SK119098A3 - Process for oxidising starch - Google Patents
Process for oxidising starch Download PDFInfo
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- SK119098A3 SK119098A3 SK1190-98A SK119098A SK119098A3 SK 119098 A3 SK119098 A3 SK 119098A3 SK 119098 A SK119098 A SK 119098A SK 119098 A3 SK119098 A3 SK 119098A3
- Authority
- SK
- Slovakia
- Prior art keywords
- carbohydrate
- starch
- acylated
- hydrogen peroxide
- viscosity
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 229920002472 Starch Polymers 0.000 title claims abstract description 13
- 235000019698 starch Nutrition 0.000 title claims abstract description 13
- 239000008107 starch Substances 0.000 title claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001720 carbohydrates Chemical class 0.000 claims description 25
- 235000014633 carbohydrates Nutrition 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000004676 glycans Chemical class 0.000 abstract description 9
- 229920001282 polysaccharide Polymers 0.000 abstract description 9
- 239000005017 polysaccharide Substances 0.000 abstract description 9
- 239000012190 activator Substances 0.000 abstract description 3
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 125000001483 monosaccharide substituent group Chemical group 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- LPTITAGPBXDDGR-IWQYDBTJSA-N [(2r,3r,4s,5r)-3,4,5,6-tetraacetyloxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@H]1OC(OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O LPTITAGPBXDDGR-IWQYDBTJSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical class O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- 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
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)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Paper (AREA)
Abstract
Description
Spôsob oxidácie škrobuProcess for starch oxidation
Oblasť technikyTechnical field
Predložený vynález sa týka spôsobu zníženia viskozity polysacharidov oxidačnou degradáciou bez kovových katalyzátorov.The present invention relates to a method for reducing the viscosity of polysaccharides by oxidative degradation without metal catalysts.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Škrob musí byť pred svojím použitím v priemyselnom meradle podrobený úprave, ktorá znižuje jeho viskozitu. Na tento účel je škrob všeobecne spracovaný oxidačné v alkalickom prostredí pri zvýšenej teplote (40 až 60 °C). Táto reakcia trvá 4 až 15 hodín napr. v prípade, keď ako oxidačné činidlo je použitý chlornan spolu s kyselinou sírovou alebo fosforečnou pri teplote asi 60 °C. Nevýhodou tohoto spôsobu je množstvo produkovanej soli a nadmerné odbúravanie škrobu.The starch must be subjected to a treatment which reduces its viscosity before being used on an industrial scale. For this purpose, starch is generally oxidized in an alkaline environment at elevated temperature (40 to 60 ° C). This reaction takes 4 to 15 hours e.g. in the case where hypochlorite is used together with sulfuric or phosphoric acid as the oxidizing agent at a temperature of about 60 ° C. The disadvantage of this method is the amount of salt produced and excessive starch degradation.
Podľa iného spôsobu sa používa peroxid vodíka spolu s prechodným kovom ako katalyzátorom. Avšak po urobenej operácii je ťažko eliminovať obvykle jedovatý katalyzátor, aj keď sa použijú zlúčeniny ako je EDTA. Ďalšou nevýhodou je zafarbenie produktu.In another method, hydrogen peroxide is used together with a transition metal catalyst. However, after the operation, it is difficult to eliminate the usually poisonous catalyst, even if compounds such as EDTA are used. Another disadvantage is the coloring of the product.
