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EP0349935B1 - Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation - Google Patents

Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation Download PDF

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Publication number
EP0349935B1
EP0349935B1 EP89112049A EP89112049A EP0349935B1 EP 0349935 B1 EP0349935 B1 EP 0349935B1 EP 89112049 A EP89112049 A EP 89112049A EP 89112049 A EP89112049 A EP 89112049A EP 0349935 B1 EP0349935 B1 EP 0349935B1
Authority
EP
European Patent Office
Prior art keywords
resin
acid
epichlorohydrin
polyamidoamine
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89112049A
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German (de)
English (en)
Other versions
EP0349935A2 (fr
EP0349935A3 (fr
Inventor
Manfred Marten
Walter Dr. Kamutzki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT89112049T priority Critical patent/ATE90405T1/de
Publication of EP0349935A2 publication Critical patent/EP0349935A2/fr
Publication of EP0349935A3 publication Critical patent/EP0349935A3/fr
Application granted granted Critical
Publication of EP0349935B1 publication Critical patent/EP0349935B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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 comparative experiments which follow below).
  • reaction products from epihalohydrin and polyamidoamines are already known from EP-A-0 131 200, the polyamidoamines being reaction products from dicarboxylic acids, aliphatic polyamines and monoalkanolamines. An alkaline aftertreatment of these reaction products is not mentioned.
  • the present invention now relates to a storage-stable, aqueous solution of a water-dilutable polyamidoamine-epichlorohydrin resin (A) obtained by converting a water-dilutable, basic polyamidoamine (B), consisting of an acid component (B1), and an amine component (B2), with epichlorohydrin (C), in an aqueous system and in a ratio of 0.6 to 2 moles per mole of basic (with (C) reactive) amino groups of the polyamidoamine (B), addition of a base (D) at 25 to 95 ° C, optionally after prior acidification of the reaction system that the pH is above 8, and subsequent addition of acid to one pH value of at most 7, the content of organically bound chlorine in the resin (A) being at most 4% by weight and the component (B2) consisting of a mixture of one or more polyamines and alkanolamines.
  • A water-dilutable polyamidoamine-epichlorohydrin resin
  • 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) are 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 polyamine and 2-aminoethanol as alkanol monoamine are particularly preferred.
  • 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, pentane methylene 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
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyamides (AREA)

Claims (13)

  1. Solution aqueuse d'une résine (A) d'une polyamidoamine-épichlorhydrine diluable à l'eau, que l'on obtient par la réaction d'une polyamidoamine (B) basique, diluable à l'eau, consistant en un composant acide (B1) et en un composant amine (B2), avec l'épichlorhydrine (C) dans un système aqueux et selon un rapport de 0,6 à 2 moles par mole des groupes amino ( réactifs avec (C)) de la polyamidoamine (B),addition d'une base (D) entre 25 et 95°C, (éventuellement après acidulation préliminaire du système de réaction), l'addition étant réalisée de manière que le pH se situe au-dessus de 8, et addition subséquente d'acide pour obtenir un pH valant 7 au maximum, la teneur en du chlore lié à des fragments organiques ("chlore organique") étant dans la résine (A) de 4 % au maximum, en poids, et le composant (B2) consistant en un mélange d'une ou plusieurs polyamines et alcanolamines.
  2. Solution de résine selon la revendication 1, caractérisée en ce que le pH se situe entre 1,5 et 5.
  3. Solution de résine selon la revendication 1 et/ou 2, caractérisée en ce que la résine (A) présente un poids moléculaire moyen M n valant au moins 1000.
  4. Solution de résine selon l'une au moins des revendications 1 à 3, caractérisée en ce que la teneur en chlore organique présent dans la résine (A) est de 1 à 4 % en poids.
  5. Solution de résine selon l'une au moins des revendications 1 à 4, caractérisée en ce que la teneur en résine (A) se situe entre 8 et 25 % en poids.
  6. Solution de résine selon au moins une des revendications 1 à 5, caractérisée en ce que l'épichlorhydrine (C) est utilisée en une quantité de 0,6 à 2,0 moles par mole des groupes amino basiques de la polyamidoamine (B).
  7. Procédé pour préparer des solutions de résine selon l'une au moins des revendications 1 à 6, caractérisé en ce qu'on fait réagir dans un système aqueux des polyamidoamines (B) basiques, hydrosolubles, avec l'épichlorhydrine (C) selon un rapport de 0,6 à 2 moles par mole des groupes amino basiques ( réactifs avec (C)) de la polyamidoamine (B), puis, éventuellement après une acidulation préliminaire du système réactionnel, on fait réagir ce système, entre 25 et 95°C , avec une quantité d'une base (D) telle que le pH se situe à une valeur supérieure à 8, puis, par addition d'un acide, on règle le pH à une valeur n'excédant pas 7.
  8. Procédé selon la revendication 7, caractérisé en ce que la quantité de base (D) est de 0,1 à 0,6 mole par mole d'épichlorhydrine mise en oeuvre.
  9. Procédé selon la revendication 7 et/ou 8, caractérisé en ce qu'on utilise comme base de l'hydroxyde de sodium ou de l'hydroxyde de potassium.
  10. Procédé selon l'une au moins des revendications 7 à 9, caractérisé en ce qu'on soumet le produit de réaction ainsi obtenu à un ajustement, effectué à l'aide d'un acide, de son pH à une valeur comprise entre 1,5 à 5.
  11. Procédé selon la revendication 10, caractérisé en ce qu'on utilise comme acides l'acide sulfurique, l'acide chlorhydrique, l'acide acétique ou l'acide formique.
  12. Procédé selon l'une au moins des revendications 7 à 11, caractérisé en ce que la réaction avec la base (D) a lieu entre 40 et 70°C.
  13. Utilisation de la solution aqueuse de résine selon l'une au moins des revendications 1 à 6 comme adjuvant dans l'industrie de fabrication du papier, en particulier pour augmenter la résistance du papier au mouillé.
EP89112049A 1988-07-02 1989-07-01 Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation Expired - Lifetime EP0349935B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89112049T ATE90405T1 (de) 1988-07-02 1989-07-01 Waessrige loesungen von polyamidoamin-epichlorhyrin-harzen, verfahren zu ihrer herstellung und ihre verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3822490A DE3822490A1 (de) 1988-07-02 1988-07-02 Waessrige loesungen von polyamidoamin-epichlorhyrin-harzen, verfahren zu ihrer herstellung und ihre verwendung
DE3822490 1988-07-02

Publications (3)

Publication Number Publication Date
EP0349935A2 EP0349935A2 (fr) 1990-01-10
EP0349935A3 EP0349935A3 (fr) 1991-05-08
EP0349935B1 true EP0349935B1 (fr) 1993-06-09

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EP89112049A Expired - Lifetime EP0349935B1 (fr) 1988-07-02 1989-07-01 Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation

Country Status (5)

Country Link
US (1) US5019606A (fr)
EP (1) EP0349935B1 (fr)
AT (1) ATE90405T1 (fr)
DE (2) DE3822490A1 (fr)
ES (1) ES2058408T3 (fr)

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EP0349935A2 (fr) 1990-01-10
US5019606A (en) 1991-05-28
EP0349935A3 (fr) 1991-05-08
DE3822490A1 (de) 1990-01-04
ES2058408T3 (es) 1994-11-01
ATE90405T1 (de) 1993-06-15
DE58904602D1 (de) 1993-07-15

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