EP0158247B1 - Papierhilfsmittel - Google Patents

Papierhilfsmittel Download PDF

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Publication number
EP0158247B1
EP0158247B1 EP85103840A EP85103840A EP0158247B1 EP 0158247 B1 EP0158247 B1 EP 0158247B1 EP 85103840 A EP85103840 A EP 85103840A EP 85103840 A EP85103840 A EP 85103840A EP 0158247 B1 EP0158247 B1 EP 0158247B1
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EP
European Patent Office
Prior art keywords
bis
amines
weight
groups
mole
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
Application number
EP85103840A
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German (de)
English (en)
French (fr)
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EP0158247A1 (de
Inventor
Wolf-Dieter Dr. Schröer
Janos Dr. Müszik
Günther Dr. Gramm
Otto Dr. Benn
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Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0158247A1 publication Critical patent/EP0158247A1/de
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Publication of EP0158247B1 publication Critical patent/EP0158247B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00—Wet end of machines for making continuous webs of paper
    • D21F1/66—Pulp catching, de-watering, or recovering; Re-use of pulp-water
    • D21F1/82—Pulp catching, de-watering, or recovering; Re-use of pulp-water adding fibre agglomeration compositions

Definitions

  • the present invention relates to new agents for increasing the retention of fibers, fillers and pigments and for accelerating dewatering in papermaking and as flocculants in the processing of wastewater from papermaking by filtration, sedimentation and flotation.
  • German Offenlegungsschrift 2,736,651 (EP-A-0 000 714) describes condensation products which are obtained by reacting chloropolyethylene glycol ether amines with polyamide amines and then crosslinking with polyfunctional compounds.
  • the chlorpolyethylene glycol ether amines are produced by addition of 2 moles of epichlorohydrin to 1 mole of polyethylene glycol ether catalyzed by boron trifluoride etherate and subsequent condensation of one side of the chain with special amines.
  • an ambivalent polyether building block i.e. a compound that can react with both amines and crosslinkers, but also with itself, leads to inconsistent products.
  • US Pat. No. 3,251,882 discloses polycondensates of a) epichlorohydrin and b) a precondensate of a polyalkylene polyamine and a polyoxyalkylene glycol chloride with a molecular weight of 100-800.
  • the condensates are used to break petroleum / water-based emulsions.
  • water-soluble, self-crosslinking polyamine resins are known which are produced from aminoethers and epichlorohydrin and are used as wet strength agents for paper.
  • German Offenlegungsschrift 2,434,816 describes condensates composed of polyamide amines and polyalkylene oxide derivatives which are reacted with at least equivalent amounts of epichlorohydrin at the terminal OH groups. The condensation is carried out at 20 to 100 ° C. in aqueous solution, satisfactorily effective products being obtained in particular when the polyamide amines are grafted with ethylene imine.
  • European patent applications 0 033 104 and 0 074 558 disclose water-soluble condensation products of compounds containing amino groups and water-soluble crosslinking agents, which in turn were prepared in multi-stage reactions from epichlorohydrin or dichlorohydrin and compounds containing amino groups, and their use in papermaking.
  • the contaminants form deposits and impair retention.
  • the object of the invention was therefore effective aids sensitive to impurities for the production of paper without having to graft monomeric ethyleneimine onto any component.
  • the invention further relates to a process for the preparation of these water-soluble polycondensates and their use as an agent for increasing the retention of fibers, fillers and pigments and for accelerating the dewatering in paper manufacture and for processing paper machine waste water by filtration, sedimentation and flotation.
  • the aliphatic polyol ether amines are obtained by reacting ⁇ -chloropolyethers with polyalkylene polyamines in the absence of solvents, preferably in the presence of small amounts of water (e.g. residual water of the technical polyalkylene polyamines), at a temperature of 80 to 200 ° C, preferably 100 to 180 ° C. 30 to 50% of the (o-chloropolyol ether) are advantageously brought to the reaction temperature together with the total amount of amine, and only then is the remaining amount of ⁇ -chloropolyol ether added and the reaction is completed.
