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 PDFInfo
- 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
Links
- 239000008139 complexing agent Substances 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- 125000006295 amino methylene group Chemical group [H]N(*)C([H])([H])* 0.000 title claims abstract description 6
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 14
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 238000004076 pulp bleaching Methods 0.000 claims abstract description 10
- 239000010893 paper waste Substances 0.000 claims abstract description 8
- 150000001204 N-oxides Chemical class 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 238000009988 textile finishing Methods 0.000 claims description 7
- 239000002761 deinking Substances 0.000 claims description 6
- 230000029936 alkylation Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- 238000004061 bleaching Methods 0.000 abstract description 11
- 229920002678 cellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- -1 Cl _ Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009896 oxidative bleaching Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000009895 reductive bleaching Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GWASTCVCPXFIQT-UHFFFAOYSA-N NC1OP(=O)O1 Chemical class NC1OP(=O)O1 GWASTCVCPXFIQT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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.
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- 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.
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)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2455300A (en) * | 1999-04-06 | 2000-10-23 | Minerals Technologies Inc. | Bifunctional polymers |
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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 |
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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 |
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Cited By (2)
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 |
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DE19508936A1 (de) | 1996-09-19 |
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