EP0444168A1 - Verfahren zur reduktion der quellbarkeit von stärke - Google Patents

Verfahren zur reduktion der quellbarkeit von stärke

Info

Publication number
EP0444168A1
EP0444168A1 EP90912450A EP90912450A EP0444168A1 EP 0444168 A1 EP0444168 A1 EP 0444168A1 EP 90912450 A EP90912450 A EP 90912450A EP 90912450 A EP90912450 A EP 90912450A EP 0444168 A1 EP0444168 A1 EP 0444168A1
Authority
EP
European Patent Office
Prior art keywords
starch
crosslinking
reagent
preferably according
catalyst
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Withdrawn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
EP90912450A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ivan Tomka
Ralph WILLENBÜCHER
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.)
FLUNTERA AG
Original Assignee
FLUNTERA AG
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 FLUNTERA AG filed Critical FLUNTERA AG
Publication of EP0444168A1 publication Critical patent/EP0444168A1/de
Withdrawn legal-status Critical Current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
    • C08B31/003—Crosslinking of 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch

Definitions

  • the present invention relates to a process for reducing the swellability and / or solubility of essentially starch and / or starch tablets or extrudates from starch in essentially water.
  • the strongly hydrophilic character of starch means that it has a considerable water absorption. In a humid atmosphere resp. In the environment, the water absorption of the starch can be up to 20% or more, based on the total weight of starch and water.
  • starch When placed in water or an aqueous solution, the strong hydrophilicity causes the starch to swell and even partially dissolve on its surface.
  • Starch uses in the food industry, in pharmaceuticals, etc., where the partial water resistance of the starch is desired or at least not a nuisance, the starch is increasingly used in technical fields where the swellability or inconsistency of the starch in water is undesirable or at least bothersome.
  • starch as a raw material in so-called technical fields of application is becoming more and more important, since it is a natural product that is constantly available in nature, that is inexpensive to manufacture or use. in its production and in its processing it is physiologically harmless and ultimately biodegradable. It is all the more important to modify starch in such a way that, despite its hydrophilicity towards water, it exhibits increased resistance or. no longer swells in a damp environment.
  • the object of the present invention is therefore primarily to propose a method according to which at least partially water-resistant or non-swellable molded articles or extrudates can be produced.
  • essentially thermoplastic processes are at least almost anhydrous and essentially destructured Processable starch and / or a starch derivative, such as reactive starch, is at least partially crosslinked by means of chemical modification.
  • 102.8 ppm are in contrast to 100 ppm for the native starch and in contrast to 102, 98 and 94 ppm for starch digested in water.
  • the starch melt If the networking is largely in the homogenization resp. If the starch melt is destroyed, the starch melt can hardly be processed properly, since the gel point, up to which an elastically active crosslinking is possible, before the actual shaping or extrusion of the melt is achieved.
  • the gel point may only after extrusion or be achieved after the shaping or production of the shaped body.
  • the de-structuring and homogenization of the starch is preferably carried out with the exclusion of water.
  • the homogenization of starch is known per se, with native starch being mixed with at least 5% of an additive that has a solubility parameter
  • the mixture is then melted by means of heat supply and mixed intensively, depending on the vapor pressure of the additive, the mixing must take place in a closed system. This would in itself be necessary, for example, when using water, since water would evaporate in the melting range of the starch. However, as already mentioned above, the use of water as an additive is not very useful, since the starch should then be crosslinked in an anhydrous manner. Mixing in the melt takes place until the mixture is homogeneous, which can be determined, for example, by means of X-ray diffraction measurement.
  • the crosslinking reagent As an alternative to this, it is also possible, instead of or together with the crosslinking reagent, to add or add a catalyst which is responsible for triggering the crosslinking reaction and / or is at least largely required, to the melt, the extrudate or the shaped body. In the absence of the necessary catalyst, it is also possible to use the crosslinking reagent or. in this case better known as the reagent, to add the starch or the starch melt at an earlier point in time without the crosslinking reaction starting. In this case, the starch or starch melt so modified is a so-called reactive starch.