  • water e.g. residual water of the technical polyalkylene polyamines
  • the ratio of co-chloropolyol ether to polyalkylene polyamines should be chosen so that uniform products are obtained. This requires at least almost equimolar amounts of polyalkylene polyamine. The amine excess in moles is based on the content of reactive chlorine groups in the ⁇ -chloropolyol ether.
  • the polyetheramines are obtained when 0.95 to 1.30 mol per 1 mol of chlorine in the ⁇ -chloropolyol ether
  • Polyalkylene polyamine can be used.
  • Preferably 1.05 to 1.20 moles of polyalkylene polyamine are used per mole of chlorine in the w-chloropolyol ether.
  • it can also be condensed in the presence of a large excess of polyalkylene polyamine. The removal of the unreacted polyalkylene polyamine is generally not necessary since this is incorporated into the polycondensate in the subsequent reaction with the crosslinking agents.
  • co-chloropolyol ethers are known. They can be obtained by reacting polyethylene glycols with phosgene or thionyl chloride according to DE-OS 2 934 854. Another way describes e.g. DE-OS 2 434 816. Polyethylene glycols are added with the addition of Lewis acids as catalysts, such as e.g. Tin (IV) chloride, zinc chloride, iron (III) chloride, aluminum chloride or boron trifluoride or their addition compounds on electron donors, such as e.g.
  • the polyalkylene polyols that can be used are essentially composed of ethylene oxide units. However, propylene oxide up to a content of 25 mol%, but preferably only up to 10 mol%, can also be copolymerized randomly or in blocks.
  • the average molecular weights of the polyglycols mentioned are 200 to 1200, in particular 400 to 1000.
  • Polyols suitable for the purposes of the invention contain at least two OH groups and are derived from trimethylolpropane or glycerol.
  • polyamines are, for example, ethyl bis (3-aminopropyl) amine, 2-hydroxyethyl bis (3-aminopropyl) amine, n-butyl bis (3-aminopropyl) amine , Tris (3-aminopropyl) amine and especially methyl bis (3-aminopropyl) amine.
  • a base mixture which consists of at least 60 mol% of aminoethylpiperazine, a maximum of 20 mol% of diethylenetriamine and, moreover, of other amines mentioned above is very particularly preferred.
  • Aliphatic, halogen group-free polyetheramines according to the invention can also be produced in other ways.
  • DAS 1 215 373 describes e.g. the reductive amination of polyglycol ethers.
  • the reaction of polyalkylene polyols with acrylonitrile and subsequent hydrogenation is also one way, for example, of polyetheramines according to the invention.
  • Suitable polyfunctional compounds compared to amino groups for the preparation of the polycondensates according to the invention are, in particular, those polyfunctional compounds which are able to react completely in aqueous solution at pH values above 6, preferably above 8, with the amino groups contained in the basic polyamides.
  • Halohydrins or epihalohydrins e.g. Epichlorohydrin, 1,3-dichloropropanol (2), bis (3-chloro-2-hydroxypropyl) ether, 1,4-dichloro-2,3-epoxy-butane;
  • Bis-epoxy compounds e.g. 1,2,3,4-diepoxybutane, diglycidyl ether, ethane-1,2-bis-glycidyl ether;
  • Particularly preferred compounds B are dichloroethane and epichlorohydrin.
  • the structure of the polyaminopolyamides C according to the invention is already known from the publications DE-PS 1 771 814 and DE-PS 1 771 043.
  • the weight ratios of essential component B vary greatly depending on the type and amount of A, C and D. As described above, component B is used to such an extent that water-soluble polycondensates are formed which have a viscosity of 100 to 1000 mPa ⁇ s at 25 ° C. in 25 percent aqueous solution.
  • the quantitative ratios of the polyfunctional compounds B to the other components A, C and D are expediently such that the amounts necessary to form the desired degree of condensation of the water-soluble polycondensate are not substantially exceeded.
  • the minimum amount of compounds B which are polyfunctional with respect to amino groups and which are to be used to convert reaction products with the desired high molecular weight or solutions thereof to the desired viscosity at 25 ° C. ie 100-1000 mPa.s, preferably 200 to 400 mPa.s a 25 % aqueous solution
