EP0997523B1 - Solutions aqueuses d'acides phosphoniques - Google Patents

Solutions aqueuses d'acides phosphoniques Download PDF

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Publication number
EP0997523B1
EP0997523B1 EP99121341A EP99121341A EP0997523B1 EP 0997523 B1 EP0997523 B1 EP 0997523B1 EP 99121341 A EP99121341 A EP 99121341A EP 99121341 A EP99121341 A EP 99121341A EP 0997523 B1 EP0997523 B1 EP 0997523B1
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EP
European Patent Office
Prior art keywords
weight
acids
phosphonic acids
aqueous solutions
phosphonic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99121341A
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German (de)
English (en)
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EP0997523A1 (fr
Inventor
Herbert Dr. Bachus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHT Germany GmbH
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CHT R Beitlich GmbH
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Publication of EP0997523A1 publication Critical patent/EP0997523A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen

Definitions

  • the invention relates to aqueous solutions of phosphonic acids and / or their salts and in particular their use as complexing agents for the treatment of cellulosic fiber materials used in demineralization processes and used to stabilize bleaching solutions containing peroxide become.
  • Complexing agents are used in the refinement of cellulosic fiber material, remove the interfering metal ions during a treatment or something mask that impairment of the process during treatment is reduced.
  • complexing agents are also used, whereby in textile bleaching processes mainly DTPMP and in the bleaching of non-digested Wood pulp DTPA is used (ibid., P. 426-428).
  • the described Use concentration is 0.1 - 0.2 wt .-%, based on the respective anhydrous complexing agent.
  • amino carboxylic acids are assessed unfavorably. With the exception of the technically ineffective NTA, EDTA and DTPA are not biodegradable and are also not eliminated in sewage treatment plants by adsorption. Since all amino carboxylic acids are suspected of remobilizing toxic heavy metals - SCH ⁇ BERL and HUBER, Tenside Surfactants Detergents 25 2 (1988) 105-106 - they are checked in surface waters that are used for drinking water production. Maximum quantity restrictions for NTA in household detergents up to restrictive prohibitions of any use of EDTA or DTPA already apply today in textile finishing, wood and pulp industry depending on national and regional laws and regulations.
  • Phosphonates which are better at the risk of remobilization of heavy metals be assessed, see GLEDHILL and FEIJTEL, The Handbook of Environmental Chemistry, Vol 3, Part F, pp. 261-285 (1992) are also considered not to be harmless classified because they are also not biodegradable and according to OECD 302B investigations can only be inadequately eliminated through adsoption.
  • Phosphorus levels in wastewater whether in a textile plant or pulp mill, have strict limits may be subject to any improvement in this elimination data from great interest.
  • EP 0 125 766 A1 describes phosphonic acids of the general formula I.
  • n describes the number of ethylene groups.
  • the object of the invention is to provide aqueous solutions of phosphonic acids and / or to produce their salts which have an active substance content of at least 25% by weight. %, based on free phosphonic acid or the complexing agent content at least Make liquids stable for 6 months at room temperature. Furthermore is the object of the invention to provide a new, effective and environmentally friendly process for demineralizing cellulose-containing Fiber material and for the stabilization of hydrogen peroxide Bleaching solutions for native textile fiber materials and kraft pulps.
  • the invention relates to an aqueous solution containing salts of phosphonic acids PPPMP (s) of the general formula I.
  • PPPMP salts of phosphonic acids
  • H 2 PO 3 CH 2 - [N (CH 2 PO 3 H 2 ) -CH 2 -CH 2 ] n -N (CH 2 -PO 3 H 2 ) 2 with n 3, 4 and / or 5 with an active ingredient content, based on free phosphonic acid, of at least 25% by weight, obtainable by partial neutralization of at least one phosphonic acid group per molecule.
  • aqueous solutions of the phosphonic acid mentioned and / or their Salts with an active ingredient content of at least 30% by weight, in particular To produce 40 wt .-% with the desired storage stability.
  • the mentioned partially neutralized or free phosphonic acids as complexing agents are used, it is special in the sense of the present invention preferred, this in an amount of 0.002 to 0.20 wt .-%, in particular in an amount of 0.005 to 0.05% by weight, based on the active substance To use acids and the dry amount of fiber.
  • peroxide bleaches in the event that hydrogen peroxide used as peroxide use, preferably in an amount from 0.1 to 15% by weight, in particular from 0.2 to 5% by weight, based on the dry amount of fiber used.
  • the bleach is particularly preferred at a pH in the range from 7 to 14, in particular in the range from 9 to 13.
  • the temperature can in this case, for example, in the range from 20 to 140 ° C., in particular 70 to 120 ° C. can be set. If necessary, it is also possible to suspend the magnesium salts add, the amount of magnesium by up to 0.5 wt .-%, in particular 0.01 to 0.2 wt .-% is increased.
  • Another embodiment of the present invention is its use of the above-mentioned aqueous solutions for demineralizing cellulosic fiber material, with aminophosphonic acids as complexing agents with at least 6 phosphonate groups.
  • demineralization of cellulosic fiber material is also possible directly with the above-mentioned phosphonic acids of the general formula I and / or II use as a complexing agent.
  • salts of To use phosphonic acid of the general formula I is to be understood as meaning that preferably at least one hydrogen atom of phosphonic acid is replaced by an alkali metal, alkaline earth metal, ammonium or amine ion.
  • alkali metal alkaline earth metal
  • ammonium or amine ion for the purposes of the present invention, they are particularly preferred the aqueous solutions around those of triethylenetetramine hexa (methylenephosphonic acid).
  • the weight ratio of diethylenediaminepentamethylenephosphonic acid is particularly preferably to triethylenetetramine hexa (methylenephosphonic acid) 1 to 1 to 5 to 1.
  • the final product contained 32% by weight of TTHMP. This value is usually based on the amine used related, since technical aminopolyphosphonates beginning with the ATMP consist of mixtures which, in addition to the highly phosphonomethylated and eponymous component also less phosphonomethylated Homologues and other by-products included.
  • amines especially those that are technically available in large quantities, e.g. Tetraethylene pentamine, pentaethylene hexamine, but also polyethylene imines with weight averages up to 50000.
  • Mathis-Labomat TM 100 ° C (internal temperature measurement), 90 min, 10% by weight consistency, 1.0% by weight NaOH, 1.5% by weight hydrogen peroxide.
  • the complexing agents were each adjusted to 30% by weight of active substance, based on free acid.
  • Table 3 shows that 0.05% by weight of TTHMP used as 30% by weight Active substance solution, even when reducing hydrogen peroxide 0.2% better whiteness than comparison tests without TTHMP.
  • An untreated cotton jersey was made with a solution of 30 g / l sodium hydroxide solution 50% by weight, 2 g / l Cotoblanc® TAA and 4 g / l TTHMP solution from example 1 treated for 30 minutes at 98 ° C and a liquor ratio of 1:10. Calcium decreased from 530 to 270 ppm, magnesium from 220 to 130 ppm and iron from 38 to 26 ppm. The comparison test without adding TTHMP gave 480 ppm calcium, 190 ppm magnesium and 35 ppm iron.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Claims (18)