  • the crosslinking reagent in encapsulated form or. to mix in the starch or the starch melt in microcapsules, the crosslinking reaction being triggered by the crosslinking reagent being released by destroying the capsules during or after the production of the shaped body or extrudate.
  • the crosslinking reagent can be added to the starch or starch melt in any way, such as directly as a liquid, powder, etc.
  • admixing in encapsulated form resp. in microcapsule the advantage that the cross-linking reagent already before the extrusion process or. can be added to the starch or starch melt at any location during the extrusion process and the capsule shape or Wall thickness resp. Solubility of the capsule wall like this It can be selected that the crosslinking reagent is released to the starch or starch melt at the desired, predetermined point in time and mixed with it.
  • the catalyst (s) required for the crosslinking reaction can also be admixed in encapsulated form.
  • the crosslinking reagent and the catalyst in encapsulated form can also be added to the starch or starch melt, the two components preferably being mixed separately in capsules.
  • All commonly used polymers such as acrylates, polyamides, polyesters, cellulose, gelatin derivatives etc., are suitable as wall materials of the capsules, the capsule size being selected in the range from 0.1 to 100 ⁇ m, preferably 0.1 to 5 ⁇ m.
  • At least one of the following reagents is proposed as the crosslinking reagent:
  • Formaldehyde or a formaldehyde derivative such as urotropin and trioxane is a formaldehyde derivative such as urotropin and trioxane
  • a carbonic acid derivative such as di-halide or di-ester
  • inorganic polyacids such as phosphoric acids and boric acids.
  • crosslinking reagents for crosslinking the starch or starch melt the shaped starch body or extrudate is not exhaustive and includes a number of preferred chemical substances to be used. Of course, other chemical substances are also suitable as crosslinking reagents for the starch or starch melt, as are known from the prior art.
  • At least one reagent is added to the initially native or at least partially homogenized, thermoplastically processable starch or starch melt, which reacts with a functional group on a starch molecule by complexation or coalesces with it this covalently connects, and that the starch derivative thus produced resp. the reactive starch is melted and homogenized, what immediately before or during extrusion, processing or injection molding of the starch derivative or. of the reactive starch or the shape of the starch body or extrudate, the crosslinking of the starch is essentially triggered by activating the starch derivative modified with the reagent.
  • crosslinkable starch derivatives by reacting with the starch one of the reagents defined in the characterizing part of claim 7, comprising at least two reactive groups, regardless of whether this reagent is saturated or unsaturated.
  • an anhydride of an unsaturated carboxylic acid such as maleic anhydride, acrylic anhydride or a higher unsaturated fatty acid anhydride
  • an unsaturated epoxide such as butadiene oxide, acrylic acid glycide ester, an unsaturated n-methylol compound.
  • the above-mentioned complexation of the starch molecules is preferably carried out by introducing a fatty acid residue by means of a reagent, which reagent can be any chemical substance, as mentioned above with regard to crosslinking reagents and with respect to the reagents, by means of which double bonds in the starch molecules are to be introduced.
  • a reagent can be any chemical substance, as mentioned above with regard to crosslinking reagents and with respect to the reagents, by means of which double bonds in the starch molecules are to be introduced.
  • any fatty acid esters with an unsaturated fatty acid residue are also suitable.
  • an initiator such as an organic and / or inorganic peroxide or an azo compound
  • a suitable inhibitor or Delayers are added that the incubation time of the crosslinking reaction, respectively. Polymerization coincides with the end of the shaping.
  • an unsaturated starch derivative with auxo- chromium groups for example produced from natural starch with cinnamic acid, or from a starch derivative, defined according to the wording according to one of claims 10 or 11, is assumed and the crosslinking is triggered by light or UV, where as photo-initiated radical initiator for UV or light curing one of the following compounds can be used:
  • DMPA a-dimethoxy-a-phenylacetophenone
  • thermoplastically processable starch or starch melt are at least partially attached to the hydroxyl group substituents with a free primary amino group and that the amine derivative of starch thus produced is melted and homogenized and by means of a special crosslinking reagent which does not or only slightly reacts with the unmodified starch, such as an anhydride, a polybasic carboxylic acid, a dichloroalkane and / or a diepoxide is at least partially networked.