  • the polycondensates can be prepared from the polyether amines A and, if appropriate, the polyamide amines C and / or the polyalkylene polyamines D, by processes known per se, e.g. by stirring mixtures of A, if appropriate C and / or D, and the compounds B which are polyfunctional with amino groups in aqueous media at pH values above 6 and at temperatures between 0 and 150 ° C. until a sample of the reaction mixture in the form of a 10% aqueous solution at 25 ° C has a viscosity of at least 10 mPa-s.
  • the polyfunctional compounds are added gradually to the mixture of A and / or C and / or D in an aqueous medium under otherwise identical reaction conditions until the desired viscosity is reached.
  • the content of reaction products in the reaction solution which is preferably between 10 and 30% by weight, if the reaction has been carried out at a higher concentration, is then adjusted to the desired final value by dilution with water.
  • it is necessary to stop the action after reaching the desired viscosity by adjusting the pH of the reaction solution by adding acids, e.g. Hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid to adjust to pH 6, preferably to 4 to 5. This is especially true in the event that the minimum amount of functional compounds required to form the desired degree of condensation of the water-soluble polycondensate has been significantly exceeded.
  • the condensation can also be carried out in a closed vessel at temperatures above the boiling point of the compound B which is polyfunctional with respect to amino groups, in particular when using dihaloalkanes, preferably between 90 to 150 ° C. and pressures between 3-8 bar. It is normally not necessary to stop the reaction by adding acid.
  • the total concentration of the components in the aqueous reaction mixture should be 10 to 50 percent by weight.
  • the reaction of the polyfunctional compound B need not necessarily take place with a mixture of A and / or C and / or D. It is also possible to first allow one of the three components A or C or D or combinations of two of these compounds to react with the polyfunctional compound B to form a precondensate and then to implement this in a second stage with the other component.
  • the polycondensates are characterized by a minimum molecular weight of 2500, preferably 5000.
  • the upper limit of their molecular weight is given by their property of being water-soluble. A numerical description of the upper limit of their molecular weight is not possible, since this strongly depends on the underlying polyamines and the number of water-solubilizing groups they contain.
  • the procedure is known in such a way that the polycondensates according to the invention are added to the paper stock suspension in the form of dilute aqueous solutions before the headbox, the Dosing point is chosen so that a good distribution of the aid in the raw material suspension is ensured, but a too long contact time is avoided.
  • the amounts of polycondensate that are required to achieve the desired retentive effect and / or drainage-accelerating effect can be determined without difficulty by preliminary tests; in general, it is advisable to use 0.005 to 0.5 percent by weight of polycondensate, based on the dry weight of the paper.
  • polyamines according to the invention before the headbox of a paper machine also has an advantageous effect on the processing of the paper machine waste water by filtration, flotation or sedimentation;
  • the coagulating effect of the polycondensates according to the invention makes it much easier to separate paper constituents from the paper machine waste water.
  • the polycondensates according to the invention are used as auxiliaries in the processing of paper machine waste water by filtration, flotation or sedimentation, it is also possible to proceed in a manner known per se, preferably in such a way that the reaction products in question are expediently added to the paper machine waste water in the form of dilute aqueous solutions before entering the fabric scoop.
  • the amounts of polyamines which cause sufficient coagulation of the pulp constituents contained in paper machine wastewater are to be measured according to the composition of the wastewater and can easily be determined from case to case by preliminary tests; In general, amounts of 0.005 to 2 g of polyamine per m 3 of waste water are sufficient for this.
  • the condensates according to the invention show a rise in comparison with similar known compounds in the application range of pH 4.0-8.0 retention effectiveness, but in particular drainage acceleration.
