EP0349935A2 - Aqueous solutions of polyamidoamine-epichlorhydrine resines, process for preparing the same and use - Google Patents
Aqueous solutions of polyamidoamine-epichlorhydrine resines, process for preparing the same and use Download PDFInfo
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- EP0349935A2 EP0349935A2 EP89112049A EP89112049A EP0349935A2 EP 0349935 A2 EP0349935 A2 EP 0349935A2 EP 89112049 A EP89112049 A EP 89112049A EP 89112049 A EP89112049 A EP 89112049A EP 0349935 A2 EP0349935 A2 EP 0349935A2
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- resin
- acid
- epichlorohydrin
- polyamidoamine
- resin solution
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Classifications
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- 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
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Definitions
- US Pat. No. 3,352,833 describes, inter alia, an alkaline aftertreatment of polyamidoamine-epichlorohydrin resins for reactivating the wet strength activity.
- the acidified resin solutions are then reacted with 0.25 to 2.5 equivalents of base per equivalent of acid in aqueous solution.
- the base is added before using the resin for papermaking, and the resin solution is left to age for four hours and then used immediately.
- the reworking of the alkaline aftertreatment specified in this US patent shows that this does not result in resin solutions which are sufficiently stable in storage and / or low in chlorine (cf. the further comparative experiments below).
- the present invention now relates to a storage-stable, aqueous resin solution with a pH of at most 7, containing as resin a water-dilutable, preferably water-soluble polyamidoamine-epichlorohydrin resin (A) obtained by converting a water-dilutable, preferably water-soluble, basic polyamidoamine (B) , consisting of an acid component (B1) and an amine component (B2), with epichlorohydrin (C), the content of organically bound chlorine in the resin (A) being at most 4% by weight and the component (B2) - if the acid component (B1) is an aliphatic or aromatic carboxylic acid or its functional derivatives, optionally in admixture with an amino carboxylic acid or its lactams - consists of a mixture of polyamines and alkanol monoamines.
- A water-dilutable, preferably water-soluble polyamidoamine-epichlorohydrin resin
- A water-dilutable
- the invention relates to a process for the preparation of these resin solutions and their use.
- stable in storage is intended here to mean that no noticeable gelation or precipitation occurs during storage for at least three months at room temperature (or for at least 10 days at 50 ° C.).
- solution is also intended to include a colloidal solution.
- the pH of the resin solution according to the invention is preferably between 1.5 and 5.
- the viscosity of a 12.5% solution at 25 ° C. is generally about 10 to 200, preferably 15 to 80 mPa.s.
- the content of resin (A) in the solution according to the invention is generally between 8 and 25% by weight, preferably 10 and 15% by weight, based on the solution.
- this resin solution contains small amounts of inorganic substances (from the base treatment and the subsequent neutralization) and optionally up to 0.5% by weight, preferably 0.05 to 0.2% by weight, of antifungal agents, such as sorbic acid or Potassium sorbate and optionally other additives, such as, for example Defoaming agent.
- antifungal agents such as sorbic acid or Potassium sorbate
- other additives such as, for example Defoaming agent.
- the resin (A) generally has an average molecular weight M n of at least 500, preferably of at least 1000 and in particular of 1000 to 500,000.
- the content of organically bound chlorine is generally between 0.1 and 4, preferably between 1 and 4 and in particular between 1 and 3% by weight. In a 12.5% resin solution, this chlorine content does not exceed 0.5% by weight and is generally between 0.0125 and 0.5, preferably between 0.125 and 0.5 and in particular between 0.125 to 0.375% by weight, based on the solution.
- the amount of units in (A) derived from the epichlorohydrin is generally 20 to 50% by weight, preferably 30 to 40% by weight, based on (A).
- the process according to the invention for the preparation of the resin solutions described above is characterized in that water-soluble, basic polyamidoamines (B) are reacted with epichlorohydrin (C) in a ratio of 0.6 to 2 moles per mole of basic amino groups of the polyamidoamine (B) in an aqueous system brings, and then, optionally after prior acidification of the reaction system, with as much a base (D), generally 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol per mol of epichlorohydrin used, at 25 to 95 ° C converts that the pH is greater than 8, then adjusts the pH to at most 7 by adding acid.
- a base generally 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol per mol of epichlorohydrin used, at 25 to 95 ° C converts that the pH is greater than 8, then adjusts the pH to at most 7 by adding acid.
- the water-soluble polyamidoamine (B) generally has an average molecular weight M n (determined via the carboxyl end groups) of at least 500, preferably at least 1000 and in particular 2000 to 20,000; the amine number is usually between 200 and 400, preferably between 250 and 350 mg KOH / g and the acid number between 0 and 50, preferably 10 and 30 mg KOH / g.
- Polyamidoamines (B) which meet the conditions according to the invention are, for example, in DE-AS 1,777,824, GB-PS 865,727, US-PS 4,075,177 and 4,336,835, DE-OS 3,323,732 and EP -OS 31 899 described, to which reference is made here.
- the corresponding products according to DE-OS 3,323,732 are preferred insofar as they come under the present framework.
- Polyamidoamines (B) of this type are generally obtained by reacting the acid component (B1), such as dicarboxylic acids or their functional derivatives, and ⁇ -aminocarboxylic acids or their lactams with the amine component (B2), such as polyamines, these being present in a mixture with alkanolmonoamines if ( B1) meets the conditions mentioned above.
- These polyamines contain at least two primary amino groups and preferably at least one secondary and / or tertiary amino group.
- the quantity ratio of the components is to be chosen so that in the resulting polyamidoamine (B) there is still a sufficient number of basic (ie reactive with epichlorohydrin (C)) amino groups, no gelation occurs during the reaction and the molecular weight of (A) in the specified range.
- Reaction products of type 1) using diethylene triamine, triethylene tetramine and tetraethylene pentamine as the polyamine and 2-aminoethanol as the alkanol monoamine are particularly preferred.
- Examples of polyamines b1) and c1) are those of the formula (I) considered in the p is zero or an integer from 1 to 6, preferably 1 to 4,
- R1 is a divalent, preferably non-aromatic hydrocarbon radical having 2 to 18 carbon atoms, preferably a branched or unbranched alkylene radical having 2 to 10 carbon atoms, in particular having 2 to 6 carbon atoms, or a cycloalykylene radical having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene radical having 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms and R2, R 2 ' independently of one another for H or one of the two radicals for stand in which R1 has the same meaning as above and R3, R4 are either independently of one another H, (C1-C20) alkyl, preferably (C1-C6) alkyl, where these alkyl radicals can also carry hydroxyl groups.
- polyamines b1) are called methyl bis (3-aminopropyl) amine, ethyl bis (3-aminopropyl) amine, N- (3-aminopropyl) tetramethylene diamine, N, N'-bis (3-aminopropyl) tetramethylene diamine, Polyalkylene polyamines such as di-propylene- (1,2) -triamine, bis- (3-aminopropyl) -amine, tripropylene- (1,2) -tetramine and especially diethylene triamine, triethylene tetramine and tetraethylene pentamine.
- Polyamines c1) are, for example: ethylenediamine, propylenediamine, 1-amino-3-methylamino-propane, 2-methylpentamethylene diamine, pentanethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, neopentyl diamine, octamethylene diamine, dioxadodecane diamine, cyclialiphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexane diamine; 4,4'-methylene-bis-cyclohexylamine, isophoronediamine, menthandiamine, 4,4'-diamino-3,3'-dimethyl-di-cyclohexylmethane, 3-aminomethyl-1- (3-aminopropyl-1-methyl) -4 -methylcyclohexane, N-methylethylenediamine, N-aminoethylpiperazine, 1,3-bis-amin
- alkanol monoamines are those of the formula H2N-R1-OH (II) suitable in which R1 has the above meaning, such as 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol, 5-amino -1-pentanol, 6-amino-1-hexanol and their isomers, the hydrocarbon radical of which is branched or which carry the amino group and / or the hydroxyl group on a primary or secondary carbon atom; furthermore those which are derived from cyclic hydrocarbon radicals, preferably having 5-7 carbon atoms.
- the molar amount of dicarboxylic acid or its functional derivatives to polyamine / alkanol monoamine is such that the ratio of carboxyl groups to the sum of primary NH2 groups 1: (0.8-1.4), preferably 1: (0, 95-1.1).
- the ratio of their molar amounts is 0.6: 0.4 to 0.99: 0.01, preferably 0.8: 0.2 to 0.95: 0.05.
- the polyamidoamines (B) can be prepared in the customary manner, for example by heating the for several hours corresponding components with the exclusion of oxygen at temperatures of 125 to 250 ° C, preferably from 140 to 180 ° C, first under ordinary pressure and then under reduced pressure, with a small amount of hydrazine hydrate or hydrazides can be added to avoid the darkening of the polyamides.
- the reaction time depends on the temperatures and pressures used and is generally between 4 and 10 hours.
- dichlorohydrin (1,3-dichloro-2-hydroxypropane) can optionally also be used.
- Bases (D) which can be used include: alkali metal hydroxides, preferably sodium and potassium hydroxide, carbonates, bicarbonates, alkaline earth metal hydroxides, such as calcium hydroxide, furthermore benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or corresponding mixtures.
- the reaction products can be prepared by the process according to the invention in such a way that the polyamidoamines (B) and epichlorohydrin (C) are in a first reaction step at a concentration of the reactants of about 25 to 50%, preferably 35 to 45% and at one Temperature between 25 and 95 ° C, preferably 40 to 70 ° C, until it can react until the viscosity of a 40% solution (determined at 25 ° C) is about 100 to 600, preferably 200 to 400 mPa.s.
