EP1070086A1 - Procede de production d'esters d'amidon - Google Patents

Procede de production d'esters d'amidon

Info

Publication number
EP1070086A1
EP1070086A1 EP99907304A EP99907304A EP1070086A1 EP 1070086 A1 EP1070086 A1 EP 1070086A1 EP 99907304 A EP99907304 A EP 99907304A EP 99907304 A EP99907304 A EP 99907304A EP 1070086 A1 EP1070086 A1 EP 1070086A1
Authority
EP
European Patent Office
Prior art keywords
starch
acid
bar
carried out
anhydrides
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Withdrawn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
EP99907304A
Other languages
German (de)
English (en)
Inventor
Rolf Kakuschke
Inno Rapthel
Hartmut Stoye
Dietmar Runkel
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.)
Dow Olefinverbund GmbH
Original Assignee
Buna Sow Leuna Olefinverbund GmbH
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 Buna Sow Leuna Olefinverbund GmbH filed Critical Buna Sow Leuna Olefinverbund GmbH
Publication of EP1070086A1 publication Critical patent/EP1070086A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/16—Ether-esters
    • 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
    • C08B31/18—Oxidised starch
    • 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
    • C08B31/18—Oxidised starch
    • C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B35/00—Preparation of derivatives of amylopectin
    • C08B35/02—Esters

