WO2000015669A1 - Amidon cationique, elaboration et utilisation - Google Patents

Amidon cationique, elaboration et utilisation Download PDF

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Publication number
WO2000015669A1
WO2000015669A1 PCT/FI1999/000748 FI9900748W WO0015669A1 WO 2000015669 A1 WO2000015669 A1 WO 2000015669A1 FI 9900748 W FI9900748 W FI 9900748W WO 0015669 A1 WO0015669 A1 WO 0015669A1
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WO
WIPO (PCT)
Prior art keywords
starch
paper
cationic starch
produced
betaine
Prior art date
Application number
PCT/FI1999/000748
Other languages
English (en)
Inventor
Hanna GRANÖ
Anneli Hase
Jari Tapani Yli-Kauhaluoma
Jouko KÄKI
Kari Nurmi
Original Assignee
Raisio Chemicals Ltd
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 Raisio Chemicals Ltd filed Critical Raisio Chemicals Ltd
Priority to AU57490/99A priority Critical patent/AU5749099A/en
Publication of WO2000015669A1 publication Critical patent/WO2000015669A1/fr

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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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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

Definitions

  • the object of this invention is a novel cationic starch, its preparation and use as an additive in the manufacture of paper.
  • Water-soluble cationic starches are used as an additive at the wet end in the manufacture of paper to increase i.a. the retention and improve the tensile strength of paper.
  • the cationization of the starch is accomplished by processing starch with reagents having cationic groups.
  • a cationizing reagent of this kind can contain cationic amino, immonium, ammonium, sulphonium or phosphonium groups, but nowadays industrially the most important cationic starches have been produced by etherifying a starch with compounds containing tertiary amino groups or quaternary ammonium groups.
  • starches containing quaternary ammonium groups are the most popular, while they are, unlike the cationic starches containing amino groups, cationic under acidic, neutral as well as alkaline conditions.
  • Quaternary starches are produced by forming ether or ester bonds between the hydroxyl groups of the starch structure and the cationizing reagent.
  • the industrial cationic starches are also often modified by esterifying or etherifying the starch structure with short-chained carbohydrates, as well as by anionizing and cross-linking the cationic starch.
  • the first cationic starches used as a paper additive were patented in the US patent No. 2,813,093 in 1957, and since then cationic starches have been among the most common chemicals at the wet end in the manufacture of paper (cf. e.g. Modified Starches: Properties and Uses, Ed. O. B. Wurzburg, CRC Press, Boca Raton 1986). Cationic starches are still being developed for paper and other applications. At the moment, the cationic tertiary or quaternary aminoalkyl ethers of the starch are the most common additives in the manufacture of paper.
  • the paper strength is increased and the amount of the fines in paper mill's white water is reduced, i.e. the binding of the fines and pigments to the paper web is improved, and in addition to that, the water retention in the web is reduced.
  • the textile feel of the web can be improved by using cationic starches, and in wastewater treatment the retention of the anionic impurities is increased in the flocculation processes.
  • the starch has been cationized with compounds of petrochemical origin.
  • efforts are made in finding more ecological solutions by saving non- renewable natural resources and utilizing renewable natural resources by indicating novel uses i.a. for the by-products of agricultural production.
  • a novel cationized starch has now been invented which can be produced from natural products.
  • the further advantage of the starch according to the invention is that it can excellently be applied to the cationizing necessary for foodstuffs and to paper and board used in foodstuff packages, because it is non-toxic, food grade and because betaine has useful nutritive properties.
  • a cationized starch can be produced by esterifying starch with betaine, ie. trimethyl glycine.
  • betaine ie. trimethyl glycine.
  • the thus produced water-soluble cationic starch, ie. starch betaine can be used as a food grade additive at the wet end in the manufacture of paper to improve i.a. retention, water permeability and the strength of the produced paper.
  • Betaine is an inner salt which contains a cationic quaternary trimethyl ammonium group. Betaine is a natural substance which is commonly found in wild plants, and sugar beet contains an especially large amount of it. Betaine is thus a natural and a renewable product, and as such it differs totally from the cationizing reagents of petrocemical origin known thus far which are very toxic.
  • the structural formula of betaine is presented in the following figure.
  • the starch can be any natural starch, for example tuber-related starch (e.g. potato), root starch (e.g.. tapioca, arrowroot or sweet potato), or cereal starch (e.g. barley, wheat, rice or durra).
  • tuber-related starch e.g. potato
  • root starch e.g.. tapioca, arrowroot or sweet potato
  • cereal starch e.g. barley, wheat, rice or durra
  • waxy starches, modified starches, hydrolyzed or oxidized starches, acid-treated starches or even other long-chained polysaccharides can be used.
  • Starch esters their production and properties as well as applications have already been known per se for decades, as they have been presented i.a. in the book Starch: Chemistry and Technology, 2 nd Ed., edited by R. L. Whistler, J. N. BeMiller and E. F. Paschall, Academic Press Inc. 1984, and in the book Modified Starches: Properties and Uses, edited by O. B. Wurzburg, CRC Press, Boca Raton, 1986. Starch esters are used especially as plastics and their additives, in textiles and in the manufacture of paper, particularly for paper coating.
