EP2115009A1 - Procédé de préparation d'un dérivé d'amidon hydrophobe, dérivé d'amidon hydrophobe et application du procédé - Google Patents

Procédé de préparation d'un dérivé d'amidon hydrophobe, dérivé d'amidon hydrophobe et application du procédé

Info

Publication number
EP2115009A1
EP2115009A1 EP08707508A EP08707508A EP2115009A1 EP 2115009 A1 EP2115009 A1 EP 2115009A1 EP 08707508 A EP08707508 A EP 08707508A EP 08707508 A EP08707508 A EP 08707508A EP 2115009 A1 EP2115009 A1 EP 2115009A1
Authority
EP
European Patent Office
Prior art keywords
starch
anhydride
starch derivative
hours
hydrophobic
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.)
Withdrawn
Application number
EP08707508A
Other languages
German (de)
English (en)
Inventor
Kay Hettrich
Waltraud Vorwerg
Jan Dijksterhuis
Karl Ludwig Woll
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.)
Emsland Staerke GmbH
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Emsland Staerke GmbH
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Emsland Staerke GmbH, Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Emsland Staerke GmbH
Publication of EP2115009A1 publication Critical patent/EP2115009A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • D21H21/16—Sizing or water-repelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/06—Esters
    • 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 describes a process for the preparation of a hydrophobic starch derivative by esterification of alcoholic functions with organic acid anhydrides in aqueous salt solutions.
  • the obtained hydrophobic starch derivatives improve e.g. the water stability of papers.
  • starch In addition to cellulose, starch is already a renewable raw material used in many areas. In many plants, starch is a reserve carbohydrate and in the form of 1 to 200 .mu.m starch granules in various parts of plants, eg. In tubers or roots (potatoes, cassava, potatos), cereal seeds (wheat, maize, rye, rice, barley, millet, oats), fruit (chestnuts, acorns, peas, peas, bananas) and marrow (Sago palm) saved. Potatoes, corn and wheat are considered as suppliers of starch in Europe.
  • starch consists essentially of 3 different D-glucopyranose polymers: amylose, amylopectin and a so-called intermediate fraction, also referred to as abnormal amylopectin, and 10 to 20% water, depending on the variety and storage conditions, in smaller quantities Protein, fats and phosphoric ester groups. Depending on the variety, the contents of the listed ingredients vary.
  • Starch is used primarily in the paper and food industry, but also increasingly for the production of cosmetics, and as detergent raw material. Due to the hydrophilicity of the polysaccharide starch, its use as a thickener and binder almost approaches. The property of water binding is also adjustable as gel formation, depending on the molecular composition. After the introduction of ionic substituents, the water-binding capacity can be increased to the point of use as an absorber.
  • starch derivatives which must have specific solid state or surface strength properties, require stability to varying relative humidity and wettability with water.
  • the paper industry needs suitable water-stable products, eg for the production of decorative and tissue paper. When in contact with water, tear resistance should be obtained for these types of paper stay.
  • adhesives for paper, corrugated cardboard or packaging tubes in addition to wet strength, mechanical stability is also required.
  • various modifications are conceivable.
  • the water stability is achieved by adding melamine or resorcinol / formaldehyde resins, ie by crosslinking reactions.
  • the resulting products can contain up to 12% of these resins. Recycling these products is very problematic from an environmental point of view.
  • Modification of the starch with hydrophobic residues is another way to increase the water stability of the polysaccharide.
  • the advantage of such derivatizations is that, depending on the reagent used, the desired hydrophobic properties can already be achieved at very low degrees of substitution (DS.ltoreq.0.2), so that from an economic point of view the use of the relatively expensive hydrophobizing reagents can be achieved acceptable minimum can be reduced.
  • the disadvantage is that due to the structure of starch, the introduction of long-chain residues is achieved very slowly and in poor yields even with only small DS values in the slurry.
  • Hydrophobizing reagents for modifying starch contain, in addition to a reactive group for the realization of the ester or ether group, long-chain radicals.
  • Verether ⁇ ngsreagenzien come e.g. epoxidized fatty acids or fatty acid derivatives in question.
  • esterification reagents is mainly the use of acid anhydrides and acid chlorides which contain long-chain groups.
  • One possibility for representing hydrophobic starches is the reaction of starch with alkenylsuccinic anhydrides (ASA).
  • ASA is available on an industrial scale. It is used predominantly as a sizing agent and thus as a quality-improving additive in papermaking.
  • the aim of the sizing is the hydrophobing of the natural fiber fleece, whereby the penetration of water is limited or prevented.
  • Table 1 gives an overview of the currently commercially available alkenyl succinic anhydrides.
