EP2904146B1 - Verfahren zur herstellung einer stabilen emulsion aus alkenylbernsteinsäureanhydrid in einer wässrigen lösung aus einem kationischen stärkehaltigen material, hergestellte emulsion und verwendung davon - Google Patents

Verfahren zur herstellung einer stabilen emulsion aus alkenylbernsteinsäureanhydrid in einer wässrigen lösung aus einem kationischen stärkehaltigen material, hergestellte emulsion und verwendung davon Download PDF

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Publication number
EP2904146B1
EP2904146B1 EP13782800.0A EP13782800A EP2904146B1 EP 2904146 B1 EP2904146 B1 EP 2904146B1 EP 13782800 A EP13782800 A EP 13782800A EP 2904146 B1 EP2904146 B1 EP 2904146B1
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Prior art keywords
emulsion
asa
cationic starch
starch material
preferentially
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EP13782800.0A
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English (en)
French (fr)
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EP2904146A1 (de
Inventor
Nicolas Leroy
Gilles DUTHOIT
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Roquette Freres SA
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Roquette Freres SA
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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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch

Definitions

  • the present invention relates to a method for producing an alkenyl succinic anhydride (ASA) emulsion in an aqueous solution of cationic starchy material, it being understood that the oily phase is constituted by ASA, the starchy solution acting as a carrier of said emulsion.
  • aqueous solution of cationic starchy material is meant a composition containing at least one cationic starch in aqueous solution.
  • the method described in the present application does not implement a recirculation loop of the product at the emulsification unit, and carries out a dilution of the emulsion once it is manufactured: a product with granulometry both fine, monodisperse, and stable over time.
  • This provides an efficient method, simple to implement, especially at a papermaking production site, to deliver an emulsion that can be stored during the shutdown of the paper machine for cleaning or maintenance operations.
  • ASA alkenyl succinic anhydride
  • This chemical species which is not miscible in water must be emulsified in order to be advantageously used in the form of a liquid product: this allows a good contact between the ASA and the cellulose fibers.
  • the emulsion in question is an ASA emulsion in an aqueous solution of cationic starchy material; in the rest of the application, it may also be referred to simply as an emulsion.
  • aqueous solutions of cationic starchy materials of different natures the starchy material being optionally modified; the function of such compositions is to prevent the coalescence of the ASA particles by positive ionization of the surface of the particles, and to bring the ASA particles closer to the fibers by an ionic mechanism.
  • a dry weight ratio of cationic starchy material / ASA of between 0.2 and 4 is used. Examples of such emulsions are described in the documents US 4,606,773 A , WO 2006/096216 A1 and DE 3105903 A1 .
  • the ASA emulsion in the aqueous solution of cationic starchy material must have a number of characteristics. In particular, it must have a great fineness of particle sizes, as well as a narrow spectrum of distribution of these sizes ("monodisperse" product). As explained in the document WO 97/35068 A1 these parameters condition the effectiveness of the bonding composition vis-à-vis the hydrophobicity properties it is supposed to confer.
  • the Applicant has recently developed a method of manufacturing an ASA emulsion in a composition of cationic starchy material, leading to a narrow particle size distribution and centered on an interval of between 1 ⁇ m and 1.5 ⁇ m and this, without temperature rise of the emulsion, a phenomenon that accelerates the hydrolysis of ASA.
  • the resulting emulsions indeed confer excellent hydrophobizing properties on the papers in which they are intended to be used. This process is described in the document WO 2013/186491 A1 .
  • the key to this process is based on a step of emulsifying an ASA / aqueous cationic amylaceous material in a single pass (that is to say without recirculation loop as in the prior art), while by adjusting the dry matter content of the initial aqueous solution of cationic starch material to between about 7% and 12% of its total weight.
  • the emulsions thus manufactured do not exhibit a stable particle size distribution. It has thus been found that the average diameter of said particles is rapidly changing over time, sometimes to values of greater than 4 ⁇ m: it therefore deviates substantially from the optimum value sought by the paper manufacturer and as defined above, with a view to get an effective collage of the sheet of paper. However, it is not uncommon for the paper machine to be stopped for several minutes, or even hours, for cleaning or maintenance operations. In this respect, it is essential that the particle size distribution of the particle sizes of the emulsion does not vary.
  • Step d) is therefore the crucial step of the process that is the subject of the present invention.
  • the dilution of the emulsion is carried out by adding water thereto, from all the means well known to those skilled in the art.
  • the dilution factor is therefore between 1.5 and 3.5; dilution is understood to mean the dilution of the cationic starchy material with respect to the water contained in said emulsion.
  • the particle size of the emulsion is less stable over time if a dilution factor of between 1.5 and 3.5 is applied.
