WO1998007755A1 - Verfahren zur herstellung biologisch abbaubarer stärkeester - Google Patents
Verfahren zur herstellung biologisch abbaubarer stärkeester Download PDFInfo
- Publication number
- WO1998007755A1 WO1998007755A1 PCT/DE1997/001705 DE9701705W WO9807755A1 WO 1998007755 A1 WO1998007755 A1 WO 1998007755A1 DE 9701705 W DE9701705 W DE 9701705W WO 9807755 A1 WO9807755 A1 WO 9807755A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- starch
- carboxylic
- reaction
- acid
- starches
- Prior art date
Links
Classifications
-
- 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
-
- 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
Definitions
- the invention relates to a process for the production of biodegradable starch esters, which can be processed thermoplastically with suitable plasticizers to form extrudates, moldings and foils, as well as cast foils and deep-drawn moldings.
- esterification variants described in DE 4 114 185 represent a further development of the process mentioned by MARK and MEHLTRETTER in US Pat. No. 3,795,670, but significant excesses of acid anhydride are still required here too, and the degree of substitution is only adjusted here via the reaction time.
- the alkaline activated starch is precipitated from the aqueous phase, dried and esterified in a separate reaction step. Crystal-clear to yellowish starch esters with very good mechanical properties are obtained.
- the disadvantage of this process is the costly and energy-intensive two-stage variant with intermediate precipitation and drying.
- the use of anhydrous acetic acid / acetic anhydride mixtures as acetylation reagents is also known. So CA. Burkhard (Rayon Text. Month ,, 23 (1942), 340 ff) after about 40 hours of reaction at reflux temperature produce starch triacetate.
- the object of the invention is to avoid the disadvantages of the prior art set out and to propose an economically advantageous process for the preparation of starch esters with defined degrees of substitution with largely homogeneous distribution of substituents.
- the starch esters produced by the process according to the invention are white, free-flowing powders which dissolve almost completely in solvents such as chloroform, acetone, ethyl methyl ketone, ethyl acetate, clear cloudiness only being recognizable at degrees of substitution below DS ⁇ 2.0. With degrees of substitution between 1.8 and 2.7, the starch esters according to the invention can be processed alone or with suitable plasticizers to form biodegradable, clear, brilliant moldings, foils or deep-drawn articles with good mechanical properties.
- the precipitated maize starch dcate is washed 3-5 times with water and dried.
- acetic anhydride 950 g are heated in a 10 l stirred reactor with a reflux condenser to about 120 ° C. and 30 min. kept at this temperature. Then over 15 min. another 1,900 g of acetic anhydride and 1000 g of glacial acetic acid were metered in and then kept at reflux at about 125 ° C. for 5 h. After cooling to 90 ° C, the reaction mixture is diluted with 2 kg of glacial acetic acid and precipitated in water.
- 1,050 g of acetic anhydride are heated in a 10 l stirred reactor with a reflux condenser to about 120 ° C. and 60 min. kept at this temperature. Thereafter, 1000 g of acetic anhydride are added quickly, the reaction mixture is refluxed at about 128 ° C. for 2 hours. After adding a mixture of 1 100 g of sigklareanhydrid and 2.000 g of glacial acetic acid is held, the reaction mixture still for 8 hours at about 125 ⁇ C at reflux. After cooling to 90 ° C, the reaction mixture is diluted with 3 kg of glacial acetic acid and precipitated in water. The precipitated pea starch acetate is washed 3-5 times with water and dried. Yield: 1,950 g DS: 2.6
- 1,200 g of acetic anhydride are heated in a 10 l stirred reactor with reflux condenser to about 120 ° C and 60 min. kept at this temperature. Then over 60 min. another 400 g of acetic anhydride are metered in and then 4 h at approx. Held at reflux. After cooling to 90 ⁇ C, the reaction mixture is precipitated in water.