- This solution is then set in a second reaction step with an aqueous solution of a base (D) which is used in an amount of generally 0.1 to 1.0, preferably 0.1 to 0.6, mol per mol of epichlorohydrin (C) is contained, at a concentration of the reactants of 10 to 40%, preferably 15 to 25%, and a temperature between 25 to 95 ° C, preferably 40 to 70 ° C, until the viscosity a 12.5% solution (determined at 25 ° C.) is 10-200 mPa.s, preferably 15 to 80 mPa.s.
- the pH in this second reaction step is greater than 8, preferably between 9 and 12.
- the mixture is expediently added to the mixture in order to terminate the action and to stabilize the self-crosslinking reaction products, so much acid or acid derivatives that the pH the aqueous solution is 1 to 7, preferably between 1.5 and 5, and adjusts the solids content of the reaction solution to 8 to 25% by weight by dilution with water.
- acid can be added to the solution during or after the reaction of polyamidoamine (B) and epichlorohydrin (C) and the pH can be adjusted to less than 7, preferably 1.5 and 5.
- Sufficient base (D) is then added to this acidic reaction mixture such that the pH is greater than 8, preferably between 9 and 12, and this system is then used for a period of 0.5 to 8 hours, preferably 1 to 4 hours at a temperature of 25 to 95 ° C, preferably 40 to 70 ° C.
- Halogen-free acids such as sulfuric, phosphoric or acetic acid are particularly suitable as acids and corresponding anhydrides or acidic salts as acid derivatives.
- the amount of epichlorohydrin (C) is generally 0.6 to 2 mol, preferably 1.0 to 1.4 mol, per mol of basic amino groups (primary, secondary or tertiary) in the polyamidoamine (B) and the amount of base (D) 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol, per mol of epichlorohydrin used.
- the resins or resin solutions according to the invention have a considerably lower level than the previously known reaction products of polyamidoamine and epichlorohydrin organically bound chlorine content and are therefore ideally suited to significantly reduce the organic chlorine content of wastewater, including paper mills.
- the reaction products which have hitherto been used to improve the wet strength effectiveness of paper do not possess this valuable property to the same extent. Due to the high storage stability of the resin solutions according to the invention, their wet strength effectiveness remains constant even after months of storage.
- the wet strength of paper - including paper made from unbleached cellulose - can be outstandingly improved. In some cases, depending on the type of paper or as desired, it is also possible to increase the absorbency. It is noteworthy that the reaction products practically do not affect the whiteness of paper made from bleached pulp. It should also be mentioned that the speed at which the reaction products to be used according to the invention crosslink on the paper or in the pulp is high and that the reaction products are also used as retention aids for fillers used in papermaking, drainage aids to improve the papermaking speed and flocculants to remove fine particles Particles from dirty water, for example industrial waste water, can be used.
- the resins in question in the form of aqueous solutions to the aqueous suspension of the paper raw material before processing into paper.
- the amounts of resin required to achieve the desired wet strength can be determined by Determine preliminary tests without difficulty.
- the polyamidoamine was diluted with 570 g of water.
- the solution had a solids content of 59.8% (1 g, 1 hour, 125 ° C.) and a viscosity at 25 ° C. of 1174 mPa.s.
Abstract
Description
Aus der DE-Auslegeschrift 1.177.824 ist es bekannt, Polyamine mit mindestens drei Aminogruppen mit C₃- C₁₀-Dicarbonsäuren umzusetzen und die so erhaltenen Polyamide mit Epichlorhydrin in wasserlösliche Kondensationsprodukte zu überführen. Dabei kann das Epichlorhydrin in einem Molverhältnis zu den sekundären Aminogruppen des Polyamids von etwa (0,5 bis 1,8) : 1 verwendet werden. Die gewonnenen Produkte können zur Verbesserung der Naßfestigkeit von Papier eingesetzt werden.From DE-Auslegeschrift 1,177,824 it is known to react polyamines having at least three amino groups with C₃- C₁₀ dicarboxylic acids and to convert the polyamides thus obtained into water-soluble condensation products with epichlorohydrin. The epichlorohydrin can be used in a molar ratio to the secondary amino groups of the polyamide of about (0.5 to 1.8): 1. The products obtained can be used to improve the wet strength of paper.
Weiterhin ist bekannt (z.B. aus der britischen Patentschrift 865.727), daß solche wäßrigen Kondensationsprodukte, hergestellt aus Polyamidoaminen und Epichlorhydrin, unter anderem Chlorhydrin-Struktureinheiten der Formel
In der US-Patentschrift 3.352.833 wird unter anderem auch eine alkalische Nachbehandlung von Polyamidoamin-Epichlorhydrin-Harzen zur Reaktivierung der Naßfestwirksamkeit beschrieben. Danach werden die sauer eingestellten Harzlösungen mit 0,25 bis 2,5 Equivalent Base pro Equivalent Säure in wäßriger Lösung zur Reaktion gebracht. Nach Beispiel 10 der US-Patentschrift 3.352.833 wird die Base vor der Verwendung des Harzes zur Papierherstellung zugegeben, und die Harzlösung vier Stunden altern gelassen und dann sofort verwendet. Angaben über den Abbau des organisch gebundenen Chlors finden sich in diesen Druckschriften nicht. Die Nacharbeitung der in dieser US-Patentschrift angegebenen alkalischen Nachbehandlung zeigt jedoch, daß dabei keine ausreichend lagerstabilen und/oder ausreichend chlorarmen Harzlösungen entstehen (vgl. die weiter unter folgenden Vergleichsversuche). Ein weiterer Nachteil dieser Alkali-Aktivierung vor der Verarbeitung, beispielsweise in der Papiermasse, sind die zusätzlichen betrieblichen Einrichtungen wie Behälter, Rührwerke und Dosiereinrichtungen, die diese Methode erfordert. Zur optimalen Verwendung der alkalisch zu aktivierenden Polyamidoamin-Epichlorhydrin-Harze ist es außerdem nötig, die Alkalizugaben genau zu dosieren, bestimmte Standzeiten einzuhalten und wegen einer eintretenden Lagerstabilitätsverminderung der alkalischen Lösung diese innerhalb eines bestimmten Zeitraumes zu verbrauchen.US Pat. No. 3,352,833 describes, inter alia, an alkaline aftertreatment of polyamidoamine-epichlorohydrin resins for reactivating the wet strength activity. The acidified resin solutions are then reacted with 0.25 to 2.5 equivalents of base per equivalent of acid in aqueous solution. According to Example 10 of U.S. Patent 3,352,833 the base is added before using the resin for papermaking, and the resin solution is left to age for four hours and then used immediately. There is no information in these publications on the degradation of organically bound chlorine. The reworking of the alkaline aftertreatment specified in this US patent, however, shows that this does not result in resin solutions which are sufficiently stable in storage and / or low in chlorine (cf. the further comparative experiments below). Another disadvantage of this alkali activation before processing, for example in the pulp, is the additional operational equipment such as containers, agitators and metering devices, which this method requires. For optimal use of the alkaline-activated polyamidoamine-epichlorohydrin resins, it is also necessary to meter the alkali addition precisely, to adhere to certain idle times and to consume the alkaline solution within a certain period of time due to a reduction in storage stability.
Die vorliegende Erfindung betrifft nunmehr eine lagerstabile, wäßrige Harzlösung mit einem pH-Wert von höchstens 7, enthaltend als Harz ein wasserverdünnbares, vorzugsweise wasserlösliches Polyamidoamin-Epichlorhydrin-Harz (A), erhalten durch Umsatz eines wasserverdünnbaren, vorzugsweise wasserlöslichen, basischen Polyamidoamins (B), bestehend aus einer Säurekomponente (B₁) und einer Aminkomponente (B₂), mit Epichlorhydrin (C), wobei der Gehalt an organisch gebundenem Chlor in dem Harz (A) höchstens 4 Gew.-% beträgt und wobei die Komponente (B₂) - falls die Säurekomponente (B₁) eine aliphatische oder aromatische Carbonsäure oder deren funktionelle Derivate, gegebenenfalls in Abmischung mit einer Aminocarbonsäure oder deren Lactamen darstellt - aus einem Gemisch aus Polyaminen und Alkanolmonoaminen besteht.The present invention now relates to a storage-stable, aqueous resin solution with a pH of at most 7, containing as resin a water-dilutable, preferably water-soluble polyamidoamine-epichlorohydrin resin (A) obtained by converting a water-dilutable, preferably water-soluble, basic polyamidoamine (B) , consisting of an acid component (B₁) and an amine component (B₂), with epichlorohydrin (C), the content of organically bound chlorine in the resin (A) being at most 4% by weight and the component (B₂) - if the acid component (B₁) is an aliphatic or aromatic carboxylic acid or its functional derivatives, optionally in admixture with an amino carboxylic acid or its lactams - consists of a mixture of polyamines and alkanol monoamines.
Weiterhin bezieht sich die Erfindung auf ein Verfahren zur Herstellung dieser Harz-Lösungen sowie deren Verwendung.Furthermore, the invention relates to a process for the preparation of these resin solutions and their use.
Das Merkmal "lagerstabil" soll hierbei bedeuten, daß während einer Lagerung von mindestens drei Monaten bei Raumtemperatur (oder von mindestens 10 Tagen bei 50°C) keine merkliche Gelierung oder Ausfällung eintritt.The characteristic "stable in storage" is intended here to mean that no noticeable gelation or precipitation occurs during storage for at least three months at room temperature (or for at least 10 days at 50 ° C.).