  • the examples also demonstrate that the dilution of the initial solution of cationic starchy material does not constitute a satisfactory response: it leads to emulsions whose average diameter is too large (of the order of 2 ⁇ m).
  • Step a) of producing the aqueous solution of cationic starchy material either consists in providing an aqueous solution of cationic starchy material, as commercially available, or else in diluting it with water, in order to obtain the desired dry matter content.
  • cationic starchy material designates a starchy material obtained by any of the known methods of cationisation in aqueous medium, in a solvent medium or in a dry phase, since this process allows one or more a plurality of nitrogen group (s) of electropositive nature to be attached to said starchy material.
  • s nitrogen group
  • aqueous solution of cationic starchy materials that can be used according to the present invention
  • examples of aqueous solution of cationic starchy materials that can be used according to the present invention, mention may be made of the products marketed under the VECTOR® SC and IC (ROQUETTE®) range, Raisabond® 15 (CHEMIGATE), Licocat® P (SUEDSTAERKE®), Lyckeby® LP 2145 and LP 1140 (LYCKEBY®), Redisize® 205 and Redibond® 4000 (NATIONAL STARCH®) and Raifix® 25035 and 01035 (CIBA RAISIO®).
  • VECTOR® SC and IC ROQUETTE®
  • Licocat® P SUVEDSTAERKE®
  • Lyckeby® LP 2145 and LP 1140 LYCKEBY®
  • Redisize® 205 and Redibond® 4000 NATIONAL STARCH®
  • Raifix® 25035 and 01035 CIBA RAISIO®
  • Step b) consists, from conventional mixing means, in particular for controlling the mass concentrations of the constituents, to achieve mixing between the aqueous solution of cationic starch material from step a) and the ASA.
  • the dry weight ratio cationic starchy material / ASA is preferably between 0.2 and 0.6, and very preferably between 0.3 and 0.5.
  • Said mixture and the ASA are brought to a mixer which is ideally a static mixer, but may also consist of a dynamic mixer, or a mixer called "venturi", according to the expression well known to those skilled in the art .
  • Step c) consists of circulating in a single pass the mixture which has been obtained in step b), in an emulsification unit.
  • This unit designates all the devices well known to those skilled in the art, and having in particular mechanical means whose purpose is to micronize and disperse homogeneously the liquid that is to be emulsified.
  • Such devices are in particular the Process Pilot DR 2000/4 (IKA®) or Ytron Z (YTRON®) materials.
  • the apparatus within the meaning of the present invention must be understood as devices capable of implementing the method according to the invention, on an industrial scale.
  • the manufacture of the emulsion consumes at least 5 liters of ASA per hour, preferably at least 10 liters of ASA per hour.
  • the process according to the present invention is also characterized in that the ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts.
  • ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts.
  • Chemsize® A 180 (CHEMEC®).
  • This process is also characterized in that the aqueous solution of cationic starchy material has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% by dry weight of nitrogen relative to the total weight of cationic starchy material.
  • This cationic starchy material may optionally be modified from an operation chosen from hydrolysis, chemical and physical, mechanical, thermomechanical or even thermal transformations.
  • a hydrolysis operation very directly aimed at reducing the molecular weight and, in most cases, reducing the viscosity, can be conducted by various means such as chemical, commonly by the action of an acid, a base or an oxidizing agent or by an enzymatic action, most commonly by amylase.
  • the common chemical modifications are of different types such as oxidation, especially with hypochlorite, esterification, such as acetylation, etherification, for example by cationization, carboxymethylation or hydroxypropylation.
  • Physical treatments may be practiced by thermomechanical means, such as extrusion or pre-gelatinization, or thermal, such as those known to those skilled in the art as Hot Moisture Treatment (HMT) or Annealing .
  • HMT Hot Moisture Treatment
  • This emulsion is also characterized in that the ASA it contains is a product preferably of synthetic origin.
  • the cationic starch material which it comprises has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% by dry weight of nitrogen relative to the total weight of cationic starchy material.
  • Said cationic starchy material may optionally be modified from an operation selected from hydrolysis, chemical and physical, mechanical, thermomechanical or thermal transformations as previously indicated.
  • Another object of the present invention is a sizing composition containing the ASA emulsion in an aqueous solution of starchy material as described above.
  • a final object of the present invention is the use of said emulsion in a gluing operation of a sheet of paper or cardboard.
  • This example is intended to illustrate the manufacture of ASA emulsion in an aqueous solution of cationic starchy material in the context of a device according to the invention free of a recirculation loop at the unit level. emulsification, and with a device according to the prior art. It also aims to illustrate the influence of the dry matter content of the initial aqueous solution of cationic starchy material on the particle size of the emulsion produced.
  • ASA which is the Chemsize® A180 product marketed by CHEMEC®, is also used. This product contains 0.5% by weight sodium dioctyl sulfosuccinate as surfactant (also called "DOSS").