- acetic anhydride 650 g are heated in a 10 l stirred reactor with reflux condenser to about 120 ° C and 30 min. kept at this temperature. Thereafter rapidly added 1,200 g önanthklareanhydrid min and after heating to about 135 C for about ⁇ 60th 750 g of acetic anhydride were added. After another 60 min. 1,500 g of glacial acetic acid are added and the reaction mixture is stirred for a further 4 h at approx. 130 ° C.
- reaction mixture After cooling to 90%, the reaction mixture is diluted with 2 kg of glacial acetic acid and precipitated in water.
- the precipitated corn starch diester is washed 3-5 times with water and dried.
- acetic anhydride 600 g are heated in a 10 l stirred reactor with reflux condenser to about 130 X and 15 min. kept at this temperature. Then 900 g of lauric anhydride are quickly added and after heating to approx. 135 X 60 min. touched. Then over 120 min. 800 g of acetic anhydride are metered in. After 60 min. 1,500 g of glacial acetic acid are added and the reaction time is 120 minutes. stirred at about 130X.
- reaction mixture After cooling to 90%, the reaction mixture is diluted with 2 kg of glacial acetic acid and precipitated in water.
- the resulting corn starch diester suspension is centrifuged twice and washed with water and for 15 min. stripped at about 95X with water vapor.
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
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97937445A EP0931098A1 (de) | 1996-08-20 | 1997-08-11 | Verfahren zur herstellung biologisch abbaubarer stärkeester |
JP10510250A JP2000516282A (ja) | 1996-08-20 | 1997-08-11 | 生分解性澱粉エステルの製造方法 |
US09/242,851 US20010037018A1 (en) | 1996-08-20 | 1999-02-22 | Process for the manufacture of biodegradable starch esters |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19633474.8 | 1996-08-20 | ||
DE19633474A DE19633474A1 (de) | 1996-08-20 | 1996-08-20 | Verfahren zur Herstellung biologisch abbaubarer Stärkeester |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/242,851 Continuation US20010037018A1 (en) | 1996-08-20 | 1999-02-22 | Process for the manufacture of biodegradable starch esters |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998007755A1 true WO1998007755A1 (de) | 1998-02-26 |
Family
ID=7803078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE1997/001705 WO1998007755A1 (de) | 1996-08-20 | 1997-08-11 | Verfahren zur herstellung biologisch abbaubarer stärkeester |
Country Status (5)
Country | Link |
---|---|
US (1) | US20010037018A1 (de) |
EP (1) | EP0931098A1 (de) |
JP (1) | JP2000516282A (de) |
DE (1) | DE19633474A1 (de) |
WO (1) | WO1998007755A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999041287A1 (de) * | 1998-02-11 | 1999-08-19 | Buna Sow Leuna Olefinverbund Gmbh | Verfahren zur herstellung von stärkeestern |
DE19856507A1 (de) * | 1998-12-08 | 2000-06-15 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung biologisch abbaubarer hochtransparenter Gießfolien aus Stärkeestern |
DE102009012161A1 (de) | 2009-03-06 | 2010-09-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von Polysaccharidderivaten |
DE102017126340A1 (de) | 2017-11-10 | 2019-05-16 | Innovent E.V. | Oberflächenbeschichtungszusammensetzung, verfahren zu ihrer herstellung und ihre verwendung |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19827312A1 (de) * | 1998-06-19 | 1999-12-23 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung von thermoplastisch verarbeitbaren Stärkeestern mit erhöhter Wärmeformbeständigkeit |
DE19857996A1 (de) * | 1998-12-16 | 2000-06-21 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung von thermoplastisch verareitbaren Stärkeestern |
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 |