  • there are also mixtures of various anhydrides for example, between C 2 and C 14, C 6 and C 18 as well as anhydrides with branched alkenyl nylketten, including i-DDSA or i-ODSA.
  • starch is first suspended in a solution of sodium carbonate or caustic soda
  • hydrophobization is then carried out after removal of the catalyst by etherification or esterification reagents.
  • this method only succeeds in greatly degraded starches.
  • it is a homogeneous process, which is not desired by the starch-processing industry.
  • usable hydrophobing reagents such as isocyanates, epoxides, methylene- ⁇ -lactones, and alkenyl succinic anhydrides.
  • EP 332,027 describes the preparation of hydrophobic or hydrophobic and hydrophilic substituted esters of acid, amylolytically or thermally prehydrolyzed starch or of hydrolyzed derivatives after esterification.
  • the esterification of the respective starch is carried out heterogeneously with OSA according to US 2,661,349 after the degree of hydrolysis.
  • Starch succinates with DS values up to 1.5 can be obtained by the method of Shogren (Shogren 2003). It is dried in a vacuum in
  • Glacial acetic acid reacted with the anhydride at temperatures between 120 and 180 0 C.
  • the reactions give mixed esters with good yields.
  • the high temperatures and high pressures during the synthesis make this method
  • claim 17 specifies a correspondingly producible hydrophobic starch derivative.
  • Claim 18 describes one way of using the method.
  • a process for the preparation of a hydrophobic starch derivative with the following successive working steps is proposed: a) dispersing starch and / or starch derivatives in an aqueous salt solution, b) adding carboxylic acid anhydrides, c) setting a temperature of the reaction mixture ULTRASONIC between 0 0 C and 60 0 C, d) stopping the reaction by adding a Alkohl-water mixture.
  • the concentration of the salt solution has a molarity between 0.2 m and 7 m.
  • the optimum concentration is determined by way of a dependence of the solubility product of the salt used in water.
  • the salts are selected from the group of inorganic salts.
  • the cations of the inorganic salts are preferably selected from Li, Mg, Al, Cu, Zn.
  • the anions of the inorganic salts are not particularly limited, but it is advantageous if the anions are selected from chloride, sulfate and / or Nitrate.
  • the process according to the invention can be carried out with any desired starches and / or starch derivatives.
  • starches for example, potatoes, corn, peas or cereals can serve as a source of starch.
  • Starch and / or starch derivatives are untreated, partially substituted, partially oxidized and / or partially degraded. According to the invention, it is likewise possible to use mixtures of the abovementioned starches and / or starch derivatives.
  • the pH of the reaction medium to a value between 3 and 9, preferably between 4 and 8.5, is set.
  • step b) the carboxylic acid anhydrides are added in a molar ratio with respect to the starch, depending on the desired DS value, between 0.01 and 1.0, preferably between 0.05 and 0.5.
  • the advantage of the method according to the invention over the prior art is clear, since in the prior art ever greater amounts of carboxylic acid anhydrides with respect to the strength had to be added to soften a corresponding degree of substitution (DS).
  • Alkenyl succinic anhydrides can preferably be used according to the invention as carboxylic anhydrides. Very particularly preferred are those in Table 1 specified.
  • the reaction time to be maintained in step c) may advantageously be from 2 hours to 200 hours, preferably from 2 to 96 hours, more preferably from 2 to 48 hours.
  • a mixture of alcohols and water is added according to the invention.
  • all alcohols that are miscible with water can be used. Examples are: ethanol, 2-propanol, methanol, tert. Butanol.
  • the degree of substitution of the hydrophobic starch derivatives can be adjusted to between 0.01 and 1 according to the invention.
  • the adjustment of the degree of substitution can be done by the appropriate amount of acid anhydride, but also by stopping the reaction at the given time.
  • the method finds use in the production of paper products.
  • the paper (base paper Inkjet withoutRIC- mung having a basis weight of 80 g / m 2) can be dealt with in a laboratory sizing press of Fa. Mathis at a liquor temperature of 50 0 C with 8% sodium starch solution. The leaves are then using
  • the contact angle or contact angle forms at the phase boundary of three immiscible phases, e.g. in the limited wetting of a solid by a liquid.
  • the contact angle characterizes the degree of wetting and gives e.g. Notes on the printability of paper.
  • Fig. 1 shows a synthesis scheme for the preparation of a starch derivative according to the invention.
  • the reaction step according to the invention in which the hydrolysis of the acid anhydride used is largely avoided, is contrasted with the undesired secondary reaction.
  • the carboxyl function is observed.
  • the alkyl groups such as CH 3 , CH 2 , and CH are found between 10 and 50 ppm.
  • the DS value is determined by integration of the NMR signals and comparison of the resulting areas and the peaks.
  • the ratio of the integrals of the alkyl groups of the octenyl radical, eg the methyl Group, to strength AGU Ci signal determines the DS value.
  • OSA hydrophobized potato starch, DS 0.05

