EP0931098A1 - Process for the manufacture of biodegradable starch esters - Google Patents
Process for the manufacture of biodegradable starch estersInfo
- Publication number
- EP0931098A1 EP0931098A1 EP97937445A EP97937445A EP0931098A1 EP 0931098 A1 EP0931098 A1 EP 0931098A1 EP 97937445 A EP97937445 A EP 97937445A EP 97937445 A EP97937445 A EP 97937445A EP 0931098 A1 EP0931098 A1 EP 0931098A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- carboxylic
- reaction
- acid
- starches
- 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- Withdrawn
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.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19633474A DE19633474A1 (en) | 1996-08-20 | 1996-08-20 | Process for the production of biodegradable starch esters |
DE19633474 | 1996-08-20 | ||
PCT/DE1997/001705 WO1998007755A1 (en) | 1996-08-20 | 1997-08-11 | Process for the manufacture of biodegradable starch esters |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0931098A1 true EP0931098A1 (en) | 1999-07-28 |
Family
ID=7803078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97937445A Withdrawn EP0931098A1 (en) | 1996-08-20 | 1997-08-11 | Process for the manufacture of biodegradable starch esters |
Country Status (5)
Country | Link |
---|---|
US (1) | US20010037018A1 (en) |
EP (1) | EP0931098A1 (en) |
JP (1) | JP2000516282A (en) |
DE (1) | DE19633474A1 (en) |
WO (1) | WO1998007755A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19805367A1 (en) * | 1998-02-11 | 1999-08-12 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of starch esters |
DE19827312A1 (en) * | 1998-06-19 | 1999-12-23 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of compostable, thermoplastically formable starch esters |
DE19856507A1 (en) * | 1998-12-08 | 2000-06-15 | Buna Sow Leuna Olefinverb Gmbh | High transparency, biodegradable cast film production for composite packaging and communication involves extruding starch esters with polyalkylene glycol, heating, increasing solids content and pressure molding |
DE19857996A1 (en) * | 1998-12-16 | 2000-06-21 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of thermoplastically processable starch esters |
DE19924772A1 (en) * | 1999-05-29 | 2000-11-30 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of water-redispersible agglomerates from biodegradable starch esters |
DE19935476A1 (en) * | 1999-07-28 | 2001-02-01 | Buna Sow Leuna Olefinverb Gmbh | Preparation of thermoplastic starch ester graft copolymers with improved transparency, by grafting carboxylic acid starch ester reaction mixtures with monomers using aqueous hydrogen peroxide in the presence of acetic anhydride |
DE19935475A1 (en) * | 1999-07-28 | 2001-02-01 | Buna Sow Leuna Olefinverb Gmbh | Preparation of starch esters with improved transparency, comprises bleaching carboxylic acid starch ester reaction mixtures with aqueous hydrogen peroxide in the presence of carboxylic anhydride |
DE10062848C1 (en) | 2000-12-11 | 2002-04-04 | Biop Biopolymer Gmbh | Thermoplastic starch material, used for making moldings, films or fibrous raw materials and melt coating, is obtained by extruding natural starch in the presence of destructurization agent and storage for retrogradation |
DE102009012161B8 (en) | 2009-03-06 | 2012-12-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the preparation of polysaccharide derivatives |
CN103570838B (en) * | 2013-10-17 | 2015-09-02 | 广州大学 | A kind of preparation method of composite modified high amylose starch |
JP2018053192A (en) * | 2016-09-30 | 2018-04-05 | 日本コーンスターチ株式会社 | Esterificated starch and starch-based plastic composition |
DE102017126340A1 (en) | 2017-11-10 | 2019-05-16 | Innovent E.V. | SURFACE COATING COMPOSITION, PROCESS FOR THEIR PREPARATION AND THEIR USE |
DE102022117375A1 (en) * | 2022-07-12 | 2024-01-18 | Robert Boyle - Thüringisches Institut für BioWasserstoff- und Umweltforschung e.V. | Process for producing thermoplastic polysaccharide esters |
Family Cites Families (10)
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 |
ATE43612T1 (en) * | 1985-05-08 | 1989-06-15 | Akzo Nv | PROCESS FOR THE PREPARATION OF AN ESTER OF STARCH AND A MONOCARBONIC ACID AND COMPOSITION BASED ON STARCH THUS PREPARED. |
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 (en) * | 1993-08-04 | 1995-02-09 | Buna Gmbh | Biodegradable, thermoplastically mouldable materials made from starch esters |
DE4423681A1 (en) * | 1994-06-23 | 1996-01-04 | A U F Analytik Umwelttechnik F | Prepn. of starch acetate with high deg. of substitution |
DE4442605A1 (en) * | 1994-11-30 | 1996-06-05 | Degussa | Swellable starch ester, process for its production and use |
DE4442606C2 (en) * | 1994-11-30 | 1998-09-17 | Degussa | Swellable starch ester, process for its production and use |
-
1996
- 1996-08-20 DE DE19633474A patent/DE19633474A1/en not_active Withdrawn
-
1997
- 1997-08-11 JP JP10510250A patent/JP2000516282A/en active Pending
- 1997-08-11 EP EP97937445A patent/EP0931098A1/en not_active Withdrawn
- 1997-08-11 WO PCT/DE1997/001705 patent/WO1998007755A1/en not_active Application Discontinuation
-
1999
- 1999-02-22 US US09/242,851 patent/US20010037018A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO9807755A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE19633474A1 (en) | 1998-02-26 |
WO1998007755A1 (en) | 1998-02-26 |
US20010037018A1 (en) | 2001-11-01 |
JP2000516282A (en) | 2000-12-05 |
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Legal Events
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