  • anthranilate esters are formed containing primary amino groups which can be cationized, if desired, either at low pH or by alkylation with alkyl halides, sulphonates or other alkylation reagents.
  • isatoic anhydride or quinolinic anhydride, i.e. 2,3- pyridinedicarboxyl acid anhydride in the esterification of starch has been described in the patent US 3,052,561 (1962). The produced products are recommended to be used in the preparation of cationized starches.
  • a natural amino acid, betaine is used for cationizing starch.
  • a natural, strongly or weakly cationized starch depending on the degree of substitution of the product, is obtained directly.
  • the product is suitable for a retention agent in the manufacture of paper, for decreasing the water retention capacity of pulp and for increasing the strength of paper.
  • the cationized starch described in this invention can preferably be used also for the purification of process water from fines for example in connection with the thermomechanical pulp preparation, as has been described by V. Bobacka, J. Nasman and D. Eklund in 1998 (Journal of Pulp and Paper Science 24, 1998, 78). Due to its physiologically accepted properties, a betainyl ester of starch is applicable especially as an additive of food paper and food board and to effluent treatment.
  • Cationic starch betainate is produced by esterifying hydroxyl groups of starch with betainyl chloride or betainyl anhydride.
  • the betainyl chloride used in the esterification is produced from anhydrous betaine, betaine hydrochloride or other inorganic or organic betaine salts.
  • Betainyl chloride is an acid chloride which can easily be produced from betaine by known processes for the preparation of acid chloride.
  • Betainyl chloride can preferably be produced from betaine by using i.a. tionyl chloride or oxalyl chloride in the presence of N,N-dimethyl formamide.
  • Betainyl anhydride is in turn an acid anhydride, which is produced from betaine, betaine hydrochloride or other inorganic or organic betaine salts by water elimination (dehydration).
  • starch betainate The structural formula of starch betainate is presented in the following.
  • St represents the polymeric structure of the starch.
  • the esterification reaction is carried out in an organic solvent, preferably in 1,4-dioxan or toluene, by using a tertiary amine, preferably pyridine, as an esterification catalyte.
  • the reaction is carried out at a quite high temperature, preferably near the reflux temperature of the used solvent.
  • the reaction time is 1-24 h, preferably 2-6 h.
  • an example of carrying out an esterification reaction is presented.
  • betaine anhydride the esterification can also be carried out in an alkaline water mixture.
  • the starch was stirred in refluxing pyridine for 30 min.
  • 150 ml of 1,4-dioxan and 9.5 g of betainyl chloride was added, and the reaction mixture was refluxed for 4 hours under argon at the temperature of 110°C.
  • the solvent was poured from the reaction vessel, and the product was dissolved in water.
  • the product was precipitated from water by adding ethanol, and the formed deposit was filtrated.
  • the product was recovered, washed with a mixture of ethanol and diethyl ether and dried in vacuum.
  • the yield was 11.83 g (60.6%) and the degree of substitution of the product was 0.39 (theoretical: 0.75).
  • the starch was stirred in refluxing pyridine for 30 min. 60 ml of toluene and 6.3 g of betainyl chloride was added, and the reaction mixture was refluxed for 4 hours under argon at the temperature of 115°C. The solvent was poured from the reaction vessel, and the product was dissolved in water. The product was precipitated from water by adding ethanol, and the formed deposit was filtrated. The product was recovered, washed with ethanol and water and dried in vacuum. The yield was 1.12 g (11.2%).
  • the betaine anhydride was stirred in pyridine at room temperature. 1 g of potato starch was added, and the reaction mixture was heated to the temperature of 125°C. The reaction was allowed to continue for 6 h under argon at the temperature of 125°C. 100 ml of ethanol was poured to the reaction mixture, and the product was recovered by filtrating. The product was washed with a mixture of ethanol and diethyl ether. The yield was 1.54 g.
  • the produced cationic, water-soluble starch betainate is added to the wet end in the manufacture of paper 0.1-2% based on the amount of the chemical pulp fibre to improve the retention of fines and pigments, water permeability and the strength of the produced paper.
  • the cationized starch according to the invention can also be used as an auxiliary in textile industry and in the treatment of effluents, especially ligneous effluents, and in the waste reclamation.

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

Abstract

La présente invention concerne un amidon cationique constitué de produits naturels tels que l'amidon et la bétaïne. Dans le produit, la bétaïne est liée par covalence au moyen d'une liaison ester à une partie des groupes hydroxyles de l'amidon, lorsque le produit respecte la formule structurelle suivante (I), auquel cas St représente la structure polymère de l'amidon.
PCT/FI1999/000748 1998-09-15 1999-09-14 Amidon cationique, elaboration et utilisation WO2000015669A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57490/99A AU5749099A (en) 1998-09-15 1999-09-14 New cationic starch, its preparation and use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI981991 1998-09-15
FI981991A FI107387B (fi) 1998-09-15 1998-09-15 Uusi kationinen tärkkelys, sen valmistus ja käyttö

Publications (1)

Publication Number Publication Date
WO2000015669A1 true WO2000015669A1 (fr) 2000-03-23