  • the polycondensates according to the invention show a particularly low sensitivity to enriched contaminants in closed water circulation systems.
  • reaction product 50 parts by weight of the reaction product were stirred at room temperature with a mixture of 42 parts by weight of AEP, 4 parts by weight of DETA and 8 parts by weight of BAPMA and heated to 100.degree. At this temperature, a further 100 parts by weight of the reaction product were then added in 1 hour and stirring was continued at 120 ° C. for 3 hours. After cooling to 90-95 ° C., 204 parts by weight of water were stirred in with further cooling.
  • reaction product from polyethylene glycol and epichlorohydrin 150 parts by weight of reaction product from polyethylene glycol and epichlorohydrin were prepared and cooled from 80 to 60 ° C. At this temperature, the mixture of 42 parts by weight of AEP, 4 parts by weight of DTRA and 8 parts by weight of BAPMA was stirred in for 1 hour. The mixture was then heated to 120 ° C. for 3 hours, cooled to 90-95 ° C. and adjusted to a solids content of 50% by weight with water.
  • a reaction vessel with a gas inlet tube and a descending cooler 108 g (1.05 mol) of diethylenetriamine are mixed with 146 g (1 mol) of adipic acid with the addition of 9 g (0.05 mol) of adipic acid dihydrazide, and the mixture is stirred and Transfer of oxygen-free nitrogen heated to 190 ° C within 3-4 hours, the reaction temperature being increased in the range of 150-190 ° C to such an extent that the water formed distilled off uniformly. After about 30 g of water and small amounts of diethylenetriamine have distilled over, the reaction mixture is stirred at 190-180 ° C.
  • a) 108 g (1.05 mol) of diethylenetriamine, 146 g (1.0 mol) of adipic acid and 28 g (0.25 mol) of ⁇ -caprolactam are added with the addition of 9 g (0.05 mol) of adipic acid dihydrazide, such as described in the preparation of the reaction product C 1, converted to the corresponding basic polyamide.
  • Solids content 27.2% by weight.
  • Solids content 25.8% by weight.
  • Solids content 29.2% by weight.
  • Solids content 27.7% by weight.
  • Solids content 26.9% by weight.
  • Solids content 24.5% by weight.
  • Solids content 25.8% by weight.
  • Solids content 24.1% by weight.
  • the 1% aqueous solutions of the condensation products 1 to 8 were metered in by means of a metering pump.
  • 1% dilutions of the known retention agent 1 according to Example 1 of DE-PS 1 771 814 or of the known retention agent 11 according to Example 1 from DE-OS 2 736 651 (EP-A-0 000 714) or of the known retention agent III (US Pat. No. 3,972,939, Example 1) metered in.
  • the solids content in the wastewater of the paper machine was determined as a measure of the retention effect. The lower this solids content, the better the retention effect.
  • Table 2 illustrates that the polyamines according to the invention have a very good retention effect both in the acidic and in the neutral range and that this is better than that which is obtained when the known retention agents are used.
  • the amounts added relate to the weight of the air-dry pulp and the 25% solution of the retention aid.
  • the so-called drainage time was determined as a measure of the drainage acceleration to be expected on a paper machine. This is determined by measuring the time required in the Schopper-Riegler grinding degree tester to set a certain degree of grinding or water volume in the outlet cup. The shorter the time, the better the drainage acceleration that can be achieved.
  • 200 ml of the 1% paper pulp suspension prepared according to a) or b) were in each case in row A with fresh water, in row B with a circulating water (closed circuit, fresh water requirement 10 - 12 I / kg paper, 27 ° dH total hardness, 2480 mg evaporation residue / I, 1149 mg 0 2/1 COD value) to 1000 ml and filled the Schopper-Riegler apparatus determined by means of the drainage time.
  • the additional quantities each relate to the weight of the air-dry paper stock and to the 25% solution of the condensation products 1 to 8.
  • Table 3 illustrates the good dewatering effect of the polyalkylene polyamines according to the invention both in the acidic and in the neutral range.
  • the known retention agents listed in Application Example 1 were also metered in.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
EP85103840A 1984-04-11 1985-03-29 Papierhilfsmittel Expired EP0158247B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843413567 DE3413567A1 (de) 1984-04-11 1984-04-11 Papierhilfsmittel
DE3413567 1984-04-11