Der Begriff "Lösung" soll hier auch eine kolloidale Lösung miteinschließen.The term "solution" is also intended to include a colloidal solution.
Der pH-Wert des erfindungsgemäßen Harzlösung liegt vorzugsweise zwischen 1,5 und 5. Die Viskosität einer 12,5-%igen Lösung beträgt bei 25°C im allgemeinen etwa 10 bis 200, vorzugsweise 15 bis 80 mPa.s.The pH of the resin solution according to the invention is preferably between 1.5 and 5. The viscosity of a 12.5% solution at 25 ° C. is generally about 10 to 200, preferably 15 to 80 mPa.s.
Der Gehalt an Harz (A) in der erfindungsgemäßen Lösung liegt im allgemeinen zwischen 8 und 25 Gew.-%, vorzugsweise 10 und 15 Gew.-%, bezogen auf die Lösung.The content of resin (A) in the solution according to the invention is generally between 8 and 25% by weight, preferably 10 and 15% by weight, based on the solution.
Daneben enthält diese Harzlösung geringe Mengen an anorganischen Stoffen (von der Basenbehandlung und der anschließenden Neutralisation) sowie gegebenenfalls bis 0,5 Gew.-%, vorzugsweise 0,05 bis 0,2 Gew.-%, an antifungizid wirkenden Mitteln, wie Sorbinsäure bzw. Kaliumsorbat sowie gegebenenfalls weitere Additive, wie z.B. Entschäumungsmittel.In addition, this resin solution contains small amounts of inorganic substances (from the base treatment and the subsequent neutralization) and optionally up to 0.5% by weight, preferably 0.05 to 0.2% by weight, of antifungal agents, such as sorbic acid or Potassium sorbate and optionally other additives, such as, for example Defoaming agent.
Das Harz (A) besitzt im allgemeinen ein mittleres Molekulargewicht
Die Menge an Einheiten in (A), die sich von dem Epichlorhydrin ableiten, beträgt im allgemeinen 20 bis 50 Gew.-%, vorzugsweise 30 bis 40 Gew.-%, bezogen auf (A).The amount of units in (A) derived from the epichlorohydrin is generally 20 to 50% by weight, preferably 30 to 40% by weight, based on (A).
Das erfindungsgemäße Verfahren zur Herstellung vorstehend beschriebener Harzlösungen ist dadurch gekennzeichnet, daß man wasserlösliche, basische Polyamidoamine (B) mit Epichlorhydrin (C) in einem Verhältnis von 0,6 bis 2 Mol pro Mol basischer Aminogruppen des Polyamidoamins (B) in wäßrigem System zur Reaktion bringt, und dann, gegebenenfalls nach vorheriger Ansäuerung des Reaktionssystems, mit soviel einer Base (D), im allgemeinen 0,1 bis 1,0 Mol, vorzugsweise 0,1 bis 0,6 Mol pro Mol eingesetztes Epichlorhydrin, bei 25 bis 95°C umsetzt, daß der pH-Wert bei größer als 8 liegt, anschließend den pH-Wert durch Zugabe von Säure auf höchstens 7 einstellt.The process according to the invention for the preparation of the resin solutions described above is characterized in that water-soluble, basic polyamidoamines (B) are reacted with epichlorohydrin (C) in a ratio of 0.6 to 2 moles per mole of basic amino groups of the polyamidoamine (B) in an aqueous system brings, and then, optionally after prior acidification of the reaction system, with as much a base (D), generally 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol per mol of epichlorohydrin used, at 25 to 95 ° C converts that the pH is greater than 8, then adjusts the pH to at most 7 by adding acid.
Das wasserlösliche Polyamidoamin (B) besitzt im allgemeinen ein mittleres Molekulargewicht
Polyamidoamine (B), welche die erfindungsgemäßen Bedingungen erfüllen, sind beispielsweise in der DE-AS 1.777.824, der GB-PS 865.727, den US-PSen 4.075.177 und 4.336.835, der DE-OS 3.323.732 und der EP-OS 31 899 beschrieben, auf die hier Bezug genommen wird.
Bevorzugt sind dabei die entsprechenden Produkte gemäß der DE-OS 3.323.732, soweit sie unter den vorliegenden Rahmen fallen.Polyamidoamines (B) which meet the conditions according to the invention are, for example, in DE-AS 1,777,824, GB-PS 865,727, US-PS 4,075,177 and 4,336,835, DE-OS 3,323,732 and EP -OS 31 899 described, to which reference is made here.
The corresponding products according to DE-OS 3,323,732 are preferred insofar as they come under the present framework.
Generell werden derartige Polyamidoamine (B) durch Umsetzung der Säurekomponente (B₁), wie Dicarbonsäuren oder deren funktionellen Derivaten sowie von ω-Aminocarbonsäuren oder deren Lactamen mit der Aminkomponente (B₂), wie Polyamine erhalten, wobei diese im Gemisch mit Alkanolmonoaminen vorliegen, falls (B₁) die weiter oben genannten Bedingungen erfüllt. Diese Polyamine enthalten dabei mindestens zwei primäre Aminogruppen und vorzugsweise mindestens eine sekundäre und/oder tertiäre Aminogruppe. Das Mengenverhältnis der Komponenten ist dabei so zu wählen, daß im resultierenden Polyamidoamin (B) noch eine genügende Zahl an basischen (d.h. mit Epichlorhydrin (C) reaktiven) Aminogruppen vorhanden ist, keine Gelierung bei der Reaktion eintritt und das Molekulargewicht von (A) in dem angegebenen Bereich liegt.Polyamidoamines (B) of this type are generally obtained by reacting the acid component (B₁), such as dicarboxylic acids or their functional derivatives, and ω-aminocarboxylic acids or their lactams with the amine component (B₂), such as polyamines, these being present in a mixture with alkanolmonoamines if ( B₁) meets the conditions mentioned above. These polyamines contain at least two primary amino groups and preferably at least one secondary and / or tertiary amino group. The quantity ratio of the components is to be chosen so that in the resulting polyamidoamine (B) there is still a sufficient number of basic (ie reactive with epichlorohydrin (C)) amino groups, no gelation occurs during the reaction and the molecular weight of (A) in the specified range.
Bei den Polyamidoaminen (B) handelt es sich beispielsweise um Umsetzungsprodukte von
- a) gesättigten oder olefinisch-ungesättigten aliphatischen C₃-C₁₀-Dicarbonsäuren oder deren funktionellen Derivaten bzw. mindestens 3 C-Atome enthaltenden ω-Aminocarbonsäuren oder deren Lactamen mit
- b1) aliphatischen Polyaminen, die mindestens zwei primäre und mindestens eine weitere, und zwar sekundäre und/oder tertiäre Aminogruppe enthalten, oder
- b2) einem Gemisch der Polyamine b1) mit
- c1) Polyaminen, die mindestens eine primäre und gegebenenfalls mindestens eine sekundäre Aminogruppe enthalten und nicht unter die Definition b1) fallen, wobei die zusätzlichen Polyamine in solchen Mengen verwendet werden können, daß deren Anteil an primären Aminogruppen, bezogen auf die Gesamtmenge der primären Aminogruppen, 70 %, vorzugsweise 50 % und insbesondere 30 % nicht übersteigt, und/oder
- c2) Alkanolmonoaminen mit 2 bis 20 C-Atomen, vorzugsweise 2 bis 6 C-Atomen und 1 bis 3, vorzugsweise 1 oder 2 OH-Gruppen und insbesondere mit einer OH-Gruppe. Vorzugsweise besitzen diese Alkanolmonoamine die weiter unten angegebene Formel (II).
- a) saturated or olefinically unsaturated aliphatic C₃-C₁₀ dicarboxylic acids or their functional derivatives or ω-aminocarboxylic acids containing at least 3 carbon atoms or their lactams with
- b1) aliphatic polyamines which contain at least two primary and at least one further, namely secondary and / or tertiary amino group, or
- b2) with a mixture of the polyamines b1)
- c1) polyamines which contain at least one primary and optionally at least one secondary amino group and do not fall under definition b1), it being possible for the additional polyamines to be used in amounts such that their proportion of primary amino groups, based on the total amount of the primary Amino groups, 70%, preferably 50% and in particular 30% does not exceed, and / or
- c2) Alkanol monoamines with 2 to 20 C atoms, preferably 2 to 6 C atoms and 1 to 3, preferably 1 or 2 OH groups and in particular with one OH group. These alkanol monoamines preferably have the formula (II) given below.
Als wasserlösliche Polyamidoamine (B) kommen insbesondere in Betracht:
- 1. Umsetzungsprodukte von a) gesättigten aliphatischen C₃-C₁₀-Dicarbonsäuren. wie Bernsteinsäure, Glutarsäure, Adipinsäure, Sebazinsäure, Malonsäure oder deren funktionellen Derivaten, wie Anhydriden und Estern, wobei die drei erstgenannten Säuren bevorzugt sind, mit den vorstehend unter b) genannten Gemischen von Polyaminen mit Alkanolmonoaminen.