US-A-5,362,868 ukazuje spôsob, podľa ktorého je viskozita (hydroxyetyl) škrobu znížená oxidáciou s použitím peroxykyseliny. Ako peroxykyselina sú používané napr. kyselina peroxosírová ( H2 SO5) alebo kyselina peroctová. Kyselina peroxosírová musí byť pripravená na mieste z peroxidu vodíka a kyseliny sírovej alebo inak musí byť použitá soľ tejto kyseliny, čo má nevýhodu vytvárania príslušných solí ako vedľajších produktov. Reaktivita kyseliny peroctovej je nižšia a výsledkom sú dlhšie reakčné doby. V US-A5,362,868 je taktiež opísané, že reakcia s peroxidom vodíka vykazuje neprijateľné reakčné časy.US-A-5,362,868 shows a process according to which the viscosity of (hydroxyethyl) starch is reduced by oxidation using a peroxyacid. As peroxyacids, e.g. peroxosulphuric acid (H 2 SO 5 ) or peracetic acid. Peroxosulphuric acid must be prepared on site from hydrogen peroxide and sulfuric acid, or otherwise a salt of this acid must be used, which has the disadvantage of forming the respective salts as by-products. The reactivity of peracetic acid is lower and results in longer reaction times. It is also disclosed in US-A5,362,868 that reaction with hydrogen peroxide exhibits unacceptable reaction times.
Podľa DE-A-4035053 materiály na báze celulózy, ako napr. bavlna, môžu byť bielené ich reakciou s kyselinou peroctovou bez aktivátorov a súčasne ich vystavením pôsobeniu ultrazvuku (35 kHz).According to DE-A-4035053 cellulose-based materials such as e.g. cotton, they can be bleached by reacting them with activators without activators and simultaneously exposing them to ultrasound (35 kHz).
Podstata vynálezuSUMMARY OF THE INVENTION
Cieľom tohto vynálezu je poskytnúť spôsob na zníženie viskozity škrobu a iných polysacharidov jednoduchými prostriedkami bez toho, aby sa použili ťažké kovy a činidlá poskytujúce soli a bez organických vedľajších produktov.It is an object of the present invention to provide a method for reducing the viscosity of starch and other polysaccharides by simple means without using heavy metals and salt-providing agents and without organic by-products.
Tento cieľ sa dosahuje pomocou spôsobu, podľa ktorého je karbohydrát oxidovaný použitím peroxidu vodíka v prítomnosti acylovaného karbohydrátu ako katalyzátora.This object is achieved by a process according to which the carbohydrate is oxidized using hydrogen peroxide in the presence of an acylated carbohydrate catalyst.
Ako karbohydrát, ktorý môže byť spracovaný spôsobom podľa tohoto vynálezu, môže byť použitý hocaký, celkom alebo čiastočne, vodorozpústny polysacharid. Tieto zahŕňajú predovšetkým škrob a jeho frakcie a deriváty, ako napr. amylózu, etoxylovaný a karboxymetylovaný škrob. Okrem toho môže byť daným spôsobom podľa vynálezu zlepšená rozpustnosť derivátov celulózy a inulínu a jeho derivátov rovnako môže byť znížená ich viskozita.Any carbohydrate that can be processed by the process of the present invention can be any, wholly or partially, water-soluble polysaccharide. These include, in particular, starch and its fractions and derivatives, such as e.g. amylose, ethoxylated and carboxymethylated starch. In addition, the solubility of the cellulose and inulin derivatives and their derivatives can also be improved by the method of the invention, and their viscosity reduced.
Acylovaný karbohydrát použitý ako katalyzátor môže byť hocaký mono-, di- alebo polysacharid, ktorý je úplne alebo čiastočne acylovaný. Bolo zistené, že na zaistenie reakcie je nutné iba malé množstvo acylovaného karbohydrátu. Je postačujúce, ak na každých 100 jednotiek anhydroglukózy (alebo ahydrofruktózy) je prítomná jedna jednotka tetraacylovaného monosacharídu alebo ekvivalentné množstvo, tj. štyri monoacylované monosacharídové jednotky. Všeobecne je použitý ekvivalent 1 - 50 hm. % acylovaného karbohydrátu vzhľadom k celkovému množstvu karbohydrátu a acylovaného karbohydrátu, skôr však 2-20 hm. %. Termín „acylované“ zahŕňa alkanoylované (acetylované, propionylované, atď.), benzylované, sulfatované, fosforylované atď.The acylated carbohydrate used as the catalyst may be any mono-, di- or polysaccharide that is wholly or partially acylated. It has been found that only a small amount of acylated carbohydrate is required to effect the reaction. It is sufficient if for each 100 units of anhydroglucose (or ahydrofructose) one unit of tetraacylated monosaccharide or equivalent is present, ie. four monoacylated monosaccharide units. Generally, an equivalent of 1-50 wt. % of acylated carbohydrate relative to the total amount of carbohydrate and acylated carbohydrate, but rather 2-20 wt. %. The term "acylated" includes alkanoylated (acetylated, propionylated, etc.), benzylated, sulfated, phosphorylated, and the like.