  • the water supply is from an existing distribution network.
  • the transfers and assays of the ASA and the aqueous solution of cationic starchy material to this emulsification platform are made from their mobile container or respective storage tank, by means of hoses and volumetric pumps, whose speeds of rotation are subject to the desired flow rate and target ratio cationic starch (dry) / ASA.
  • the aqueous solution of cationic starchy material is diluted in line.
  • the dilution water flow rate is regulated by the flow rate of the aqueous solution of commercial cationic starchy material, depending on the desired solids content.
  • a static mixer allows to homogenize this dilute aqueous solution.
  • the ASA is then introduced online in the dilute and homogeneous aqueous solution of cationic starchy material.
  • This mixture "aqueous solution of cationic starchy material / ASA" is then conveyed via a pipe to the emulsifier.
  • This single-pass and continuous emulsification system has a series of 3 consecutive rotors / stators, each rotor and each stator is composed of 3 rows of concentric serrated crowns. This process operates at variable speed; the speed of rotation depends on the hydraulic flow rate, the nature of the constituents and their proportions, the pressure in the emulsion chamber, as well as the fineness of the desired emulsion.
  • the output of the emulsifier is provided with a temperature sensor, a pressure sensor, a valve for maintaining a pressure of 3 bars in the process, and a flow meter.
  • the dry matter content of the aqueous solution of cationic starchy material was varied from 3% to 20%, the dry cationic starch content / ASA ratio from 0.3 to 0.5, the flow rate at the outlet of the emulsifier from 80 to 140 kg / h, the peripheral speed of the rotor of the emulsifier being set at 40 m / s.
  • the temperature T ° C of the emulsion at the outlet of the emulsification unit is measured, and a granulometric analysis is carried out according to the protocol already explained, so as to determine the average diameter as well as the parameter % ⁇ 2 ⁇ m.
  • the emulsion at the outlet of the emulsification unit is recovered, and according to test No. 6, the emulsion is recirculated at least once more in the said emulsion. unit.
  • Tests Nos. 1 to 4 demonstrate that, at two given MA / ASA ratios and for a dry extract of cationic starchy material that is too low (3% and 5%), the result is a too large average diameter (in particular much greater than 2 ⁇ m for tests 3 and 4) and / or at a value of% ⁇ 2 ⁇ m too low.
  • An optimal quantity of particles having a diameter of between 1 ⁇ m and 1.5 ⁇ m is therefore not available, which means that particles of larger size are generated which can cause fouling problems.
  • tests No. 6 and 7 carried out with a large dry extract of starchy material do not give the desired particle size.
  • Example 2 it is placed under the optimum conditions according to Example 1 namely, use of an aqueous solution of cationic starchy material whose content in dry matter is equal to 8%, in combination with ASA so as to obtain a dry weight ratio cationic starchy material / ASA equal to 0.3.
  • Emulsions are produced under the same operating conditions as before. We are interested here in the evolution of the average diameter of the emulsion in time, depending on whether the emulsion is diluted or not. The hydrophobicity of a paper made with a diluted or non-diluted emulsion is measured after various storage times.
  • emulsion 1 Part of the manufactured emulsion is stored: this product is called “emulsion 1".
  • the other part is diluted by a factor of 2 as regards the dry cationic starch content relative to water: this product is called “emulsion 2”.
  • Each emulsion is stored at room temperature.
  • the value of the average diameter of each emulsion 1 and 2 is determined according to the method already indicated.
  • a portion of each emulsion (diluted or not) is also taken in order to produce sheets of paper. laboratory, and to measure the degree of hydrophobicity (Cobb60).
  • these sheets of laboratory paper also known as formettes, are manufactured from a FRET (retention form) device marketed by TECHPAP.
  • FRET retention form
  • Such forms have characteristics close to the industrial customer paper, especially with regard to flocculation and retentions.
  • the method of manufacturing the formette uses a pulp which is a pulp of virgin fibers (50% resinous, 50% hardwood) with a refining level of 35 ° Schopper (° SR). 35% (by dry weight relative to the total weight of the dough) of natural calcium carbonate marketed by OMYA® under the name Omyalite® 50.
  • the filled fibrous suspension has a concentration of 2.5 g / l. 0.3% (dry equivalent / paper) of a HICAT® 5163AM (ROQUETTE®) glue is then added. Finally, 0.35% (relative to the paper) of the ASA emulsion is added. This produces a form having a grammage of 70 g / m 2 .
  • the form After manufacture of the form, it is placed between 2 blotters and the set is passed twice in a TECHPAP brand roller press. The form is then separated from the blotters and is placed on a TECHPAP brand dryer for 5 minutes at 100 ° C. A ripening of the forms is then carried out, placing them for 30 minutes in an oven at 110 ° C, to allow the bonding agent to give the paper its hydrophobic character. The sheets are then placed for a minimum of 24 hours in a room conditioned at 23 ° C (+/- 1 ° C) and 50% relative humidity (+/- 2%) (ISO 187: 1990 and Tappi T402 standards). 08).
  • Table 2 summarizes the average diameter values ( ⁇ m) obtained for emulsions 1 and 2 at different storage times and the Cobb60 values (g / m 2 ) measured on the forms prepared with these 2 emulsions.