- 2. Umsetzungsprodukte von solchen gesättigten modifizierten Dicarbonsäuren bzw. deren Derivaten, die durch Anlagerung von aliphatischen, cycloaliphatischen, araliphatischen oder heterocyclischen Polyaminen, die mindestens zwei Aminogruppen, und zwar primäre und/oder sekundäre, enthalten, an α,β-olefinisch-ungesättigte Carbonsäureester, deren Alkoholrest 1 bis 8, vorzugsweise 1 bis 3 C-Atome hat, wie Acrylsäureethylester und Methacrylsäuremethylester, erhalten und dann mit den vorstehend unter b₁)/c₁) genannten Polyaminen bzw. deren Gemischen, gegebenenfalls in Abmischung mit Alkanolmonoaminen, umgesetzt werden.
- 3. Umsetzungsprodukte von mindestens drei Kohlenstoffatome enthaltenden ω-Aminocarbonsäuren oder deren Lactamen, z.B. 6-Aminocapronsäure und 8-Aminocaprylsäure bzw. 6-Caprolactam und 8-Capryllactam, mit den vorstehend unter b) genannten Gemischen von Polyaminen mit Alkanolmonoaminen.
- 4. Umsetzungsprodukte von olefinisch ungesättigten Dicarbonsäuren, wie Maleinsäure oder Fumarsäure bzw. deren funktionellen Derivaten, wie Anhydriden oder Estern, mit den vorstehend unter b₁)/c₁) genannten Polyaminen bzw. deren Gemischen, gegebenenfalls in Abmischung mit Alkanolmonoaminen.
- 5. Solche Umsetzungsprodukte, denen außer den unter 1. genannten gesättigten, aliphatischen C₃-C₁₀-Dicarbonsäuren und den unter 4. genannten ungesättigten Dicarbonsäuren noch ω-Aminocarbonsäuren oder deren Lactame des unter 3. angeführten Typs und außerdem unter b1) angeführten Polyaminen noch mindestens eine primäre und gegebenenfalls eine sekundäre Aminogruppe, also z.B. eine primäre oder eine sekundäre Aminogruppe, enthaltende aliphatische, cycloaliphatische, araliphatische oder heterocyclische Polyamine und Alkanolamine zugrunde liegen. Hierbei sind diejenigen Polyamidoamine zu bevorzugen, denen außer den vorstehend unter b₁)/c₁) genannten Polyaminen bzw. deren Gemischen, gegebenenfalls in Abmischung mit Alkanolmonoaminen und außer den gesättigten C₃-C₁₀-Dicarbonsäuren noch ω-Aminocarbonsäuren oder deren Lactame des unter 3. angeführten Typs zugrunde liegen.
- 1. reaction products of a) saturated aliphatic C₃-C₁₀ dicarboxylic acids. such as succinic acid, glutaric acid, adipic acid, sebacic acid, malonic acid or their functional derivatives, such as anhydrides and esters, the first three acids being preferred, with the mixtures of polyamines with alkanol monoamines mentioned under b) above.
- 2. Reaction products of such saturated modified dicarboxylic acids or their derivatives, which by addition of aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamines which contain at least two amino groups, namely primary and / or secondary, on α, β-olefinically unsaturated carboxylic acid esters , whose alcohol radical has 1 to 8, preferably 1 to 3 carbon atoms, such as ethyl acrylate and methyl methacrylate, obtained and then reacted with the polyamines mentioned above under b₁) / c₁) or their mixtures, optionally in admixture with alkanol monoamines.
- 3. reaction products of ω-aminocarboxylic acids containing at least three carbon atoms or their lactams, eg 6-aminocaproic acid and 8-aminocaprylic acid or 6-caprolactam and 8-capryllactam, with the mixtures of polyamines with alkanol monoamines mentioned under b) above.
- 4. reaction products of olefinically unsaturated dicarboxylic acids, such as maleic acid or fumaric acid or their functional derivatives, such as anhydrides or esters, with the polyamines mentioned above under b₁) / c₁) or their mixtures, optionally in a mixture with alkanol monoamines.
- 5. Such reaction products, which in addition to the saturated, aliphatic C₃-C₁₀ dicarboxylic acids mentioned under 1. and the unsaturated dicarboxylic acids mentioned under 4. still ω-aminocarboxylic acids or their lactams of the type mentioned under 3. and also under b1) polyamines at least a primary and optionally a secondary amino group, for example a primary or a secondary amino group, containing aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamines and alkanolamines. Here, those polyamidoamines are to be preferred which, in addition to the polyamines mentioned above under b₁) / c₁) or their mixtures, optionally in a mixture with alkanol monoamines and in addition to the saturated C₃-C₁₀ dicarboxylic acids, ω-aminocarboxylic acids or their lactams listed under 3 Type.
Umsetzungsprodukte vom Typ 1) unter Verwendung von Diethylentriamin, Triethylentetramin und Tetraethylenpentamin als Polyamin und 2-Aminoethanol als Alkanolmonoamin sind besonders bevorzugt.Reaction products of type 1) using diethylene triamine, triethylene tetramine and tetraethylene pentamine as the polyamine and 2-aminoethanol as the alkanol monoamine are particularly preferred.
Als Polyamine b1) und c1) kommen beispielsweise solche der Formel (I)
p Null oder eine ganze Zahl von 1 bis 6, vorzugsweise 1 bis 4 ist,
R₁ einen zweiwertigen, vorzugsweise nichtaromatischen Kohlenwasserstoffrest mit 2 bis 18 C-Atomen, vorzugsweise einen verzweigten oder unverzweigten Alkylenrest mit 2 bis 10 C-Atomen, insbesondere mit 2 bis 6 C-Atomen, oder einen Cycloalykylenrest mit 5 bis 12 C-Atomen, vorzugsweise 6 bis 10 C-Atomen, oder einen Aralkylenrest mit 7 bis 12 C-Atomen, vorzugsweise 8 bis 10 C-Atomen darstellt und
R₂, R2′ unabhängig voneinander für H oder einer der beiden Reste für
R₃, R₄ entweder unabhängig voneinander für H, (C₁-C₂₀)-Alkyl, vorzugsweise (C₁-C₆)Alkyl, stehen, wobei diese Alkylreste auch Hydroxygruppen tragen können.Examples of polyamines b1) and c1) are those of the formula (I)
p is zero or an integer from 1 to 6, preferably 1 to 4,
R₁ is a divalent, preferably non-aromatic hydrocarbon radical having 2 to 18 carbon atoms, preferably a branched or unbranched alkylene radical having 2 to 10 carbon atoms, in particular having 2 to 6 carbon atoms, or a cycloalykylene radical having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene radical having 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms and
R₂, R 2 ' independently of one another for H or one of the two radicals for
R₃, R₄ are either independently of one another H, (C₁-C₂₀) alkyl, preferably (C₁-C₆) alkyl, where these alkyl radicals can also carry hydroxyl groups.
Als Polyamine b1) seien z.B. genannt Methyl-bis-(3-aminopropyl)-amin, Ethyl-bis-(3-aminopropyl)-amin, N-(3-Aminopropyl)-tetramethylendiamin, N,N′-Bis-(3-aminopropyl)-tetramethylendiamin, Polyalkylenpolyamine, wie Di-propylen-(1,2)-triamin, Bis-(3-amino-propyl)-amin, Tripropylen-(1,2)-tetramin und vor allem Diethylentriamin, Triethylentetramin und Tetraethylenpentamin.Examples of polyamines b1) are called methyl bis (3-aminopropyl) amine, ethyl bis (3-aminopropyl) amine, N- (3-aminopropyl) tetramethylene diamine, N, N'-bis (3-aminopropyl) tetramethylene diamine, Polyalkylene polyamines such as di-propylene- (1,2) -triamine, bis- (3-aminopropyl) -amine, tripropylene- (1,2) -tetramine and especially diethylene triamine, triethylene tetramine and tetraethylene pentamine.
Polyamine c1) sind beispielsweise: Ethylendiamin, Propylendiamin, 1-Amino-3-methylamino-propan, 2-Methylpentamethylendiamin, Pentanethylendiamin, Hexamethylendiamin, Trimethylhexamethylendiamin, Neopentyldiamin, Octamethylendiamin, Dioxadodecandiamin, cyclialiphatische Diamine wie 1,2-, 1,3- oder 1,4-Cyclohexandiamin; 4,4′-Methylen-bis-cyclohexylamin, Isophorondiamin, Menthandiamin, 4,4′-Diamino-3,3′-dimethyl-di-cyclohexylmethan, 3-Aminomethyl-1-(3-aminopropyl-1-methyl)-4-methylcyclohexan, N-Methylethylendiamin, N-Aminoethylpiperazin, 1,3-Bis-aminomethylbenzol.Polyamines c1) are, for example: ethylenediamine, propylenediamine, 1-amino-3-methylamino-propane, 2-methylpentamethylene diamine, pentanethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, neopentyl diamine, octamethylene diamine, dioxadodecane diamine, cyclialiphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexane diamine; 4,4'-methylene-bis-cyclohexylamine, isophoronediamine, menthandiamine, 4,4'-diamino-3,3'-dimethyl-di-cyclohexylmethane, 3-aminomethyl-1- (3-aminopropyl-1-methyl) -4 -methylcyclohexane, N-methylethylenediamine, N-aminoethylpiperazine, 1,3-bis-aminomethylbenzene.