Acylovaný karbohydrát môže byť jednoducho získaný reakciou karbohydrátu s acylačným činidlom, ako napr. acetanhydridom, s použitím štandardných metód. Niektoré acylované karbohydráty sú dostupné komerčne, ako napr. peracetylglukóza, -galaktóza a sacharóza a acetylovaný škrob majúci DS asi 2,5 %.The acylated carbohydrate can be easily obtained by reacting the carbohydrate with an acylating agent, such as e.g. acetic anhydride, using standard methods. Some acylated carbohydrates are available commercially, such as e.g. peracetylglucose, -galactose and sucrose, and acetylated starch having a DS of about 2.5%.
Výhodou používania karbohydrátu je, že oxidačná reakcia prebieha hladko a nevznikajú žiadne nežiadúce vedľajšie produkty ; acylovaný karbohydrát alebo jeho oxidačný produkt môže byť časťou spracovaného karbohydrátového produktu bez akýchkoľvek ťažkostí.The advantage of using a carbohydrate is that the oxidation reaction proceeds smoothly and no unwanted by-products are formed; the acylated carbohydrate or its oxidation product may be part of the processed carbohydrate product without any difficulty.
Množstvo peroxidu vodíka, ktoré má byť použité, je celkom závislé od žiadaného stupňa oxidácie. Množstvo 1 hm. % je všeobecne postačujúce ne dosiahnutie účinného stupňa viskozity. S výhodou je používané 1 - 40 hm. %, zvlášť potom 2 - 20 hm. % peroxidu vodíka, vzhľadom k celkovému množstvu karbohydrátu a acetylovaného karbohydrátu.The amount of hydrogen peroxide to be used is entirely dependent on the desired degree of oxidation. Quantity 1 wt. % is generally sufficient to achieve an effective degree of viscosity. Preferably, 1-40 wt. %, especially 2 - 20 wt. % hydrogen peroxide, based on the total amount of carbohydrate and acetylated carbohydrate.
Reakcia môže byť robená pri teplote miestnosti, ale radšej pri zvýšenej teplote, všeobecne od 20 do 90 0 C , najlepšie potom od 40 0 C do 60 0 C. Reakčná doba je od niekoľko minút po niekoľko hodín pri teplote, ktorá závisí od príslušného karbohydrátu a požadovaného stupňa viskozity.The reaction may be conducted at the room temperature, but rather at an elevated temperature, generally between 20 and 90 0 C, more preferably from 40 0 C to 60 0 C. The reaction time is from several minutes to several hours at a temperature which depends on the particular carbohydrate and the desired degree of viscosity.
Príklad uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
K suspenzii škrobu ( 70 g suchej hmotnosti v 130g vody : 35 hm. %) boli pridané 2 g pentaacetátu pri 50 0 C. Potom sa naraz pridá roztok 10 ml peroxidu vodíka (30 hm.%). Pomocou 1 N roztoku kyseliny chlorovodíkovej sa pH zníži na 1,4. Po uplynutí reakčnej doby v rozsahu medzi 15 minútami a 6 hodinami je reakčná zmes zneutralizovaná a oxidovaný škrob je oddelený filtráciou, premytý vodou a sušený acetónom. Viskozita suspenzie 20 g produktu v 380 ml vody je určená Brabendorovým viskozimetrom.To a suspension of starch (70 g dry weight in 130 g water: 35 wt%) was added 2 g pentaacetate at 50 ° C. Then a solution of 10 ml hydrogen peroxide (30 wt%) was added in one portion. The pH is lowered to 1.4 with 1N hydrochloric acid. After a reaction time of between 15 minutes and 6 hours, the reaction mixture is neutralized and the oxidized starch is collected by filtration, washed with water and dried with acetone. The viscosity of a suspension of 20 g of product in 380 ml of water is determined by a Brabendor viscometer.