DE19935476A1 (de) * | 1999-07-28 | 2001-02-01 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung von thermoplastischen Stärkeester-Pfropfcopolymeren mit hoher optischer Transparenz |
DE19935475A1 (de) * | 1999-07-28 | 2001-02-01 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung von Stärkeestern mit verbesserten optischen Eigenschaften |
DE10062848C1 (de) | 2000-12-11 | 2002-04-04 | Biop Biopolymer Gmbh | Wasserformbeständiges, thermoplastisches Stärkematerial, Verfahren zu dessen Herstellung und dessen Verwendung |
CN103570838B (zh) * | 2013-10-17 | 2015-09-02 | 广州大学 | 一种复合改性高直链淀粉的制备方法 |
JP2018053192A (ja) | 2016-09-30 | 2018-04-05 | 日本コーンスターチ株式会社 | エステル化澱粉及び澱粉系プラスチック組成物 |
DE102022117375A1 (de) * | 2022-07-12 | 2024-01-18 | Robert Boyle - Thüringisches Institut für BioWasserstoff- und Umweltforschung e.V. | Verfahren zur Herstellung von thermoplastischen Polysaccharidestern |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB487020A (en) * | 1936-10-29 | 1938-06-14 | British Celanese | Improvements in or relating to the manufacture of esters of polysaccharides |
GB535949A (en) * | 1939-11-11 | 1941-04-28 | Calico Printers Ass Ltd | An improved process for the manufacture of acetic esters of starch |
US4501888A (en) * | 1984-01-24 | 1985-02-26 | A. E. Staley Manufacturing Company | Process for producing esters of carbohydrate materials |
EP0204353A1 (de) * | 1985-05-08 | 1986-12-10 | Akzo N.V. | Verfahren zur Herstellung eines Esters von Stärke und einer Monocarbonsäure und Zusammensetzung auf Basis von so hergestellter Stärke |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5205863A (en) * | 1991-11-14 | 1993-04-27 | International Communications & Energy | Agricultural biodegradable plastics |
US5320669A (en) * | 1992-12-14 | 1994-06-14 | Iowa State University Research Foundation, Inc. | Cereal grain-based biodegradable thermoplastic compositions |
DE4326118A1 (de) * | 1993-08-04 | 1995-02-09 | Buna Gmbh | Bioabbaubare, thermoplastisch verformbare Materialien aus Stärkeestern |
DE4423681A1 (de) * | 1994-06-23 | 1996-01-04 | A U F Analytik Umwelttechnik F | Verfahren zur Herstellung partiell substituierter Stärkeacetate |
DE4442606C2 (de) * | 1994-11-30 | 1998-09-17 | Degussa | Quellbarer Stärkeester, Verfahren zu dessen Herstellung sowie Verwendung |
DE4442605A1 (de) * | 1994-11-30 | 1996-06-05 | Degussa | Quellbarer Stärkeester, Verfahren zu dessen Herstellung sowie Verwendung |
-
1996
- 1996-08-20 DE DE19633474A patent/DE19633474A1/de not_active Withdrawn
-
1997
- 1997-08-11 JP JP10510250A patent/JP2000516282A/ja active Pending
- 1997-08-11 WO PCT/DE1997/001705 patent/WO1998007755A1/de not_active Application Discontinuation
- 1997-08-11 EP EP97937445A patent/EP0931098A1/de not_active Withdrawn
-
1999
- 1999-02-22 US US09/242,851 patent/US20010037018A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB487020A (en) * | 1936-10-29 | 1938-06-14 | British Celanese | Improvements in or relating to the manufacture of esters of polysaccharides |
GB535949A (en) * | 1939-11-11 | 1941-04-28 | Calico Printers Ass Ltd | An improved process for the manufacture of acetic esters of starch |
US4501888A (en) * | 1984-01-24 | 1985-02-26 | A. E. Staley Manufacturing Company | Process for producing esters of carbohydrate materials |
EP0204353A1 (de) * | 1985-05-08 | 1986-12-10 | Akzo N.V. | Verfahren zur Herstellung eines Esters von Stärke und einer Monocarbonsäure und Zusammensetzung auf Basis von so hergestellter Stärke |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999041287A1 (de) * | 1998-02-11 | 1999-08-19 | Buna Sow Leuna Olefinverbund Gmbh | Verfahren zur herstellung von stärkeestern |
DE19856507A1 (de) * | 1998-12-08 | 2000-06-15 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur Herstellung biologisch abbaubarer hochtransparenter Gießfolien aus Stärkeestern |