Als Alkanolmonoamine sind z.B. solche der Formel
H₂N-R₁-OH (II)
geeignet, in der R₁ die obige Bedeutung hat, wie 2-Aminoethanol, 1-Amino-2-propanol, 3-Amino-1-propanol, 2-Amino-1-butanol, 4-Amino-1-butanol, 5-Amino-1-pentanol, 6-Amino-1-hexanol und deren Isomere, deren Kohlenwasserstoffrest verzweigt ist oder die die Aminogruppe und/oder die Hydroxylgruppe an einen primären oder sekundären C-Atom tragen; ferner solche, die sich von cyclischen Kohlenwasserstoffresten, vorzugsweise mit 5-7 C-Atomen, ableiten.Examples of alkanol monoamines are those of the formula
H₂N-R₁-OH (II)
suitable in which R₁ has the above meaning, such as 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol, 5-amino -1-pentanol, 6-amino-1-hexanol and their isomers, the hydrocarbon radical of which is branched or which carry the amino group and / or the hydroxyl group on a primary or secondary carbon atom; furthermore those which are derived from cyclic hydrocarbon radicals, preferably having 5-7 carbon atoms.
Die zur Erzielung wasserlöslicher Polyamidoamine (B) mit optimalen Eigenschaften einzuhaltenden Mengenverhältnisse der in Betracht kommenden Komponenten lassen sich durch Vorversuche leicht ermitteln. Im allgemeinen ist die Mol-Menge an Dicarbonsäure oder deren funktionelle Derivate zu Polyamin/Alkanolmonoamin so, daß das Verhältnis von Carboxylgruppen zu der Summe von primären NH₂-Gruppen 1: (0,8-1,4), vorzugsweise 1: (0,95-1,1) beträgt. Im Falle von Mischungen von Polyaminen und Alkanolmonoaminen liegt das Verhältnis ihrer Molmengen bei 0,6:0,4 bis 0,99:0,01, vorzugsweise 0,8:0,2 bis 0,95:0,05.The quantitative ratios of the components in question to be maintained to achieve water-soluble polyamidoamines (B) with optimal properties can easily be determined by preliminary tests. In general, the molar amount of dicarboxylic acid or its functional derivatives to polyamine / alkanol monoamine is such that the ratio of carboxyl groups to the sum of primary NH₂ groups 1: (0.8-1.4), preferably 1: (0, 95-1.1). In the case of mixtures of polyamines and alkanol monoamines, the ratio of their molar amounts is 0.6: 0.4 to 0.99: 0.01, preferably 0.8: 0.2 to 0.95: 0.05.
Die Herstellung der Polyamidoamine (B) kann in üblicher Weise erfolgen, z.B. durch mehrstündiges Erhitzen der entsprechenden Komponenten unter Ausschluß von Sauerstoff auf Temperaturen von 125 bis 250°C, vorzugsweise von 140 bis 180°C, zunächst unter gewöhnlichem Druck und dann unter vermindertem Druck, wobei zur Vermeidung der Dunkelfärbung der Polyamide geringe Menge an Hydrazinhydrat oder Hydraziden zugesetzt werden können. Die Reaktionszeit hängt von den angewendeten Temperaturen und Drucken ab und liegt im allgemeinen zwischen 4 und 10 Stunden.The polyamidoamines (B) can be prepared in the customary manner, for example by heating the for several hours corresponding components with the exclusion of oxygen at temperatures of 125 to 250 ° C, preferably from 140 to 180 ° C, first under ordinary pressure and then under reduced pressure, with a small amount of hydrazine hydrate or hydrazides can be added to avoid the darkening of the polyamides. The reaction time depends on the temperatures and pressures used and is generally between 4 and 10 hours.
Anstelle des Epichlorhydrins (B) kann gegebenenfalls auch das Dichlorhydrin (1,3-Dichlor-2-hydroxypropan) eingesetzt werden.Instead of epichlorohydrin (B), dichlorohydrin (1,3-dichloro-2-hydroxypropane) can optionally also be used.
Als Basen (D) können unter anderem eingesetzt werden: Alkalihydroxide, bevorzugt Natrium- und Kaliumhydroxid, Carbonate, Bicarbonate, Erdalkalihydroxide, wie Calciumhydroxid, weiterhin Benzyltrimethylammoniumhydroxid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid oder entsprechende Gemische.Bases (D) which can be used include: alkali metal hydroxides, preferably sodium and potassium hydroxide, carbonates, bicarbonates, alkaline earth metal hydroxides, such as calcium hydroxide, furthermore benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or corresponding mixtures.
Die Herstellung der Reaktionsprodukte nach dem erfindungsgemäßen Verfahren kann in der Weise erfolgen, daß man die Polyamidoamine (B) und Epichlorhydrin (C) in einem ersten Reaktionsschritt bei einer Konzentration der Reaktionsteilnehmer von etwa 25 bis 50 %, vorzugsweise 35 bis 45 % und bei einer Temperatur zwischen 25 und 95°C, vorzugsweise 40 bis 70°C, solange reagieren läßt, bis die Viskosität einer 40 %igen Lösung (bestimmt bei 25°C) etwa 100 bis 600, vorzugsweise 200 bis 400 mPa.s beträgt. Anschließend setzt man diese Lösung in einem zweiten Reaktionsschritt mit einer wäßrigen Lösung einer Base (D), die in einer Menge von im allgemeinen 0,1 bis 1,0, vorzugsweise 0,1 bis 0,6 Mol pro Mol eingesetztes Epichlorhydrin (C) enthalten ist, bei einer Konzentration der Reaktionsteilnehmer von 10 bis 40 %, vorzugsweise 15 bis 25 %, und einer Temperatur zwischen 25 bis 95°C, vorzugsweise 40 bis 70°C, solange um, bis die Viskosität einer 12,5 %igen Lösung (bestimmt bei 25°C) 10-200 mPa.s, vorzugsweise 15 bis 80 mPa.s beträgt. Der pH-Wert in diesem zweiten Reaktionsschritt liegt bei größer als 8, vorzugsweise zwischen 9 und 12. Danach gibt man der Mischung zur Beendigung der Einwirkung und zur Stabilisierung der an sich selbstvernetzenden Reaktionsprodukte zweckmäßig so viel Säure oder Säurederivate zu, daß der pH-Wert der wäßrigen Lösung bei 1 bis 7, vorzugsweise zwischen 1,5 und 5 liegt, und stellt den Feststoffgehalt der Reaktionslösung durch Verdünnen mit Wasser auf 8 bis 25 Gew.-% ein.The reaction products can be prepared by the process according to the invention in such a way that the polyamidoamines (B) and epichlorohydrin (C) are in a first reaction step at a concentration of the reactants of about 25 to 50%, preferably 35 to 45% and at one Temperature between 25 and 95 ° C, preferably 40 to 70 ° C, until it can react until the viscosity of a 40% solution (determined at 25 ° C) is about 100 to 600, preferably 200 to 400 mPa.s. This solution is then set in a second reaction step with an aqueous solution of a base (D) which is used in an amount of generally 0.1 to 1.0, preferably 0.1 to 0.6, mol per mol of epichlorohydrin (C) is contained, at a concentration of the reactants of 10 to 40%, preferably 15 to 25%, and a temperature between 25 to 95 ° C, preferably 40 to 70 ° C, until the viscosity a 12.5% solution (determined at 25 ° C.) is 10-200 mPa.s, preferably 15 to 80 mPa.s. The pH in this second reaction step is greater than 8, preferably between 9 and 12. Then the mixture is expediently added to the mixture in order to terminate the action and to stabilize the self-crosslinking reaction products, so much acid or acid derivatives that the pH the aqueous solution is 1 to 7, preferably between 1.5 and 5, and adjusts the solids content of the reaction solution to 8 to 25% by weight by dilution with water.
In einer anderen, weniger bevorzugten Ausführungsform kann man während oder nach der Umsetzung von Polyamidoamin (B) und Epichlorhydrin (C) der Lösung zunächst Säure zugeben und den pH-Wert auf kleiner als 7, vorzugsweise 1,5 und 5 einstellen. Diese saure Reaktionsmischung wird dann mit soviel an Base (D) versetzt, daß der pH-Wert bei größer als 8, vorzugsweise zwischen 9 und 12 liegt, und dieses System wird dann für eine Zeitdauer von 0,5 bis 8 Stunden, vorzugsweise 1 bis 4 Stunden bei einer Temperatur von 25 bis 95°C, vorzugsweise 40 bis 70°C gehalten.In another, less preferred embodiment, acid can be added to the solution during or after the reaction of polyamidoamine (B) and epichlorohydrin (C) and the pH can be adjusted to less than 7, preferably 1.5 and 5. Sufficient base (D) is then added to this acidic reaction mixture such that the pH is greater than 8, preferably between 9 and 12, and this system is then used for a period of 0.5 to 8 hours, preferably 1 to 4 hours at a temperature of 25 to 95 ° C, preferably 40 to 70 ° C.
Als Säuren kommen vor allem halogenfreie Säuren, wie Schwefel-, Phosphor- oder Essigsäure in Betracht und als Säurederivate entsprechende Anhydride oder saure Salze.Halogen-free acids such as sulfuric, phosphoric or acetic acid are particularly suitable as acids and corresponding anhydrides or acidic salts as acid derivatives.
Die Menge an Epichlorhydrin (C) beträgt im allgemeinen 0,6 bis 2 Mol, vorzugsweise 1,0 bis 1,4 Mol pro Mol basischer Aminogruppen (primär, sekundär oder tertiär) im Polyamidoamin (B) und die Menge an Base (D) 0,1 bis 1,0 Mol, vorzugsweise 0,1 bis 0,6 Mol pro Mol eingesetztes Epichlorhydrin.The amount of epichlorohydrin (C) is generally 0.6 to 2 mol, preferably 1.0 to 1.4 mol, per mol of basic amino groups (primary, secondary or tertiary) in the polyamidoamine (B) and the amount of base (D) 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol, per mol of epichlorohydrin used.