  1. Solution aqueuse contenant des sels d'acides phosphoniques de formule générale I H2PO3CH2-[N(CH2PO3H2)-CH2-CH2]n-N(CH2-PO3H2)2    avec n = 3, 4 et/ou 5, avec une teneur en matière active, rapportée à l'acide phosphonique libre, d'au moins 25 % en poids, pouvant être obtenus par neutralisation partielle d'au moins un groupe acide phosphonique par molécule.
  2. Solution aqueuse contenant des mélanges d'acides phosphoniques libres de formule générale I et de formule générale II H2PO3CH2-[N(CH2PO3H2)-CH2-CH2]n-N(CH2-PO3H2)2 H2PO3CH2-[N(CH2PO3H2)-CH2-CH2]n'-N(CH2-PO3H2)2    avec une teneur en matière active, rapportée à l'acide phosphonique libre, d'au moins 25 % en poids, avec n et n' = 1, 2, 3, 4 et/ou 5, contenant au moins deux acides phosphoniques de formule I avec n ≠ n', avec une teneur en matière active, rapportée à la quantité de complexant, d'au moins 25 % en poids.
  3. Solutions aqueuses selon la revendication 1 ou 2, caractérisées en ce que n = 3 ou 4.
  4. Solutions aqueuses selon l'une des revendications 1 à 3, avec une teneur en matière active d'au moins 30 % en poids, en particulier 40 % en poids.
  5. Solution aqueuse selon la revendication 1, caractérisée en ce qu'au moins 1 atome d'hydrogène de l'acide phosphonique est remplacé par un ion d'un métal alcalin, d'un métal alcalino-terreux, ammonium ou d'amine.
  6. Solution aqueuse selon la revendication 1, caractérisée en ce que l'acide phosphonique de formule générale I est l'acide triéthylènetétraminehexa(méthylènephosphonique).
  7. Solution aqueuse selon la revendication 1 ou 2, caractérisée en ce que les acides phosphoniques de formules générale I et/ou II se présentent en combinaison avec d'autres complexants.
  8. Solution aqueuse selon la revendication 2, caractérisée en ce que le mélange comprend de l'acide diéthylènetriaminepenta(méthylènephosphonique) et de l'acide triéthylènetétraminehexa(méthylènephosphonique).
  9. Solution aqueuse selon la revendication 8, caractérisée en ce que le rapport de mélange de l'acide diéthylènetriaminepenta(méthylènephosphonique) à l'acide triéthylènetétraminehexa(méthylènephosphonique) est compris dans la plage de 1 : 1 à 5 : 1.
  10. Utilisation de solutions aqueuses selon l'une des revendications 1 à 9 pour le blanchiment au peroxyde de pâte kraft et de matières fibreuses natives dans le blanchiment des textiles, auquel cas on utilise en tant que stabilisant des acides aminophosphoniques ayant au moins 6 groupes phosphonates.
  11. Utilisation selon la revendication 10, caractérisée en ce qu'on utilise le complexant en une quantité, exprimée par la teneur en acides phosphoniques libres, de 0,002 à 0,20 % en poids, en particulier de. 0,005 à 0,05 % en poids, par rapport à la quantité de matière fibreuse sèche.
  12. Utilisation selon la revendication 10, caractérisée en ce qu'on utilise le composé peroxydé peroxyde d'hydrogène en une quantité de 0,1 à 15 % en poids, en particulier de 0,2 à 5 % en poids, par rapport à la quantité de matière fibreuse sèche.
  13. Utilisation selon la revendication 10, caractérisée en ce qu'on met en oeuvre le blanchiment à un pH compris dans la plage de 7 à 14 et en particulier de 7 à 13.
  14. Utilisation selon la revendication 10, caractérisée en ce qu'on met en oeuvre le blanchiment à une température comprise dans la plage de 20 à 140°C et en particulier dans la plage de 70 à 120°C.
  15. Utilisation selon la revendication 10, caractérisée en ce qu'on ajoute à la matière fibreuse en suspension un sel de magnésium qui augmente la quantité des ions magnésium de jusqu'à 0,5 % en poids, en particulier de 0,01 à 0,2 % en poids.
  16. Utilisation selon la revendication 10, caractérisée en ce qu'on procède au blanchiment en présence d'activateurs de peroxyde.
  17. Utilisation de solutions aqueuses selon l'une des revendications 1 à 9 pour déminéraliser une matière fibreuse cellulosique, où on utilise en tant que complexant des acides aminophosphoniques ayant au moins 6 groupes phosphonates.
  18. Utilisation de solutions aqueuses selon l'une des revendications 1 à 9 pour déminéraliser une matière fibreuse cellulosique, où on utilise en tant que complexant des acides phosphoniques selon les formules générales I et/ou II.
EP99121341A 1998-10-27 1999-10-26 Solutions aqueuses d'acides phosphoniques Expired - Lifetime EP0997523B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19849379A DE19849379A1 (de) 1998-10-27 1998-10-27 Wäßrige Lösungen von Phosphonsäuren
DE19849379 1998-10-27