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  • Paper (AREA)

Claims (11)

  1. Verfahren zur Herstellung einer Emulsion aus ASA (Alkenylbernsteinsäureanhydrid) in einer wässrigen Lösung eines kationischen stärkehaltigen Materials, welches die folgenden Schritte umfasst:
    a) Herstellen einer wässrigen Lösung eines kationischen stärkehaltigen Materials, deren Gehalt an Trockenmasse zwischen 7% und 12% des Gesamtgewichts beträgt,
    b) Mischen des ASA und der wässrigen Lösung eines kationischen stärkehaltigen Materials aus Schritt a), um ein Verhältnis Trockenmasse kationisches stärkehaltiges Materials/ASA von weniger als 1, vorzugsweise von 0,2 bis 0,6 und sehr stark bevorzugt von 0,3 bis 0,5 zu erhalten,
    c) in einem einzigen Arbeitsgang und in einer Emulgierungseinheit Herstellen einer Emulsion auf der Grundlage der Mischung aus Schritt b) ohne Rezirkulierungsschleife,
    d) Verdünnen der Emulsion aus Schritt c) in einem Faktor zwischen 1,5 und 3,5 bezüglich des Trockenmasse-Gehalts des kationischen stärkehaltigen Materials im Verhältnis zu Wasser.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die wässrige Lösung eines kationischen stärkehaltigen Materials einen Stickstoffgehalt aufweist, der auf unter 3,5 %, vorzugsweise 0,3% bis 3,5%, sehr stark bevorzugt auf 0,7% bis 2% Stickstoff-Trockenmasse im Verhältnis zur Gesamttrockenmasse des kationischen stärkehaltigen Materials festgelegt wird.
  3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das ASA ein synthetisch hergestelltes Produkt ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das kationische stärkehaltige Material durch einen Arbeitsgang modifiziert wird, welcher gewählt ist aus Hydrolyse, chemische und physikalische, mechanische, thermomechanische oder auch thermische Transformationen.
  5. Vorrichtung, welche umfasst:
    a') eine Speichereinheit einer wässrigen Lösung eines kationischen stärkehaltigen Materials,
    a) b') eine Mischeinheit von ASA und wässriger Lösung eines kationischen stärkehaltigen Materials, in Verbindung mit Einheit a'),
    c') Emulgiereinheit der Mischung aus ASA und wässriger Lösung eines kationischen stärkehaltigen Materials, in Verbindung mit Einheit b') und ohne Rezirkulierungsschleife,
    b) d') Emulsionsverdünnungseinheit in Verbindung mit Einheit c').
  6. Emulsion aus ASA in einer wässrigen Lösung eines kationischen stärkehaltigen Materials, welche aufweist:
    - ein Verhältnis Trockenmasse des kationischen stärkehaltigen Materials/ASA von weniger als 1, vorzugsweise von 0,2 bis 0,6 und sehr stark bevorzugt von 0,3 bis 0,5,
    - eine Größenverteilung der Partikel, so dass wenigstens 80 Volumenprozent der Partikel einen Durchmesser von weniger als 2 µm aufweisen sowie einen mittleren Durchmesser von 1µm bis 1,5 µm, bestimmt mittels Lasergranulometrie mit einem von der Firma MALVERN vertriebenen Gerät namens Mastersizer 2000,
    - einen Trockenmasse-Gehalt des kationischen stärkehaltigen Materials von 4% bis 6% im Verhältnis zu in der Emulsion enthaltenem Wasser.
  7. Emulsion nach Anspruch 6, dadurch gekennzeichnet, dass das darin enthaltene ASA bevorzugt ein synthetisch hergestelltes Produkt ist.
  8. Emulsion nach einem der Ansprüche 6 oder 7, dadurch gekennzeichnet, dass das darin enthaltene kationische stärkehaltige Material einen Stickstoffgehalt von unter 3,5 %, vorzugsweise 0,3% bis 3,5%, sehr stark bevorzugt 0,7% bis 2% Stickstoff-Trockenmasse im Verhältnis zur Gesamtmasse des kationischen stärkehaltigen Materials aufweist.
  9. Emulsion nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass das kationische stärkehaltige Material durch einen Arbeitsgang modifiziert ist, welcher gewählt ist aus Hydrolyse, chemische und physikalische, mechanische, thermomechanische oder auch thermische Transformationen.
  10. Klebezusammensetzung, umfassend eine ASA-Emulsion in einer wässrigen Lösung eines kationischen stärkehaltigen Materials nach einem der Ansprüche 6 bis 9.
  11. Verwendung einer Emulsion nach einem der Ansprüche 6 bis 9 oder einer Zusammensetzung
    nach Anspruch 10 bei einem Klebevorgang eines Blatts Papier oder Karton.
EP13782800.0A 2012-10-04 2013-10-04 Verfahren zur herstellung einer stabilen emulsion aus alkenylbernsteinsäureanhydrid in einer wässrigen lösung aus einem kationischen stärkehaltigen material, hergestellte emulsion und verwendung davon Active EP2904146B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1259423A FR2996555B1 (fr) 2012-10-04 2012-10-04 Procede de fabrication d'une emulsion stable d'anhydride alkenyle succinique (asa) dans une solution aqueuse de matiere amylacee cationique, emulsion obtenue et son utilisation
PCT/FR2013/052365 WO2014053788A1 (fr) 2012-10-04 2013-10-04 Procede de fabrication d'une emulsion stable d'anhydride alkenyle succinique (asa) dans une solution aqueuse de matiere amylacee cationique, emulsion obtenue et son utilisation