Die erfindungsgemäßen Harze bzw. Harzlösungen weisen gegenüber den bisher bekannten Reaktionsprodukten aus Polyamidoamin und Epichlorhydrin einen erheblich geringeren organisch gebundenen Chlorgehalt auf und eignen sich deshalb in hervorragender Weise dazu, den organischen Chlorgehalt von Abwässern, u.a. von Papierfabriken, erheblich zu senken. Diese wertvolle Eigenschaft besitzen die Reaktionsprodukte, die bisher zur Verbesserung der Naßfestwirksamkeit von Papier verwendet worden sind, nicht in gleichem Umfang. Aufgrund der hohen Lagerstabiliät der erfindungsgemäßen Harzlösungen bleibt deren Naßfestwirksamkeit auch nach monatelanger Lagerung konstant.The resins or resin solutions according to the invention have a considerably lower level than the previously known reaction products of polyamidoamine and epichlorohydrin organically bound chlorine content and are therefore ideally suited to significantly reduce the organic chlorine content of wastewater, including paper mills. The reaction products which have hitherto been used to improve the wet strength effectiveness of paper do not possess this valuable property to the same extent. Due to the high storage stability of the resin solutions according to the invention, their wet strength effectiveness remains constant even after months of storage.
Mit Hilfe der nach dem erfindungsgemäßen Verfahren hergestellten Reaktionsprodukte gelingt es, die Naßfestigkeit von Papier - auch von Papier aus ungebleichtem Zellstoff - hervorragend zu verbessern. In manchen Fällen ist es - je nach Art des Papiers bzw. nach Wunsch - auch möglich, die Saugfähigkeit zu erhöhen. Bemerkenswert ist, daß die Reaktionsprodukte den Weißgrad von Papier, das aus gebleichtem Zellstoff hergestellt ist, praktisch nicht beeinträchtigen. Erwähnt sei ferner, daß die Geschwindigkeit, mit der die erfindungsgemäß zu verwendenden Reaktionsprodukte auf dem Papier bzw. im Zellstoff vernetzen, hoch ist und daß die Reaktionsprodukte auch als Retentionshilfsmittel für bei der Papierherstellung verwendete Füllstoffe, Drainagehilfsstoffe zur Verbesserung der Papierherstellungsgeschwindigkeit und Flockungsmittel zur Entfernung feiner Teilchen aus Schmutzwasser, zum Beispiel industriellem Abwasser, verwendet werden können.With the help of the reaction products produced by the process according to the invention, the wet strength of paper - including paper made from unbleached cellulose - can be outstandingly improved. In some cases, depending on the type of paper or as desired, it is also possible to increase the absorbency. It is noteworthy that the reaction products practically do not affect the whiteness of paper made from bleached pulp. It should also be mentioned that the speed at which the reaction products to be used according to the invention crosslink on the paper or in the pulp is high and that the reaction products are also used as retention aids for fillers used in papermaking, drainage aids to improve the papermaking speed and flocculants to remove fine particles Particles from dirty water, for example industrial waste water, can be used.
Um die Naßfestigkeit von Papier gemäß der vorliegenden Erfindung zu erhöhen, kann man beispielsweise so vorgehen, daß man die in Betracht kommenden Harze in Form wäßriger Lösungen bereits der wäßrigen Suspension des Papierrohstoffes vor der Verarbeitung zu Papier zusetzt. Die Mengen an Harz, die zur Erzielung der gewünschten Naßfestigkeit erforderlich sind, lassen sich durch Vorversuche ohne Schwierigkeiten ermitteln. Im allgemeinen empfiehlt es sich, 0,05 bis 2, vorzugsweise 0,1 bis 1,6 Gew.-Teile Festharz auf 100 Gew.-Teile Papierrohstoff einzusetzen, zweckmäßig in Form einer wäßrigen Lösung, deren Gehalt an Reaktionsprodukten 8 bis 25, vorzugsweise 10 bis 15 Gew.-% beträgt.In order to increase the wet strength of paper according to the present invention, one can proceed, for example, by adding the resins in question in the form of aqueous solutions to the aqueous suspension of the paper raw material before processing into paper. The amounts of resin required to achieve the desired wet strength can be determined by Determine preliminary tests without difficulty. In general, it is advisable to use 0.05 to 2, preferably 0.1 to 1.6 parts by weight of solid resin per 100 parts by weight of paper stock, advantageously in the form of an aqueous solution, the content of reaction products of which is preferably 8 to 25 10 to 15 wt .-% is.
Die folgenden Beispiele sollen die Erfindung näher veranschaulichen. Sofern nicht anders angegeben, bedeutet Prozent Gewichtsprozente. Der organische Chlorgehalt wurde aus der Differenz des nach der Verbrennungsmethode von Wickbold (Bezugsvorschriften: DIN 53 188, Abs. 13 und DIN 53 474, Abs. 5.5; 6.3) ermittelten Chlorgehaltes und dem ionischen Chlorgehalt bestimmt.The following examples are intended to illustrate the invention in more detail. Unless otherwise stated, percent means percentages by weight. The organic chlorine content was determined from the difference between the chlorine content and the ionic chlorine content determined using the Wickbold combustion method (reference specifications: DIN 53 188, paragraph 13 and DIN 53 474, paragraph 5.5; 6.3).
392 g Diethylentriamin (3,8 Mol) und 24,4 g (0,4 Mol) 2-Amino-ethanol wurden in einen Vierhalskolben, der mit Rührer, Thermometer und Destillationsapparatur versehen war, gefüllt und innerhalb von 30 Minuten 584 g Adipinsäure (4 Mol) portionsweise zugegeben, so daß die Temperatur nicht über 100°C stieg. Dann wurde unter Stickstoff in 3 Stunden auf 150°C geheizt, eine Stunde bei dieser Temperatur gehalten und weiter auf 170°C erwärmt, wobei das gebildete Wasser gleichmäßig herausdestillierte. Nach einer Haltezeit von etwa 2 Stunden hatte das Kondensat eine Säurezahl von 20 mgKOH/g und eine Aminzahl von 251 mgKOH/g. Nach Entfernen der Heizung wurde das Polyamidoamin mit 570 g Wasser verdünnt. Die Lösung hatte einen Festkörpergehalt von 59,8 % (1 g, 1 Stunde, 125°C) und eine Viskosität bei 25°C von 1174 mPa.s.392 g of diethylenetriamine (3.8 mol) and 24.4 g (0.4 mol) of 2-aminoethanol were placed in a four-necked flask equipped with a stirrer, thermometer and distillation apparatus, and 584 g of adipic acid ( 4 mol) was added in portions so that the temperature did not rise above 100.degree. The mixture was then heated to 150.degree. C. under nitrogen in 3 hours, held at this temperature for one hour and further heated to 170.degree. C., the water formed distilling out uniformly. After a holding time of about 2 hours, the condensate had an acid number of 20 mgKOH / g and an amine number of 251 mgKOH / g. After removing the heater, the polyamidoamine was diluted with 570 g of water. The solution had a solids content of 59.8% (1 g, 1 hour, 125 ° C.) and a viscosity at 25 ° C. of 1174 mPa.s.
- a) 322 g der Polyamidoamin-Vorproduktlösung aus Beispiel 1 (entsprechend 0,857 Val NH) und 321 g Wasser wurden in einem Dreihalskolben mit Rührer, Thermometer und Kühler gegeben und unter Rühren 111 g Epichlorhydrin (1,20 Mol) zugesetzt. In 30 Minuten wurde auf 55 bis 60°C erwärmt und bei dieser Temperatur gehalten. Nach 6 Stunden betrug die Gardner-Viskosität I.a) 322 g of the polyamidoamine precursor solution from Example 1 (corresponding to 0.857 val NH) and 321 g of water were placed in a three-necked flask with a stirrer, thermometer and condenser and 111 g of epichlorohydrin (1.20 mol) were added with stirring. The mixture was heated to 55-60 ° C. in 30 minutes and held at this temperature. After 6 hours the Gardner viscosity was I.
- b) Es wurden 352 g Wasser zugegeben, auf 60 bis 65°C erwärmt und bei dieser Temperatur gehalten. Nach 3 Stunden betrug die Gardner-Viskosität F. Dann wurden 1295 g Wasser, in denen 2,5 g Kaliumsorbat gelöst waren, zugegeben und gekühlt. Danach wurde mit 14 g 48 %iger Schwefelsäure auf pH 3,70 eingestellt. Die Harzlösung hatte einen Festkörpergehalt von 12,6 % (1 g, 1 Stunde, 100°C) und eine Viskosität bei 25°C von 21 mPa.s.b) 352 g of water were added, heated to 60 to 65 ° C and kept at this temperature. After 3 hours the Gardner viscosity was F. Then 1295 g of water, in which 2.5 g of potassium sorbate was dissolved, were added and cooled. The pH was then adjusted to 3.70 with 14 g of 48% sulfuric acid. The resin solution had a solids content of 12.6% (1 g, 1 hour, 100 ° C.) and a viscosity at 25 ° C. of 21 mPa.s.