Publications (2)

Publication Number Publication Date
EP0997523A1 EP0997523A1 (fr) 2000-05-03
EP0997523B1 true EP0997523B1 (fr) 2002-12-04

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EP99121341A Expired - Lifetime EP0997523B1 (fr) 1998-10-27 1999-10-26 Solutions aqueuses d'acides phosphoniques

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EP (1) EP0997523B1 (fr)
AT (1) ATE229065T1 (fr)
DE (2) DE19849379A1 (fr)
ES (1) ES2188086T3 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20040162A1 (it) 2004-02-02 2004-05-02 Bozzetto Giovanni Spa Uso di polliaaminometilenfosfonati quali agenti disperdenti

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4304762A (en) * 1978-09-27 1981-12-08 Lever Brothers Company Stabilization of hydrogen peroxide
GB8308003D0 (en) * 1983-03-23 1983-04-27 Albright & Wilson Phosphonates
GB8826431D0 (en) * 1988-11-11 1988-12-14 Albright & Wilson Phosphate composition
WO1996002624A1 (fr) * 1994-07-13 1996-02-01 So-Safe Specialty Products Pty. Ltd. Kit, composition et procedes de nettoyage
DE69427348T2 (de) * 1994-09-01 2002-06-13 Solutia Europ Nv Sa Hexamethylene Phosphonatkonzentrat
DE19528843A1 (de) * 1995-08-04 1997-02-06 Cht R Beitlich Gmbh Verfahren zur Stabilisierung von alkalischen peroxidenthaltenden Bleichflotten für die Bleiche von Zellstoffen und anderen Faserstoffen

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Publication number Publication date
ATE229065T1 (de) 2002-12-15
DE59903638D1 (de) 2003-01-16
ES2188086T3 (es) 2003-06-16
EP0997523A1 (fr) 2000-05-03
DE19849379A1 (de) 2000-05-04

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