Definitions

  • the invention relates to a process for the production of compostable starch esters which can be further processed into thermoplastically deformable products.
  • a disadvantage of such an alkaline activation is the increased consumption of esterification reagent (acetic anhydride) by reaction with the alkali and the need to remove all alkali residues from the end product by complex washing processes, since traces of alkali can cause discoloration and decomposition reactions during further processing with thermoplastic.
  • esterification reagent acetic anhydride
  • the method according to DE 19633474 is more advantageous, but the activation proposed there with an acetic acid / acetic anhydride mixture after the esterification reaction has been carried out requires the removal of a relatively large amount of acetic acid during product drying, which requires increased effort, particularly in the case of continuous process design.
  • the object of the invention is to avoid the disadvantages of the prior art and to propose an inexpensive process for the production of starch esters with a defined adjustable degree of substitution with an approximately homogeneous distribution of substituents, which process can be carried out both continuously and discontinuously.
  • the activation is carried out either continuously or discontinuously in a device which is able to press the acid anhydride rapidly into the starch granules by mechanical energy or pressure or cavitation, for example in an ultrasound cell, a mill, a disperser, a high-pressure disintegrator, a kneader, a Jet cooker or a combination of the devices mentioned, preferably in a ball mill or in a disperser.
  • the activation is carried out in the temperature range between 10 ° C - 140 ° C and at pressures between 0.001 - 1400 bar, preferably in the temperature range between 15 ° - 100 ° C and at pressures between 0.01 - 1000 bar.
  • the reaction of the residual moisture is completed by increasing the temperature or temperature and pressure and the esterification reaction is carried out, the desired degree of substitution being set by the amount of carboxylic anhydride.
  • the esterification can be carried out continuously or batchwise in a stirred or kneading reactor in the temperature range from 60 to 200 ° C. at pressures from 0.5 to 400 bar, preferably in the temperature range from 110 to 180 ° C. and at pressures from 1 to 300 bar become.
  • native starches such as corn, wheat, potato, rice, pea, tapioca, waxy maize or high amylose-containing corn, potato or pea starches, as well as their derivatives, such as hydroxyethylated, hydroxypropylated, acetalized , phosphorylated, sulfated, oxidized, carboxyalkylated, ni- starches, allyl starches, xanthate starches with degrees of substitution of 0.001-2.5, preferably 0.05-1.8, can be used in a naturally moist or predried state.
  • native starches such as corn, wheat, potato, rice, pea, tapioca, waxy maize or high amylose-containing corn, potato or pea starches, as well as their derivatives, such as hydroxyethylated, hydroxypropylated, acetalized , phosphorylated, sulfated, oxidized, carboxyalkylated, ni- starches, allyl starches,
  • the acid anhydride components are the anhydrides of aliphatic carboxylic acids with chain lengths C 2 to C 6 , preferably C 2 to C 5 , or mixtures of the carboxylic anhydrides mentioned or mixtures of the carboxylic anhydrides mentioned with the cyclic anhydrides of maleic acid, malonic acid, succinic acid, glutaric acid, phthalic acid , pyromellitic acid or trimellitic acid and their derivatives.
  • the starch esters produced by the process according to the invention are white to slightly yellowish powders or granules, which almost completely dissolve in solvents such as chloroform, ethyl methyl ketone or methyl acetate at degrees of substitution above DS 2,0 2.0.
  • starch esters according to the invention can be processed on their own or with suitable plasticizers to compostable, biodegradable moldings, films or thermoformed articles with good mechanical properties.
  • a slurry of 1600 g wheat starch (13% moisture) and 3400 g acetic anhydride is activated in a temperature-controlled continuous ball mill with an average residence time of 5 min under normal pressure at 90 ° C.
  • the activated slurry is transferred to a 5 l kneading reactor, heated to 180 ° C. and acetylated at this temperature and a pressure of approx. 5 bar for 30 minutes.
  • the clear, highly viscous starch acetate solution is dried under vacuum at approx. 140 ° C, the condensed acetic acid contains approx. 1% acetic anhydride. Yield: 2200 g DS: 2.30
  • Example 2 Example 2:
  • a slurry of 1600 g pre-dried corn starch (5.5% moisture) and 2900 g acetic anhydride is degassed in a temperature-controlled ball mill for about one minute at 15 ° C and 0.1 bar and then activated for 3 minutes at 10 bar and 60 ° C.
  • the activated slurry is continuously heated to 100 ° C. by means of a pump and a preheater and acetylated in a subsequent continuous kneading reactor at 160 ° C. and 3.2 bar with an average residence time of 20 min.
  • the crystal-clear, highly viscous starch acetate solution is dried under vacuum at approx. 120 ° C, the condensed acetic acid contains approx. 2% acetic anhydride. Yield: 2550 g DS: 2.60
  • a slurry of 1600 g hydroxyethylated (DS ⁇ 0.05), high amylose corn starch (approx. 70% amylose, 13% moisture) and 2200 g acetic anhydride is first in a continuous volume flow of 3.5 kg / h with an Ultraturrax at normal pressure and 80 ° C (average residence time approx. 2.5 min) activated, heated to 150 ° C via a preheater and then acetylated in a continuous high-viscosity stirred reactor at 150 ° C and 300 bar with an average residence time of approx. 15 min.
  • the activated slurry is esterified in a continuous kneading reactor at 170 ° C. and 4 bar with an average residence time of approx. 45 min.
  • a slurry of 1600 g pea starch (13% moisture, amylose content approx. 80%) and a mixture of 3000 g acetic anhydride and 600 g trimellitic anhydride is activated in two runs at 100 ° C and 1000 bar using a Gaulin high-pressure homogenizer.
  • the activated starch paste is heated in a 5 l kneading reactor to 180 ° C. and esterified at 12 bar within 55 minutes.
  • the slightly cloudy, highly viscous starch ester solution is dried under vacuum at 130 ° C., the condensed acetic acid contains approx. 0.7% acetic anhydride. Yield: 2650 g DS: 2.25
  • a slurry of 1600 g hydroxypropylated rice starch (13% moisture, DS ⁇ 1.8) and a mixture of 3000 g acetic anhydride and 300 g maleic anhydride is degassed in a disperser (Ultraturrax) for 2 min at 0.01 bar and 20 ° C and after rapid heating to 100 ° C at normal pressure activated for 10 min.
  • the activated slurry is heated to 140 ° C. using a preheater and esterified in a continuous kneading reactor at 150 ° C. and 2.5 bar with an average residence time of approx. 35 min.
  • the clear starch ester solution is dried at 150 ° C. under a fine vacuum, the condensed acetic acid contains ⁇ 0.1% acetic anhydride. Yield: 2350 g DS (ester): 2.30
  • a slurry of 1600 g oxidized tapioca starch (0.65% carboxyl, 13% moisture) and 3300 g acetic anhydride is activated in a temperature-controlled ball mill at 90 ° C and 2.5 bar for 4 minutes.
  • the activated slurry is acetylated in a 5 l kneading reactor at 160 ° C. and 15 bar within 30 min.
  • a slurry of 1600 g pre-dried waxy maize starch (5.5% moisture) and 2700 g acetic anhydride is activated with an Ultraturrax at normal pressure and 90 ° C for 15 min.
  • the activated slurry is acetylated in a 5 l kneading reactor at 170 ° C. and 4 bar within 55 min.