- a) 207 g der Polyamidoamin-Vorproduktlösung aus Beispiel 1 (entsprechend 0,552 Val NH) und 207 g Wasser wurden in einen Dreihalskolben mit Rührer, Thermometer und Kühler gegeben und unter Rühren 66,5 g Epichlorhydrin (0,72 Mol) zugesetzt. In 60 Minuten wurde auf 60°C erwärmt und bei dieser Temperatur gehalten. Nach 3 Stunden betrug die Gardner-Viskosität M.a) 207 g of the polyamidoamine precursor solution from Example 1 (corresponding to 0.552 Val NH) and 207 g of water were placed in a three-necked flask equipped with a stirrer, thermometer and condenser and 66.5 g of epichlorohydrin (0.72 mol) were added with stirring. The mixture was heated to 60 ° C. in 60 minutes and held at this temperature. After 3 hours the Gardner viscosity was M.
- b) Es wurden 578 g Wasser zugegeben, auf 65°C erwärmt und bei dieser Temperatur gehalten. Nach 4 Stunden betrug die Gardner-Viskosität F-G. Dann wurden 442 g Wasser, in denen 1,5 g Kaliumsorbat gelöst waren, zugegeben und gekühlt. Danach wurde mit 9,2 g 48 %iger Schwefelsäure auf pH 3,9 eingestellt. Die Harzlösung hatte einen Festkörpergehalt von 12,6 % (1 g , 1 Stunde, 100°C) und eine Viskosität bei 25°C von 47 mPa.s.b) 578 g of water were added, heated to 65 ° C. and kept at this temperature. After 4 hours, the Gardner viscosity was FG. Then 442 g of water in which 1.5 g of potassium sorbate was dissolved were added and cooled. Thereafter, the pH was adjusted to 3.9 with 9.2 g of 48% strength sulfuric acid set. The resin solution had a solids content of 12.6% (1 g, 1 hour, 100 ° C.) and a viscosity at 25 ° C. of 47 mPa.s.
a) Es wurde zunächst wie in Beispiel 2a)/b) verfahren; die Wasserverdünnung in der Stufe b) erfolgte jedoch auf ca. 20 %. Die resultierende Harzlösung hatte folgende Daten:
b) In Anlehnung an die Lehre von Anspruch 11 oder US-PS 3.352.833 wurden 200 ml der Harzlösung gemäß a) bei Raumtemperatur mit 4,1 ml 10 n NaOH (entsprechend 2,5 Equivalenten NaOH pro Equivalent H₂SO₄) während 4 Stunden umgesetzt. Die Ergebnisse zeigt die Tabelle 2.
c) Die Laugenbehandlung erfolgte analog Abschnitt b), jedoch wurde die Lauge in einer Menge entsprechend Beispiel 10 der US-PS 3.352.833 eingesetzt, nämlich 17,5 ml 10 n NaOH pro 200 g Harzlösung (= Equivalent der Summe der Menge an Epichlorhydrin und H₂SO₄). Bezüglich der Ergebnisse siehe wiederum die Tabelle 2.
a) The procedure was first as in Example 2a) / b); however, the water dilution in stage b) was about 20%. The resulting resin solution had the following data:
b) Based on the teaching of claim 11 or US Pat. No. 3,352,833, 200 ml of the resin solution according to a) were reacted at room temperature with 4.1 ml of 10N NaOH (corresponding to 2.5 equivalents of NaOH per equivalent of H₂SO₄) for 4 hours . The results are shown in Table 2.
c) The lye treatment was carried out analogously to section b), but the lye was used in an amount corresponding to Example 10 of US Pat. No. 3,352,833, namely 17.5 ml of 10N NaOH per 200 g of resin solution (= equivalent to the sum of the amount of epichlorohydrin and H₂SO₄). See Table 2 for the results.
a) Es wurde zunächst wie im Beispiel 3a)/b) verfahren; die resultierende Harzlösung hatte folgende Daten:
b) Analog wie bei 4b) wurden 200 g der vorstehenden Harzlösung mit 2,85 ml 10 n NaOH (2,5 Equivalente/Equivalent H₂SO₄) während 4 Stunden bei Raumtemperatur umgesetzt. Ergebnisse siehe Tabelle 2.
c) Analog Beispiel 4c) wurden 200 g der vorstehenden Harzlösung mit 10,7 ml 10 n NaOH umgesetzt (= Equivalent der Summe der Menge an Epichlorhydrin und H₂SO₄). Bezüglich der Ergebnisse siehe die Tabelle 2.
a) The procedure was first as in Example 3a) / b); the resulting resin solution had the following data:
b) Analogous to 4b), 200 g of the above resin solution were reacted with 2.85 ml of 10N NaOH (2.5 equivalents / equivalent H₂SO₄) for 4 hours at room temperature. See Table 2 for results.
c) Analogous to Example 4c), 200 g of the above resin solution were reacted with 10.7 ml of 10N NaOH (= equivalent to the sum of the amount of epichlorohydrin and H₂SO₄). See Table 2 for the results.
- a) 207 g der Polyamidoamin-Vorproduktlösung aus Beispiel 1 (entsprechend 0,552 Val NH) und 207 g Wasser wurden in einen Dreihalskolben mit Rührer, Thermometer und Kühler gegeben und unter Rühren 66,5 g Epichlorhydrin (0,72 Mol) zugesetzt. In 45 Minuten wurde auf 60°C erwärmt und bei dieser Temperatur gehalten. Nach 3,5 Stunden betrug die Gardner-Viskosität N.a) 207 g of the polyamidoamine precursor solution from Example 1 (corresponding to 0.552 Val NH) and 207 g of water were placed in a three-necked flask equipped with a stirrer, thermometer and condenser and 66.5 g of epichlorohydrin (0.72 mol) were added with stirring. The temperature was raised to 60 ° C. in 45 minutes and held at this temperature. After 3.5 hours the Gardner viscosity was N.
- b) Es wurden 578 g 1 %ige Natronlauge zugegeben, auf 65°C erwärmt und bei dieser Temperatur gehalten. Nach 3 Stunden betrug die Gardner-Viskosität E-F. Dann wurden 442 g Wasser, in denen 1,5 g Kaliumsorbat gelöst waren, zugegeben, gekühlt und anschließend mit 11,7 g 48 %iger Schwefelsäure auf pH 3,9 eingestellt. Die Harzlösung hatte einen Festkörpergehalt von 12,7 % (1 g, 1 Stunde, 100°C) und eine Viskosität bei 25°C von 39 mPa.s.b) 578 g of 1% sodium hydroxide solution were added, heated to 65 ° C. and kept at this temperature. After 3 hours the Gardner viscosity was E-F. Then 442 g of water, in which 1.5 g of potassium sorbate were dissolved, were added, cooled and then adjusted to pH 3.9 with 11.7 g of 48% strength sulfuric acid. The resin solution had a solids content of 12.7% (1 g, 1 hour, 100 ° C.) and a viscosity at 25 ° C. of 39 mPa.s.
Nach der Arbeitsweise analog Beispiel 6, aber mit unterschiedlichen Mengen Natriumhydroxid, wurden folgende weitere Produkte hergestellt:
- 7. Im Reaktionsschritt b) wurden 578 g 1,5 %ige Natronlauge zugegeben.
Das Ansäuern erfolgte mit 24,9 g 48 %iger Schwefelsäure auf pH 1,75. Die erhaltene Harzlösung hatte einen Festkörpergehalt von 13,3 % (1 g, 1 Stunde, 100°C) und eine Viskosität bei 25°C von 34 mPa.s. - 8. Im Reaktionsschritt b) wurden 578 g 2,0 %ige Natronlauge zugegeben.
Das Ansäuern erfolgte mit 37,5 g 48 %iger Schwefelsäure auf pH 1,75. Die erhaltene Harzlösung hatte einen Festkörpergehalt von 13,5 % (1 g, 1 Stunde, 100°C) und eine Viskosität bei 25°C von 40 mPa.s.
- 7. In reaction step b) 578 g of 1.5% sodium hydroxide solution were added.
Acidification was carried out with 24.9 g of 48% sulfuric acid to pH 1.75. The resin solution obtained had a solids content of 13.3% (1 g, 1 hour, 100 ° C.) and a viscosity at 25 ° C. of 34 mPa.s. - 8. In reaction step b), 578 g of 2.0% sodium hydroxide solution were added.
Acidification was carried out with 37.5 g of 48% sulfuric acid to pH 1.75. The resin solution obtained had a solids content of 13.5% (1 g, 1 hour, 100 ° C.) and a viscosity at 25 ° C. of 40 mPa.s.
Zu 2 kg einer Suspension von 10 g gebleichtem Sulfitzellstoff mit einem Mahlgrad von 42 bis 43°C Schopper-Riegler wurde unter starkem Rühren die 12,5 %igen, wäßrigen Harzlösungen von Beispiel 2, 3, 6, 7 und 8 in einer Menge von 1 % Festharz auf Zellstoff gegeben.To 12 kg of a suspension of 10 g of bleached sulfite pulp with a freeness of 42 to 43 ° C. Schopper-Riegler was added the 12.5% strength aqueous resin solutions from Examples 2, 3, 6, 7 and 8 in an amount of 1% solid resin added to cellulose.