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Application Number Title Priority Date Filing Date
PCT/FI1999/000748 WO2000015669A1 (fr) 1998-09-15 1999-09-14 Amidon cationique, elaboration et utilisation

Country Status (3)

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AU (1) AU5749099A (fr)
FI (1) FI107387B (fr)
WO (1) WO2000015669A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2832156A1 (fr) * 2001-11-15 2003-05-16 Oreal Preparation de composes de type betainates de polysaccharides, composes obtenus, leur utilisation et les compositions les comprenant
WO2004104048A1 (fr) * 2003-05-21 2004-12-02 Ciba Specialty Chemicals Holding Inc. Procede de preparation d'esters de polymere hydroxy et leur utilisation
WO2004104049A1 (fr) * 2003-05-21 2004-12-02 Ciba Specialty Chemilcals Holding Inc. Procede de preparation d'esters de carnitine et leur utilisation
US6911114B2 (en) 2002-10-01 2005-06-28 Kimberly-Clark Worldwide, Inc. Tissue with semi-synthetic cationic polymer
US8410262B2 (en) 2005-12-08 2013-04-02 Chemigate Oy Process for the preparation of hydroxy polymer esters and their use
WO2022168011A1 (fr) * 2021-02-08 2022-08-11 Raiz - Instituto De Investigação Da Floresta E Papel Procédé d'obtention de bétaïnate d'amidon
CN114890525A (zh) * 2022-05-19 2022-08-12 合肥工业大学 一种右旋糖酐-甜菜碱阳离子絮凝剂的制备方法及其应用
WO2023287684A1 (fr) * 2021-07-13 2023-01-19 Nutrition & Biosciences USA 4, Inc. Dérivés d'ester de glucane cationique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620913A (en) * 1970-03-03 1971-11-16 Cpc International Inc A process of making paper and paper made therefrom using starch anthranilate
US4127563A (en) * 1977-06-29 1978-11-28 The United States Of America As Represented By The Secretary Of Agriculture Low pH preparation of cationic starches and flours
DE3820030C1 (fr) * 1988-06-13 1989-07-27 Th. Goldschmidt Ag, 4300 Essen, De
EP0743394A2 (fr) * 1995-05-17 1996-11-20 National Starch and Chemical Investment Holding Corporation Procédé de collage du papier avec un amidon cationique modifié

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620913A (en) * 1970-03-03 1971-11-16 Cpc International Inc A process of making paper and paper made therefrom using starch anthranilate
US4127563A (en) * 1977-06-29 1978-11-28 The United States Of America As Represented By The Secretary Of Agriculture Low pH preparation of cationic starches and flours
DE3820030C1 (fr) * 1988-06-13 1989-07-27 Th. Goldschmidt Ag, 4300 Essen, De
EP0743394A2 (fr) * 1995-05-17 1996-11-20 National Starch and Chemical Investment Holding Corporation Procédé de collage du papier avec un amidon cationique modifié

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2832156A1 (fr) * 2001-11-15 2003-05-16 Oreal Preparation de composes de type betainates de polysaccharides, composes obtenus, leur utilisation et les compositions les comprenant
EP1312616A1 (fr) * 2001-11-15 2003-05-21 L'oreal Préparation de composés de type bétainates de polysaccharides, composés obtenus, leur utilisation et les compositions les comprenant
US7211268B2 (en) 2001-11-15 2007-05-01 L'oreal S.A. Preparation of polysaccharide betainate type compounds, compounds obtained, their use and compositions comprising them
US6911114B2 (en) 2002-10-01 2005-06-28 Kimberly-Clark Worldwide, Inc. Tissue with semi-synthetic cationic polymer
WO2004104048A1 (fr) * 2003-05-21 2004-12-02 Ciba Specialty Chemicals Holding Inc. Procede de preparation d'esters de polymere hydroxy et leur utilisation
WO2004104049A1 (fr) * 2003-05-21 2004-12-02 Ciba Specialty Chemilcals Holding Inc. Procede de preparation d'esters de carnitine et leur utilisation
US8410262B2 (en) 2005-12-08 2013-04-02 Chemigate Oy Process for the preparation of hydroxy polymer esters and their use
WO2022168011A1 (fr) * 2021-02-08 2022-08-11 Raiz - Instituto De Investigação Da Floresta E Papel Procédé d'obtention de bétaïnate d'amidon
WO2023287684A1 (fr) * 2021-07-13 2023-01-19 Nutrition & Biosciences USA 4, Inc. Dérivés d'ester de glucane cationique
CN114890525A (zh) * 2022-05-19 2022-08-12 合肥工业大学 一种右旋糖酐-甜菜碱阳离子絮凝剂的制备方法及其应用
CN114890525B (zh) * 2022-05-19 2024-01-23 合肥工业大学 一种右旋糖酐-甜菜碱阳离子絮凝剂的制备方法及其应用

Also Published As

Publication number Publication date
FI107387B (fi) 2001-07-31
FI981991A (fi) 2000-03-16
AU5749099A (en) 2000-04-03
FI981991A0 (fi) 1998-09-15

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