Publications (2)

Publication Number Publication Date
EP0158247A1 EP0158247A1 (de) 1985-10-16
EP0158247B1 true EP0158247B1 (de) 1988-01-07

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EP85103840A Expired EP0158247B1 (de) 1984-04-11 1985-03-29 Papierhilfsmittel

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US (1) US4673729A (fi)
EP (1) EP0158247B1 (fi)
DE (2) DE3413567A1 (fi)
FI (1) FI851407L (fi)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988010277A1 (en) * 1987-06-22 1988-12-29 Nippon Shokubai Kagaku Kogyo Kabushiki Kaisha Process for preparing cationic, water-soluble resin and water-treating agent containing said resin
US5385639A (en) * 1993-08-27 1995-01-31 Hoechst Celanese Corporation Deinking wastepaper printed with oil-based ink
US6353055B1 (en) * 1994-11-18 2002-03-05 Supratek Pharma Inc. Polynucleotide compositions
US6221959B1 (en) * 1994-11-18 2001-04-24 Supratek Pharma, Inc. Polynucleotide compositions
EP1587854A1 (en) * 2003-01-17 2005-10-26 Clariant International Ltd. Polymeric etheramines, their production and use
DE10315606A1 (de) * 2003-04-05 2004-11-04 Voith Paper Patent Gmbh Bandreinigung
MXPA06006067A (es) * 2003-12-29 2006-08-11 Clariant Finance Bvi Ltd Uso de eteraminas polimericas para mejorar la solidez con respecto al cloro de los textiles.
EP1902177A1 (en) * 2005-07-11 2008-03-26 Hercules Incorporated Use of non-thermosetting polyamidoamines as dry-strength resins
WO2009109492A1 (en) * 2008-03-07 2009-09-11 Clariant International Ltd Dyeing auxiliary

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632559A (en) * 1967-09-28 1972-01-04 Sandoz Ltd Cationically active water soluble polyamides

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA690538A (en) * 1959-01-16 1964-07-14 Bohme Fettchemie Gmbh Process for the production and use of water soluble hardenable polyalkylene and/or polyamine condensation products containing epoxide and/or halogen hydrin groups in the molecule
US3251882A (en) * 1963-01-07 1966-05-17 Nalco Chemical Co Epichlorohydrin polyalkylene polyamine polycondensates
US3462383A (en) * 1966-03-07 1969-08-19 Dow Chemical Co Wet strength additives for cellulosic products
DE2434816C3 (de) * 1974-07-19 1981-01-22 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von stickstoffhaltigen Kondensationsprodukten und deren Verwendung als Retentionsmittel, Flockungsmittel und Entwässerungsbeschleuniger bei der Papierherstellung
DE2436386C2 (de) * 1974-07-29 1982-09-23 Basf Ag, 6700 Ludwigshafen Verwendung stickstoffhaltiger Kondensationsprodukte
DE2736651A1 (de) * 1977-08-13 1979-02-15 Wolff Walsrode Ag Hilfsmittel zur verbesserung der retention, entwaesserung und aufbereitung, insbesondere bei der papierherstellung
US4281199A (en) * 1978-06-03 1981-07-28 Basf Wyandotte Corporation Polyalkylene polyamine ether derivatives of polyoxyalkylene compounds
DE2916356C2 (de) * 1979-04-23 1982-06-09 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von wasserlöslichen Polyätheraminen
DE3003648A1 (de) * 1980-02-01 1981-08-06 Basf Ag, 6700 Ludwigshafen Verfahren zur zerstellung von wasserloeslichen, stickstoffhaltigen kondensationsprodukten und deren verwendung bei der papierherstellung
DE3135830A1 (de) * 1981-09-10 1983-03-24 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von wasserloeslichen, stickstoffhaltigen kondensationsprodukten und deren verwendung bei der papierherstellung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632559A (en) * 1967-09-28 1972-01-04 Sandoz Ltd Cationically active water soluble polyamides

Also Published As

Publication number Publication date
FI851407A0 (fi) 1985-04-09
DE3413567A1 (de) 1985-10-24
US4673729A (en) 1987-06-16
FI851407L (fi) 1985-10-12
DE3561335D1 (en) 1988-02-11
EP0158247A1 (de) 1985-10-16

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