Nach einer Aufziehzeit von mindestens 2 Minuten wurden in einem Blattbildner nach Schopper zwei Papierblätter von ca. 320 m² Fläche mit einem Flächengewicht von 100 g/m² gebildet, auf dem Trockenzylinder 5 Minuten bei 100°C erwärmt und 10 Minuten bei 120°C im Trockenschrank nachgehärtet. Nach einer Klimatisierungszeit von 24 Stunden bei 20°C und 65 % relativer Luftfeuchtigkeit wurden von Probestreifen des Papiers die Naßfestigkeiten in Newton (N) nach der Prüfvorschrift des Zelluloseinstituts der Technischen Hochschule Darmstadt gemessen. Das auf diese Weise erhaltene Papier wies eine Naßfestigkeit auf, die erheblich höher lag als die eines Papiers, das aus dem gleichen gebleichten Sulfitzellstoff ohne Zusatz der wäßrigen Lösungen der erfindungsgemäß verwendeten Produkte unter gleichen Versuchsbedingungen hergestellt wurde.After a mounting time of at least 2 minutes, two sheets of paper of approximately 320 m² in area with a basis weight of 100 g / m² were formed in a sheet former according to Schopper, heated on the drying cylinder for 5 minutes at 100 ° C. and 10 minutes at 120 ° C. in the drying cabinet post-hardened. After an air conditioning time of 24 hours at 20 ° C and 65% relative humidity, the wet strengths of the paper were measured in Newton (N) according to the test specification of the cellulose institute of the Darmstadt University of Technology. The paper obtained in this way had a wet strength which was considerably higher than that of paper which was produced from the same bleached sulfite pulp without the addition of the aqueous solutions of the products used according to the invention under the same test conditions.
Die Naßfestigkeiten in Newton (N) sind in Relativ-%, bezogen auf Vergleichsprodukt 2 = 100 %, in Tabelle 1 angegeben.
Aus dieser Tabelle 1 ist zu ersehen, daß gegenüber den Vergleichsbeispielen 2 und 3 der Gehalt an organisch gebundenem Chlor in den Beispielen 6 bis 8 deutlich erniedrigt ist, wobei in dem Beispiel 8 der Wert nur noch ca. 20 % des Vergleichsbeispiels 3 beträgt. Darüber hinaus weisen die nach dem erfindungsgemäßen Verfahren hergestellten Reaktionsprodukte ausgezeichnete Naßfestwirksamkeiten und gute Lagerstabilitäten auf.
Aus dieser Tabelle ist ersichtlich, daß die nach 4c/5c erhaltenen Produkte zu einer Abnahme des organisch gebundenen Chlorgehaltes (Zunahme an Cl⁻) führen, aber keine ausreichende Lagerstabilität aufweisen (nach 24 h Gel).From this table it can be seen that the products obtained after 4c / 5c lead to a decrease in the organically bound chlorine content (increase in Cl⁻), but do not have sufficient storage stability (after 24 h of gel).
Demgegenüber sind die nach 4b/5b erhaltenen Produkte noch nach 10 Tagen (50°C) stabil. Die Erhöhung des Cl⁻Gehaltes bleibt aber deutlich hinter den erfindungsgemäßen Harzen zurück. Im Fall von Harz 5b) errechnet sich ein Wert von organisch gebundenem Chlor von 0,42 %; bei den erfindungsgemäßen Beispielen 6, 7 und 8 wird dieser Wert unterschritten.In contrast, the products obtained after 4b / 5b are still stable after 10 days (50 ° C). However, the increase in the Cl⁻ content remains significantly behind the resins according to the invention. In the case of resin 5b), the value of organically bound chlorine is 0.42%; in Examples 6, 7 and 8 according to the invention this value is not reached.
Aus diesen Versuchen ist zu ersehen, daß nach dem in der US-Patentschrift 3.352.833 angegebenen Verfahren keine stabilen, an organ. gebundenem Chlor armen Produkte erhalten werden können, wie sie das erfindungsgemäße Verfahren liefert. Dies bestätigt, was aus der Technik bekannt ist. Die Verarbeitung alkal. aktivierter Harze muß bei genauer Alkalidosierung innerhalb einer bestimmten Zeit erfolgen, was in der Praxis als ein großer Nachteil empfunden wird.It can be seen from these experiments that no stable organ-based compounds can be obtained by the process specified in US Pat. No. 3,352,833. bound chlorine poor products can be obtained, as it provides the inventive method. This confirms what is known in the art. The processing of alkali-activated resins has to be carried out within a certain period of time with precise dosing of alkali, which in practice is perceived as a great disadvantage.
Claims (13)
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AT89112049T ATE90405T1 (en) | 1988-07-02 | 1989-07-01 | AQUEOUS SOLUTIONS OF POLYAMIDOAMINE EPIHLORHYRIN RESINS, PROCESS FOR THEIR PREPARATION AND USE. |
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EP0282862A2 (en) * | 1987-03-17 | 1988-09-21 | Bayer Ag | Nitrogen containing, water soluble compounds |
EP0332967A2 (en) * | 1988-03-16 | 1989-09-20 | Bayer Ag | Polyamide amine resin |
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- 1989-07-01 EP EP89112049A patent/EP0349935B1/en not_active Expired - Lifetime
- 1989-07-01 AT AT89112049T patent/ATE90405T1/en not_active IP Right Cessation
- 1989-07-01 ES ES89112049T patent/ES2058408T3/en not_active Expired - Lifetime
- 1989-07-01 DE DE8989112049T patent/DE58904602D1/en not_active Expired - Fee Related
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US5171795A (en) * | 1990-08-01 | 1992-12-15 | Hercules Incorporated | Process for the production of improved polyaminopolyamide epichlorohydrin resins |
US5470742A (en) * | 1991-04-24 | 1995-11-28 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
US5843763A (en) * | 1991-04-24 | 1998-12-01 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
US5871616A (en) * | 1991-04-24 | 1999-02-16 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
EP0512423A2 (en) * | 1991-05-06 | 1992-11-11 | Hoechst Aktiengesellschaft | Aqueous solutions of cationic polyamidoamine resins |
EP0512423A3 (en) * | 1991-05-06 | 1993-11-10 | Hoechst Ag | Aqueous solutions of cationic polyamidoamine resins |
WO1992022601A1 (en) * | 1991-06-19 | 1992-12-23 | Akzo N.V. | Epihalohydrin-based resins having a reduced halogen content |
EP0776923A2 (en) * | 1991-06-19 | 1997-06-04 | Akzo Nobel N.V. | Epihalohydrin-based resins having a reduced halogen content |
EP0776923A3 (en) * | 1991-06-19 | 1997-08-06 | Akzo Nobel Nv | Epihalohydrin-based resins having a reduced halogen content |
WO1993003222A1 (en) * | 1991-08-05 | 1993-02-18 | Henkel Corporation | Wet strength resin composition and method of making same |
EP0703265A1 (en) | 1994-07-22 | 1996-03-27 | Hoechst Aktiengesellschaft | Hydrophilic Hydrogels with elevated swelling capacity |
US5972691A (en) * | 1995-06-07 | 1999-10-26 | Hercules Incorporated | Dehalogenation of polyamine, neutral curing wet strength resins |
US6107432A (en) * | 1997-05-28 | 2000-08-22 | Basf Ag | Water-swellable, hydrophilic polymer compositions |
WO1999009252A1 (en) * | 1997-08-13 | 1999-02-25 | Fort James Corporation | Wet strength thermosetting resin formulations and polyaminamide polymers suitable for use in the manufacture of paper products |
US6222006B1 (en) | 1997-08-13 | 2001-04-24 | Fort James Corporation | Wet strength thermosetting resin formulations and polyaminamide polymers suitable for use in the manufacture of paper products |
US6429267B1 (en) | 1997-12-31 | 2002-08-06 | Hercules Incorporated | Process to reduce the AOX level of wet strength resins by treatment with base |
US6472478B1 (en) | 1998-02-21 | 2002-10-29 | Basf Aktiengesellschaft | Process for crosslinking hydrogels with bis- and poly-2- oxazolidinones |
US6503979B1 (en) | 1998-02-26 | 2003-01-07 | Basf Aktiengesellschaft | Method for cross-linking hydrogels with bis- and poly-2-oxazolidinones |
US6559239B1 (en) | 1998-11-26 | 2003-05-06 | Basf Aktiengesellschaft | Method for the secondary cross-linking of hydrogels with N-acyl-2-oxazolidinones |
US6657015B1 (en) | 1998-11-26 | 2003-12-02 | Basf Aktiengesellschaft | Method for the secondary cross-linking of hydrogels with 2-oxotetrahydro-1,3-oxazines |
US7175740B2 (en) | 1999-06-11 | 2007-02-13 | Hercules Incorporated | Reduced by product polyamine-epihalohydrin resins |
US7303652B2 (en) | 2000-12-09 | 2007-12-04 | Hercules Incorporated | Reduced byproduct high solids polyamine-epihalohydrin compositions |
US7183360B2 (en) | 2001-10-05 | 2007-02-27 | Basf Aktiengesellschaft | Method for crosslinking hydrogels with morpholine-2,3-diones |
US7655733B2 (en) | 2004-08-04 | 2010-02-02 | Basf Aktiengesellschaft | Postcrosslinking of water absorbing polymers with cyclic carbamates and/or cyclic ureas |
US7947771B2 (en) | 2004-11-30 | 2011-05-24 | Basf Aktiengesellschaft | Insoluble metal sulfates in water absorbing polymeric particles |
WO2008036241A1 (en) | 2006-09-18 | 2008-03-27 | Hercules Incorporated | Membrane separation process for removing residuals from polyamine-epihalohydrin resins |
Also Published As
Publication number | Publication date |
---|---|
ES2058408T3 (en) | 1994-11-01 |
US5019606A (en) | 1991-05-28 |
DE3822490A1 (en) | 1990-01-04 |
EP0349935B1 (en) | 1993-06-09 |
EP0349935A3 (en) | 1991-05-08 |
DE58904602D1 (en) | 1993-07-15 |
ATE90405T1 (en) | 1993-06-15 |
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