  • a special crosslinking reagent which does not or only slightly reacts with the unmodified starch, such as an anhydride, a polybasic carboxylic acid, a dichloroalkane and / or a diepoxide is at least partially networked.
  • crosslinking reagent for the addition of the crosslinking reagent, the special crosslinking reagent, the catalyst and / or the reagent, it is proposed that these, dissolved in a solvent, be added to the starch or starch melt, the solvent at least swelling or dissolving the starch and that Cross-linking reagent, the special cross-linking reagent, the catalyst or the reagent with the solvent has a lower reactivity than with the hydroxyl group of the starch or no reactivity at all and the distribution of cross-linking reagent, special cross-linking reagent, catalyst or reagent in the starch essentially by diffusion.
  • the two-phase emulsion can consist, for example, of an emulsifier, glycerol and oleic acid glyceride, preferably 0.5 to 5% emulsifier, .2 to 10% oleic acid glyceride and the rest glycerol being selected.
  • Suitable emulsifiers are substances with an amphiphilic character, such as lecithin, fatty acid-ethylene oxide derivatives of higher-quality alcohols, such as sugar alcohols, e.g. Tween 80 from the English company ICI, i.e. Polyoxyethylene sorbitan monooleate, and polyethylene, polypropylene copolymers, preferably with an HLB number (hydrophilic-lipophilic balance) of 10 to 15.
  • At least one additive of the order of 5 to 40% by weight, based on the starch / additive mixture be added for the homogenization and destructuring of the starch or melt, with the additive being one Solubility parameters of minimum
  • 1/2 -3/2 has at least 15 (cal • cm).
  • the additive used for the homogenization is, for example, glycerol, N-alkyl / alkenyl and vinyl pyrrolidone, a glycol and / or dimethyl sulfoxide (DMSO).
  • DMSO dimethyl sulfoxide
  • crosslinking reagent and the catalyst or the reagent and the initiator or the substituent and the special crosslinking reagent can be admixed spatially separately depending on the starch and the two starch mixtures, each containing one of the components, are then coextruded, laminated or laminated.
  • the crosslinking reaction by the two components is triggered by interdiffusion at the boundary layer and in the neighboring layer. The triggering of the crosslinking reaction resp. Depending on the type of reaction partner selected, their acceleration can be assisted by means of heat or UV / light. be accelerated.
  • the crosslinking can also be triggered by a molded starch body or an extrudate containing a reaction component being introduced into a solution or. a liquid is immersed which comprises the other reactant, in the present case as a catalyst, initiator, as a crosslinking reagent or as a reagent.
  • Liquid or the gas atmosphere can additionally also contain a further monomer, as characterized in claim 14, for regulating, controlling, accelerating or decelerating the crosslinking or. the crosslinking reaction.
  • Starch is melted as described above and 1 g of hexamethylene diisocyanate, which has been blocked with phenol, is added. The plates pressed therefrom are then hardened at 3 hours and at 100 ° C.
  • the plates produced above are placed in water for at least 24 hours.
  • Starch is melted as described in Examples 1 to 4 and two mixtures are produced therefrom.
  • One mixture is obtained by adding 6 g of N, N'-dimethylolethylene urea and the second mixture by adding 1 g of magnesium chloride to the starch melt. Sheets are then pressed from the two mixtures, which are then laminated together under the same pressing conditions. The laminates produced in this way are then post-annealed at 100 ° C. for 2 hours.
  • the starch is reacted with butadiene oxide and melted as described in the first example.
  • the catalyst is added, as described in Example 6, and then the plates are pressed from the melt. Again, post-annealing is carried out at 100 ° C. for 1 hour.
  • the starch plate is placed in 20% sodium hydroxide solution.
  • the capsules are produced by "McKinney (2)" interface polymerization as follows: 5 g of benzoyl peroxide are ground into a paste with 5 ml of acetone and 1 g of terephthaloyl chloride and 1 g of Carbowax 600. This is dispersed in a solution of 150 ml of water and 5 g of glycol. As described, the microcapsules with a diameter of 100 ⁇ m are suctioned off and isolated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP90912450A 1989-09-20 1990-09-06 Verfahren zur reduktion der quellbarkeit von stärke Withdrawn EP0444168A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3931363 1989-09-20
DE3931363A DE3931363A1 (de) 1989-09-20 1989-09-20 Verfahren zur reduktion der quellbarkeit von staerke

