EP0438548A1 - Formmasse auf der basis von stärkeether zur ausformung biologisch abbaubarer formteile - Google Patents
Formmasse auf der basis von stärkeether zur ausformung biologisch abbaubarer formteileInfo
- Publication number
- EP0438548A1 EP0438548A1 EP90909721A EP90909721A EP0438548A1 EP 0438548 A1 EP0438548 A1 EP 0438548A1 EP 90909721 A EP90909721 A EP 90909721A EP 90909721 A EP90909721 A EP 90909721A EP 0438548 A1 EP0438548 A1 EP 0438548A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- ethers
- starchy
- mouldings
- compound based
- 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- Withdrawn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
- 238000000465 moulding Methods 0.000 title claims description 6
- 150000002170 ethers Chemical class 0.000 title description 6
- 239000000206 moulding compound Substances 0.000 title 1
- 229920002472 Starch Polymers 0.000 claims abstract description 25
- 235000019698 starch Nutrition 0.000 claims abstract description 25
- 239000008107 starch Substances 0.000 claims abstract description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000003974 emollient agent Substances 0.000 abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- 229920000856 Amylose Polymers 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000006266 etherification reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- GVSOIFHQEVTXFU-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;oxirane Chemical compound C1CO1.OC(=O)CC(O)(C(O)=O)CC(O)=O GVSOIFHQEVTXFU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000003945 chlorohydrins Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- -1 hydroxypropyl groups Chemical group 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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
- C08L3/08—Ethers
-
- 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
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
Definitions
- starch in particular from the linear component of the starch, the amylsis, films and thermoplastic molded parts can be produced.
- modified starches in particular special starch ethers, can be used to produce films and moldings which often have improved performance properties. For example, Manufacture more flexible films and molded parts from starch ethers. This is based on solid, isolated starch ethers.
- Starch ethers are formally reaction products between hydroxyl groups of the glucose units of the starch molecules and alcoholic hydroxyl groups of other compounds. Moldings made from hydroxyethyl and hydroxypropyl starch ethers are particularly suitable for the production of flexible films.
- Hydroxyethyl or hydroxypropyl groups are introduced into the starch molecule by the action of the corresponding alkylene oxides on starch in aqueous alkali; chlorohydrins, e.g. Ethylene chlorohydrin and epichlorohydrin.
- chlorohydrins e.g. Ethylene chlorohydrin and epichlorohydrin.
- the conditions for producing oxyethylated starches are outlined in numerous patents, but precise details are rarely disclosed.
- the introduction of hydroxyethyl and propyl groups into the starch molecule has a major impact on the gelatinization properties of the starches.
- the paste shows greater clarity, and the retrogradation tendency in cooling and aging is much less than in the initial thicknesses.
- Another way to change the material properties is to use suitable additives.
- the number of positively tested additives is limited. Polyols such as e.g. Glycol and glycerin used.
- the invention follows the path of achieving degradable and environmentally compatible materials with a high utility value by combining starch etherification and additive addition.
- Oxethylated compounds, in particular citric acid have proven to be particularly advantageous as additives, and amylose and amylose starches have proven to be particularly suitable starches.
- mixtures of starch and citric acid can be reacted chemically with the corresponding epoxides, in particular ethylene oxide, advantageously in a one-pot reaction, provided that suitable reaction conditions are met, and with little effort, and thus obtain base materials for film and molded part production.
- base materials can be produced which, even with a low degree of oxyethylation, have good usage properties.
- the low degree of oxyethylation also means that the starch weight fraction and the citric acid weight fraction of the base materials are particularly high, and products can thus be produced from hardly modified natural products. This is because epoxies are the more expensive raw material components compared to starch and citric acid From this point of view, the method according to the invention is also considerably superior to the prior art.
- films made from a low-substituted hydroxyethyl starch (degree of substitution approx. 0.1-0.3) and 10% citric acid-ethylene oxide adduct as a plasticizer additive are much harder, hardly flexible and sometimes even brittle, as clear and transparent.
- Amylose (0.05 M) is reacted with a factor of the theoretically necessary amount of ethylene oxide (0.4 M) according to the known procedure and analogously to Example 1.
