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 No. 2 726 651 describes condensation products which are obtained by reacting chlorpolyethylene glycol ether amines with polyamide amines and subsequent 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 ie a compound that can react both with amines and with crosslinking agents, but therefore also with itself, leads to inconsistent products.
• German Offenlegungsschrift No. 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 an aqueous solution, satisfactorily effective products being obtained in particular when the polyamide amines are grafted with ethyleneimine.
• 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 reacted by reacting ⁇ -chloropolyol ethers with polyalkylene polyamines in the absence of solvents, at best in the presence of small amounts of water (for example residual water of technical polyalkylene polyamines) at a temperature of 80 to 200 ° C, preferably 100 to 180 ° C obtained.
• water for example residual water of technical polyalkylene polyamines
• 30 to 50% of the ⁇ -chloropolyol ether are 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.
• the ratio of ⁇ -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 excess of amine in moles is based on the content of reactive chlorine groups in the ⁇ -chloropolyol ether. Polyetheramines according to the invention are obtained if 0.95 to 1.30 mol of polyalkylene polyamine are used per 1 mol of chlorine in the ⁇ -chloropolyol ether. Preferably 1.05 to 1.20 moles of polyalkylene polyamine are used per mole of chlorine in the ⁇ -chloropolyol ether.
• ⁇ -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 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 per molecule, but preferably 3 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 prepared in other ways.
• DAS 12 15 373 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.
• 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, 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 200-400 mPa.s of a 25% aqueous solution) are mainly dependent on the molecular weight of the components and can easily be determined from case to case by preliminary tests.
• 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, for example by mixing mixtures of A, if appropriate C and / or D and the compounds B which are polyfunctional with respect to amino groups 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 It is often advantageous if the polyfunctional compounds are gradually added 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 is then, if the reaction has been carried out at a higher concentration, adjusted to the desired final value by dilution with water.
• 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 90-150 ° C. at pressures at 0-50 bar, preferably 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 react one of the three components A or C or D or combinations of two of these compounds with the polyfunctional compound B to form a precondensate ren and then implement this in the 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 per se so 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 effect partly involved in the processing of 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 pulp 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 an increase in the retentive activity in the application range from pH 4.0 to 8.0, but in particular an acceleration in dewatering.
• 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 the mixture was stirred at 120 ° C. for a further 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 A dipinic acid dihydrazide, and the mixture is stirred and transferred from oxygen-free nitrogen heated to 190 ° C. in the course of 3-4 hours, the reaction temperature being increased in the range from 150 ° to 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.
• the basic polyamide formed is thus obtained in the form of a 50% strength aqueous solution which has a viscosity of 300-400 cP at 25 ° C. and an equivalent weight of 340.
• 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 reten were also used tion agent I according to Example 1 of DE-PS 1 771 814 or the known retention agent II according to Example 1 from DE-OS 2 736 651 or the known retention agent III (US Pat. No. 3 972 939, Example 1).
• 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 specific grinding degree 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% pulp suspension prepared according to a) or b) were in each case in row A with fresh water, in row B with a circulation water (closed circuit, fresh water requirement 10 - 12 l / kg paper, 27 ° dH total hardness , 2480 mg evaporation residue / ltr., 1140 mg 0 2 / ltr. COD value) made up to 1000 ml and the dewatering time determined using the Schopper-Riegler device.
• 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)

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• 1984
  • 1984-04-11 DE DE19843413567 patent/DE3413567A1/de not_active Withdrawn
• 1985
  • 1985-03-29 US US06/717,410 patent/US4673729A/en not_active Expired - Fee Related
  • 1985-03-29 DE DE8585103840T patent/DE3561335D1/de not_active Expired
  • 1985-03-29 EP EP85103840A patent/EP0158247B1/fr not_active Expired
  • 1985-04-09 FI FI851407A patent/FI851407L/fi not_active Application Discontinuation

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