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EP2904146A1 EP2904146A1 (de) 2015-08-12
EP2904146B1 true EP2904146B1 (de) 2017-07-05

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EP13782800.0A Active EP2904146B1 (de) 2012-10-04 2013-10-04 Verfahren zur herstellung einer stabilen emulsion aus alkenylbernsteinsäureanhydrid in einer wässrigen lösung aus einem kationischen stärkehaltigen material, hergestellte emulsion und verwendung davon

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EP (1) EP2904146B1 (de)
ES (1) ES2641534T3 (de)
FR (1) FR2996555B1 (de)
PT (1) PT2904146T (de)
WO (1) WO2014053788A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3019823B1 (fr) * 2014-04-11 2017-10-27 Roquette Freres Procede de fabrication d'une emulsion d'anhydride alkenyle succinique
CN112538780A (zh) * 2020-12-22 2021-03-23 浙江凯丰新材料股份有限公司 一种asa施胶剂在线乳化装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3105903A1 (de) * 1981-02-18 1982-09-09 Basf Ag, 6700 Ludwigshafen Verfahren zur masseleimung von papier
US4606773A (en) * 1984-12-10 1986-08-19 Nalco Chemical Company Emulsification of alkenyl succinic anhydride sizing agents
DE19610995C2 (de) 1996-03-21 2002-12-19 Betzdearborn Inc Papierleimungsmittel und -verfahren
FR2857365B1 (fr) * 2003-07-08 2005-09-30 Roquette Freres Nouvelle composition amylacee cationique liquide et ses utilisations
JP2008531864A (ja) * 2005-03-03 2008-08-14 ケミラ オイ ウェットエンド塗布のための低せん断セルロース反応性サイズ剤

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FR2996555A1 (fr) 2014-04-11
FR2996555B1 (fr) 2014-12-05
PT2904146T (pt) 2017-10-03
ES2641534T3 (es) 2017-11-10
EP2904146A1 (de) 2015-08-12
WO2014053788A1 (fr) 2014-04-10

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