DE102009012161A1 (de) | 2009-03-06 | 2010-09-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von Polysaccharidderivaten |
WO2010100126A1 (de) | 2009-03-06 | 2010-09-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Verfahren zur herstellung von polysaccharidderivaten |
DE102017126340A1 (de) | 2017-11-10 | 2019-05-16 | Innovent E.V. | Oberflächenbeschichtungszusammensetzung, verfahren zu ihrer herstellung und ihre verwendung |
Also Published As
Publication number | Publication date |
---|---|
EP0931098A1 (de) | 1999-07-28 |
US20010037018A1 (en) | 2001-11-01 |
DE19633474A1 (de) | 1998-02-26 |
JP2000516282A (ja) | 2000-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1998007755A1 (de) | Verfahren zur herstellung biologisch abbaubarer stärkeester | |
DE629518C (de) | Verfahren zur Herstellung von Cellulosemischestern | |
DE4114185C1 (de) | ||
DE69734111T2 (de) | Hydroxylalkylstärkeester und dessen herstellung und verwendung | |
DE60107833T2 (de) | Veresterte polysaccharidprodukte, beta-lacton ringgeöffnete ketendimer-produkte enthaltende zusammensetzungen und verfahren zur deren herstellung | |
DE2230884C3 (de) | Verfahren zur Veresterung von Stärke oder Stärkederivaten | |
DE69735110T2 (de) | Verfahren zur herstellung von einem stärkeester | |
EP0668293B1 (de) | Thermoplastische biologisch abbaubare Polysaccharidderivate, Verfahren zu ihrer Herstellung und ihre Verwendung | |
DE102009012161A1 (de) | Verfahren zur Herstellung von Polysaccharidderivaten | |
DE19529409A1 (de) | Maleinsäureadditionsproduktgruppen enthaltende, thermoplastische und biologisch abbaubare Polysaccharidester/-etherester | |
DE4013344C2 (de) | Spezialamylosen und ihre Verwendung zur Herstellung biologisch abbaubarer Kunststoffe | |
DE1296795B (de) | Verfahren zum Acylieren von Staerke | |
DE4223471C2 (de) | Stärkezwischenprodukt, Verfahren zu dessen Herstellung sowie Verfahren zu dessen Weiterverarbeitung | |
EP0346648B1 (de) | Verfahren zur Imprägnierung von Fasern eines Tabakrauchfilters mit Di- oder Polycarbonsäuren bzw. Anhydriden derselben | |
WO1999041287A1 (de) | Verfahren zur herstellung von stärkeestern | |
DE4442605A1 (de) | Quellbarer Stärkeester, Verfahren zu dessen Herstellung sowie Verwendung | |
EP1035135B1 (de) | Regioselektiv substituierte Ester von Oligo- und Polysacchariden und Verfahren zu ihrer Herstellung | |
WO2004065425A1 (de) | Kohlensäurediester, verfahren zu ihrer herstellung und verfahren zur herstellung von mit polysacchariden oder polysaccharid-derivaten an freien aminogruppen gekoppelten pharmazeutischen wirkstoffen | |
DE4425688A1 (de) | Verfahren zur Herstellung von hochsubstituierten Stärkeacetaten | |
EP0761689A1 (de) | Thermoplastische biologisch abbaubare Polysaccharidderivate, Verfahren zu ihrer Herstellung und ihre Verwendung | |
DE19827312A1 (de) | Verfahren zur Herstellung von thermoplastisch verarbeitbaren Stärkeestern mit erhöhter Wärmeformbeständigkeit | |
DE4423681A1 (de) | Verfahren zur Herstellung partiell substituierter Stärkeacetate | |
DE1593168B2 (de) | Verfahren zur herstellung von staerkeacetoacetaten | |
EP1449852A1 (de) | Verfahren zur Herstellung von modifizierten Polysaccariden mit verbesserten hydrophoben Eigenschaften | |
US2265528A (en) | Cellulose esters |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1998 510250 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09242851 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1997937445 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1997937445 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: CA |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1997937445 Country of ref document: EP |