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un dérivé d'amidon hydrophobe par estérification de fonctions alcool avec des anhydres d'acides organiques dans des solutions salines aqueuses. Les dérivés d'amidon hydrophobes obtenus permettent d'améliorer par ex. la stabilité de papiers dans l'eau.
EP08707508A 2007-02-06 2008-02-01 Procédé de préparation d'un dérivé d'amidon hydrophobe, dérivé d'amidon hydrophobe et application du procédé Withdrawn EP2115009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710005927 DE102007005927B4 (de) 2007-02-06 2007-02-06 Verfahren zur Herstellung eines hydrophoben Stärkederivats
PCT/EP2008/000824 WO2008095654A1 (fr) 2007-02-06 2008-02-01 Procédé de préparation d'un dérivé d'amidon hydrophobe, dérivé d'amidon hydrophobe et application du procédé

Publications (1)

Publication Number Publication Date
EP2115009A1 true EP2115009A1 (fr) 2009-11-11

Family

ID=39209460

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08707508A Withdrawn EP2115009A1 (fr) 2007-02-06 2008-02-01 Procédé de préparation d'un dérivé d'amidon hydrophobe, dérivé d'amidon hydrophobe et application du procédé

Country Status (3)

Country Link
EP (1) EP2115009A1 (fr)
DE (1) DE102007005927B4 (fr)
WO (1) WO2008095654A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885403B (zh) * 2018-09-11 2022-08-30 上海东升新材料有限公司 一种改性淀粉乳化剂及采用该乳化剂制备的akd乳液
IT202100026102A1 (it) 2021-10-12 2023-04-12 Andreas Ramoser Piastrina distanziatrice multiuso

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2661349A (en) * 1949-02-18 1953-12-01 Nat Starch Products Inc Polysaccharide derivatives of substituted dicarboxylic acids
GB717901A (en) * 1949-12-14 1954-11-03 Nat Starch Products Inc Free-flowing starch derivative
US3839320A (en) * 1973-08-06 1974-10-01 Anheuser Busch Method of preparing starch esters
GB1585200A (en) * 1978-04-12 1981-02-25 Ahmedabad Textile Ind Method for the preparation of esters of carbohydrates and other organic compounds containing hydroxyl groups
CA1143914A (fr) * 1979-02-05 1983-04-05 Roland W. Best Methode de couchage du papier a la presse, et papier impermeable ainsi obtenu
EP0296527A3 (fr) 1987-06-23 1990-03-07 Matsushita Electric Industrial Co., Ltd. Appareil de chauffage
US4977252A (en) 1988-03-11 1990-12-11 National Starch And Chemical Investment Holding Corporation Modified starch emulsifier characterized by shelf stability
JP3206164B2 (ja) * 1992-12-21 2001-09-04 荒川化学工業株式会社 塗工紙の再湿粘着防止剤
EP0703243B1 (fr) 1994-09-26 2000-12-13 Unilever N.V. Procédé pour la préparation d'une composition détergente liquide.
US5627273A (en) 1995-01-31 1997-05-06 National Starch And Chemical Investment Holding Corporation Method for preparing hydrophobically-terminated polysaccharide polymers and detergent compositions comprising the polysaccharide polymers
US5672699A (en) * 1995-09-06 1997-09-30 National Starch And Chemical Investment Holding Corporation Process for preparation of hydrophobic starch derivatives
US5716441A (en) 1996-09-27 1998-02-10 National Starch And Chemical Investment Holding Corporation Starch-based, water resistant adhesives
US5797984A (en) * 1997-04-15 1998-08-25 National Starch And Chemical Investment Holding Corporation Water resistant starch based foams
US6001927A (en) * 1998-09-16 1999-12-14 National Starch And Chemical Investment Holding Corporation Thixotropic paint compositions containing hydrophobic starch derivatives
DE19951734A1 (de) * 1999-03-05 2000-09-07 Wolff Walsrode Ag Regioselektiv substituierte Ester von Oligo- und Polysacchariden und Verfahren zu ihrer Herstellung
US6372361B1 (en) * 2000-07-07 2002-04-16 National Starch And Chemical Investment Holding Corporation Coating for paper products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008095654A1 *

Also Published As

Publication number Publication date
WO2008095654A1 (fr) 2008-08-14
DE102007005927B4 (de) 2011-05-05
DE102007005927A1 (de) 2008-08-14

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