Landscapes

  • 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)

Abstract

L'invention concerne un procédé pour produire des esters d'amidon compostables, pouvant être transformés ultérieurement en produits déformables thermoplastiquement, ledit procédé pouvant être mis en oeuvre aussi bien de manière continue que de manière discontinue. L'activation de l'amidon avec des anhydrides d'acide carboxylique s'effectue sous l'action intensive d'énergie mécanique, d'une pression ou d'une cavitation. Ainsi, l'organophobie des particules d'amidon est surmontée de sorte que l'anhydride d'acide carboxylique pénètre rapidement et pratiquement complètement dans les particules d'amidon, sans modification de la structure partiellement cristalline de ces dernières, au moment où commence simultanément la réaction des anhydrides d'acide carboxylique avec l'humidité résiduelle des amidons naturels ou modifiés, sans déstructuration notable. Selon l'invention, l'activation est effectuée dans une plage de température comprise entre 10 et 140 DEG C, et à des pressions comprises entre 0,001 et 1400 bars, de préférence dans une plage de température comprise entre 15 et 100 DEG C, et à des pressions comprises entre 0,01 et 1000 bars.
EP99907304A 1998-02-11 1999-02-02 Procede de production d'esters d'amidon Withdrawn EP1070086A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1998105367 DE19805367A1 (de) 1998-02-11 1998-02-11 Verfahren zur Herstellung von Stärkeestern
DE19805367 1998-02-11
PCT/DE1999/000276 WO1999041287A1 (fr) 1998-02-11 1999-02-02 Procede de production d'esters d'amidon

Publications (1)

Publication Number Publication Date
EP1070086A1 true EP1070086A1 (fr) 2001-01-24

Family

ID=7857253

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99907304A Withdrawn EP1070086A1 (fr) 1998-02-11 1999-02-02 Procede de production d'esters d'amidon

Country Status (3)

Country Link
EP (1) EP1070086A1 (fr)
DE (1) DE19805367A1 (fr)
WO (1) WO1999041287A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110372806A (zh) * 2019-07-30 2019-10-25 诸城兴贸玉米开发有限公司 一种乳胶手套隔离剂用变性淀粉

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19924772A1 (de) * 1999-05-29 2000-11-30 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung von in Wasser redispergierbaren Agglomeraten aus biologisch abbaubaren Stärkeestern
DE10062848C1 (de) 2000-12-11 2002-04-04 Biop Biopolymer Gmbh Wasserformbeständiges, thermoplastisches Stärkematerial, Verfahren zu dessen Herstellung und dessen Verwendung
EP2064294A2 (fr) * 2006-09-22 2009-06-03 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Additif pour peinture
CN102115501A (zh) * 2010-12-29 2011-07-06 哈尔滨商业大学 一种酸解乙酰化复合变性淀粉的制备方法
CN105969199A (zh) * 2016-05-26 2016-09-28 广西众昌树脂有限公司 松香酯的制备方法
CN105950020A (zh) * 2016-05-26 2016-09-21 广西众昌树脂有限公司 松香酯的生产方法
CN109517080B (zh) * 2018-11-06 2023-06-16 浙江大学 辛烯基琥珀酸淀粉酯、脂溶性营养素微胶囊及制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU952852A1 (ru) * 1981-02-19 1982-08-23 Ордена Трудового Красного Знамени Институт Химии Древесины Ан Латвсср Способ активации целлюлозы
US5205863A (en) * 1991-11-14 1993-04-27 International Communications & Energy Agricultural biodegradable plastics
CA2089117A1 (fr) * 1993-02-09 1994-08-10 J. Ming Zhuang Methode servant a ameliorer l'acetylation de la cellulose
US5629416A (en) * 1995-03-31 1997-05-13 National Starch And Chemical Investment Holding Corporation Method of preparing crosslinked starch esters
DE19633474A1 (de) * 1996-08-20 1998-02-26 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung biologisch abbaubarer Stärkeester

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9941287A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110372806A (zh) * 2019-07-30 2019-10-25 诸城兴贸玉米开发有限公司 一种乳胶手套隔离剂用变性淀粉

Also Published As

Publication number Publication date
WO1999041287A1 (fr) 1999-08-19
DE19805367A1 (de) 1999-08-12

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