-02 1991-09-04 BASF Corporation Compositions de ciments contenant des dérivés de polyethylèneiminephosphonate comme agent dispersant
DE4128510A1 (de) * 1991-08-28 1993-03-04 Basf Ag Phosphonomethylierte polyacrylamide, verfahren zu ihrer herstellung und ihre verwendung
WO1995002086A2 (fr) * 1993-07-09 1995-01-19 The Dow Chemical Company Procede d'elimination des ions metal presents dans des liquides

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 (zh) * 2010-12-13 2013-09-25 巴斯夫欧洲公司 漂白催化剂
CN103328455B (zh) * 2010-12-13 2016-02-24 巴斯夫欧洲公司 漂白催化剂

Also Published As

Publication number Publication date
DE19508936A1 (de) 1996-09-19

Similar Documents

Publication Publication Date Title
DE3721426C2 (de) N-Vinylformamidcopolymere und Verfahren zu ihrer Herstellung
DE69208976T2 (de) Biologisch abbaubares, hydrophiles, vernetztes Polymer, Verfahren zu seiner Herstellung und seine Verwendung
DE69906777T2 (de) Polykationische polymersalze, deren verfahren und verwendung
DE3879526T2 (de) Waessrige aufschwemmungen von calcium enthaltenden fuellstoffen.
DE69930005T2 (de) Verfahren zur herstellung von fasern oder gruppen von fasern die mit polymeren beschichtet sind, die untereinander wechselwirken.
DE69404565T2 (de) Verfahren zur Verbesserung des Wirkungsgrads bei der Zellstoffwäsche
DE2424502A1 (de) Stilbenverbindungen
DE2928053A1 (de) Lagerstabile, konzentrierte waessrige loesungen von sulfogruppenhaltigen optischen aufhellern
DE69418669T2 (de) Verhinderung der Ablagerung von Nassfestharzen auf Papiermaschinefilzen
EP0000714B1 (fr) Agent améliorant la rétention, la séparation de l'eau et la préparation, en particulier pour la fabrication du papier
WO1996028605A1 (fr) Utilisation de polymeres contenant des groupes aminomethylenephosphono en tant qu'agents complexants
DE60006268T2 (de) Polimerischen stabilisatoren mit hoher affinität zur pulpen
DE2335330A1 (de) Polymerisate, die n-(alkylamino)- und/ oder n-(alkylammonium)-acrylamide als retentionshilfen und entwaesserungshilfsmittel bei der papierherstellung enthalten
CN103643591B (zh) 具有增强的干强度和湿强度的纸
EP2668333A1 (fr) Procédé de fabrication d'un produit de type papier
WO2014001222A1 (fr) Procédé de fabrication de papier et de carton chargés à l'aide de coacervats
CH635368A5 (en) Heat-treated nickel-based superalloy object and process for producing it
DE60014169T2 (de) Verfahren zur entfernung von schädlichen bestandteilen aus einer behandlungsflüssigkeit
DE69911073T2 (de) Bifunktionelle polymere
DE19520804C3 (de) Cellulosepartikel, die im Innern kationische Gruppen aufweisen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4128084A1 (de) Verwendung von (beta)-alanin-n,n-diessigsaeure und deren alkalimetall- oder ammoniumsalzen als komplexbildner
DE2924929A1 (de) Verfahren zur verbesserung der papierqualitaet
DE1595744A1 (de) Verfahren zur Herstellung von kationischen Vinyllactamacrylamid-Kopolymeren
DE1266270B (de) Verfahren zum Veredeln von Cellulose-Fasermaterial
DE19916078A1 (de) Verfahren zur Verbesserung von Weißgrad, Helligkeit und Farbort von Faserstoffen, von anorganischen Füllstoffen und Pigmenten sowie von Bindemitteln für die Papierherstellung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA NO US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载