- the isolated starch product then has a relatively high degree of oxethylation of approximately 1. Films made from this matrix are soft, flexible and stretchy, but not sticky like comparatively film 1.
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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3920621 | 1989-06-23 | ||
DE3920621A DE3920621A1 (de) | 1989-06-23 | 1989-06-23 | Formmasse auf der basis von staerkeether zur ausformung biologisch abbaubarer formteile |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0438548A1 true EP0438548A1 (de) | 1991-07-31 |
Family
ID=6383434
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90909721A Withdrawn EP0438548A1 (de) | 1989-06-23 | 1990-06-22 | Formmasse auf der basis von stärkeether zur ausformung biologisch abbaubarer formteile |
Country Status (6)
Country | Link |
---|---|
US (1) | US5128461A (enrdf_load_stackoverflow) |
EP (1) | EP0438548A1 (enrdf_load_stackoverflow) |
JP (1) | JPH04502344A (enrdf_load_stackoverflow) |
CA (1) | CA2019570A1 (enrdf_load_stackoverflow) |
DE (1) | DE3920621A1 (enrdf_load_stackoverflow) |
WO (1) | WO1991000313A1 (enrdf_load_stackoverflow) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4114185C1 (enrdf_load_stackoverflow) * | 1991-04-30 | 1993-02-04 | Battelle-Institut E.V., 6000 Frankfurt, De | |
DE19523803B4 (de) * | 1995-06-29 | 2004-08-12 | Sopro Bauchemie Gmbh | Baustoffelement, Baustoffelementpaket, umweltfreundliches Baustoffgebinde, und Verwendung einer Hülle aus wasserlöslichem Material als Verpackung für einen Baustoff |
US6713624B1 (en) | 2002-05-02 | 2004-03-30 | Hasbro, Inc. | Starch-based modeling compound |
US7420024B2 (en) * | 2003-01-16 | 2008-09-02 | Cornell Research Foundation, Inc. | Partially biodegradable temperature and pH sensitive hydrogel |
US7553919B2 (en) * | 2005-05-06 | 2009-06-30 | Board Of Trustees Of Michigan State University | Starch-vegetable oil graft copolymers and their biofiber composites, and a process for their manufacture |
CN115322447B (zh) * | 2022-09-20 | 2023-03-24 | 江南大学 | 一种淀粉基增韧复合材料的加工方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU37997A1 (enrdf_load_stackoverflow) * | 1959-12-01 | |||
GB935339A (en) * | 1960-10-27 | 1963-08-28 | Staley Mfg Co A E | Hydroxyalkyl amylose |
GB1044139A (en) * | 1964-07-20 | 1966-09-28 | Staley Mfg Co A E | Amylose solutions |
JPS5315542B2 (enrdf_load_stackoverflow) * | 1973-03-01 | 1978-05-25 | ||
US4112222A (en) * | 1977-01-07 | 1978-09-05 | National Starch And Chemical Corp. | Method of preparing hydroxypropylated starch derivatives |
DE2708513C3 (de) * | 1977-02-26 | 1981-01-08 | C.H. Boehringer Sohn, 6507 Ingelheim | Wasserunlösliche, physiologisch unbedenkliche Masse, Verfahren zu ihrer Herstellung und ihre Verwendung |
-
1989
- 1989-06-23 DE DE3920621A patent/DE3920621A1/de active Granted
-
1990
- 1990-06-21 CA CA002019570A patent/CA2019570A1/en not_active Abandoned
- 1990-06-22 JP JP2509186A patent/JPH04502344A/ja active Pending
- 1990-06-22 WO PCT/EP1990/000998 patent/WO1991000313A1/de not_active Application Discontinuation
- 1990-06-22 US US07/654,621 patent/US5128461A/en not_active Expired - Fee Related
- 1990-06-22 EP EP90909721A patent/EP0438548A1/de not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO9100313A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1991000313A1 (de) | 1991-01-10 |
DE3920621A1 (de) | 1991-01-03 |
CA2019570A1 (en) | 1990-12-23 |
JPH04502344A (ja) | 1992-04-23 |
US5128461A (en) | 1992-07-07 |
DE3920621C2 (enrdf_load_stackoverflow) | 1991-09-19 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19910218 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19921113 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19930324 |