Publications (1)

Publication Number Publication Date
EP0444168A1 true EP0444168A1 (de) 1991-09-04

Family

ID=6389799

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912450A Withdrawn EP0444168A1 (de) 1989-09-20 1990-09-06 Verfahren zur reduktion der quellbarkeit von stärke

Country Status (9)

Country Link
EP (1) EP0444168A1 (enExample)
JP (1) JPH0645642B2 (enExample)
KR (1) KR920701257A (enExample)
AU (1) AU6183790A (enExample)
CA (1) CA2042066A1 (enExample)
DE (1) DE3931363A1 (enExample)
HU (1) HUT58767A (enExample)
WO (1) WO1991004278A1 (enExample)
ZA (1) ZA907293B (enExample)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2149296T3 (es) 1994-08-25 2000-11-01 Topac Multimediaprint Gmbh Estuche para un soporte de registro en forma de disco.
DE19729306C2 (de) 1997-07-09 2002-04-04 Celanese Ventures Gmbh Stärke und/oder modifizierte Stärke und Weichmacher enthaltende Zusammensetzungen sowie Verfahren und Verwendung
EP1176254A1 (en) † 2000-07-24 2002-01-30 The Dow Chemical Company Use of dispersions of crosslinked cationic starch in papermaking
DE10129312B4 (de) * 2001-03-26 2008-08-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hydrophobe Stärkecarbamate und Verfahren zu ihrer Herstellung
US10260197B2 (en) 2007-12-14 2019-04-16 Johns Manville Base interlining, methods for their manufacture and application thereof
DE102007060494A1 (de) 2007-12-14 2009-06-18 Johns Manville Europe Gmbh Trägereinlage, Verfahren zu deren Herstellung und deren Verwendung
DE102008059129A1 (de) 2008-11-26 2010-05-27 Johns Manville Europe Gmbh Binderverfestigtes, textiles Flächengebilde, Verfahren zu dessen Herstellung und dessen Verwendung
DE102008059128A1 (de) 2008-11-26 2010-05-27 Johns Manville Europe Gmbh Binderverfestigtes, textiles Flächengebilde, Verfahren zu dessen Herstellung und dessen Verwendung
DE102010007939A1 (de) 2010-02-12 2011-08-18 Johns Manville Europe GmbH, 86399 Vorkonfektionierte Trägereinlage und beschichtete Dachbahnen
DE102011121589A1 (de) 2011-12-20 2013-06-20 Johns Manville Europe Gmbh Binderverfestigtes, textiles Flächengebilde, Verfahren zu dessen Herstellung und dessen Verwendung
DE102014012238A1 (de) 2014-08-21 2016-02-25 Johns Manville Europe Gmbh Binderverfestigtes, textiles Flächengebilde, Verfahren zu dessen Herstellung und dessen Verwendung
DE102016011586A1 (de) 2016-09-24 2018-03-29 Johns Manville Europe Gmbh Binderverfestigtes, textiles Flächengebilde, Verfahren zu dessen Herstellung und dessen Verwendung
WO2021195087A1 (en) 2020-03-23 2021-09-30 Bay State Milling Company Rapid high amylose wheat seed purity test
CN115926401B (zh) * 2023-01-06 2023-06-30 中北大学 反应挤出生成脲醛时原位形成核-壳淀粉增强增韧的聚酯

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE942564C (de) * 1952-12-03 1956-05-03 Taeschner & Co Verfahren zur Herstellung von Kondensationsprodukten von Staerke mit Formaldehyd und/oder Acetaldehyd
GB1528851A (en) * 1975-06-10 1978-10-18 Cellcor Corp Of Canada Ltd Process and apparatus for producing starch products
FR2414533A1 (fr) * 1978-01-12 1979-08-10 Roquette Freres Colles de dextrine
US4237271A (en) * 1979-04-24 1980-12-02 The United States Of America As Represented By The Secretary Of Agriculture Crosslinked starch halohydrins and their nitrogen-containing substitution products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9104278A1 *

Also Published As

Publication number Publication date
HU906890D0 (en) 1991-08-28
CA2042066A1 (en) 1991-03-21
JPH0645642B1 (enExample) 1994-06-15
HUT58767A (en) 1992-03-30
JPH0645642B2 (ja) 1994-06-15
AU6183790A (en) 1991-04-18
DE3931363A1 (de) 1991-03-28
WO1991004278A1 (de) 1991-04-04
KR920701257A (ko) 1992-08-11
ZA907293B (en) 1991-09-25

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