Tabuľka 1 zhrňuje výsledky produktu po 3 hodinách a po 6 hodinách. Na porovnanie je rovnako uvedený výsledok spracovania pri použití samotného peroxidu vodíka po 3 hodinách.Table 1 summarizes the product results after 3 hours and 6 hours. For comparison, the treatment result using hydrogen peroxide alone after 3 hours is also shown.
Tabuľka 1Table 1
Viskozita škrobu po oxidáciiViscosity of starch after oxidation
' Počiatočná teplota Brabenderovej krivky 2 Teplota maxima Brabenderovej krivky 3 Brabenderové jednotky pri maxime Brabenderovej krivky : 75 ot/min, tepl. gradient : 1,5°Brabender curve start temperature 2 Brabender curve maximum temperature 3 Brabender units at maximum Brabender curve: 75 rpm, temp. gradient: 1.5 °
C/min, t štart 40 °C , t kOnS-t 90 °C, udržiavacia doba : 30 minút: norma AVEBE 019142 4 Brabenderové jednotky v sedle Brabenderovej krivky (ako3)C / min, t start 40 ° C, t kO n S -t 90 ° C, holding time: 30 minutes: AVEBE 019142 4 Brabender units in the saddle of the Brabender curve (as 3 )
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1002494A NL1002494C2 (en) | 1996-02-29 | 1996-02-29 | Method for oxidizing starch. |
| PCT/NL1997/000098 WO1997031951A1 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SK119098A3 true SK119098A3 (en) | 1999-06-11 |
Family
ID=19762420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SK1190-98A SK119098A3 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0883630A1 (en) |
| JP (1) | JP2000506197A (en) |
| KR (1) | KR19990087307A (en) |
| CN (1) | CN1212708A (en) |
| AU (1) | AU723782B2 (en) |
| BG (1) | BG102731A (en) |
| BR (1) | BR9707771A (en) |
| CA (1) | CA2247109A1 (en) |
| CZ (1) | CZ266998A3 (en) |
| EA (1) | EA000896B1 (en) |
| HU (1) | HUP9901784A3 (en) |
| IL (1) | IL125942A0 (en) |
| NL (1) | NL1002494C2 (en) |
| NZ (1) | NZ331585A (en) |
| PL (1) | PL328613A1 (en) |
| SK (1) | SK119098A3 (en) |
| TR (1) | TR199801653T2 (en) |
| WO (1) | WO1997031951A1 (en) |
| YU (1) | YU37298A (en) |
| ZA (1) | ZA971785B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1007085C2 (en) * | 1997-09-19 | 1999-03-22 | Inst Voor Agrotech Onderzoek | Carbohydrate oxidation with hydrogen peroxide |
| NL1010660C2 (en) * | 1998-11-26 | 2000-05-30 | Inst Voor Agrotech Onderzoek | Method for oxidizing starch. |
| DE19953589B4 (en) | 1999-11-08 | 2005-05-25 | Sca Hygiene Products Gmbh | Polysaccharide with functional groups, process for its preparation and products made therefrom |
| KR100371866B1 (en) * | 2000-06-24 | 2003-02-11 | 주식회사 삼양제넥스 | Modified starch useful for paper surface sizing and a method thereof |
| DE10241040B4 (en) * | 2001-09-04 | 2004-11-18 | Heppe Gmbh Biotechnologische Systeme Und Materialien | Modified polysaccharide materials and process for their manufacture |
| CN101177459B (en) * | 2007-11-30 | 2010-05-19 | 四川大学 | Oxidized starch with high carbonyl content and its preparation method |
| US8641863B2 (en) * | 2011-09-30 | 2014-02-04 | Weyerhaeuser Nr Company | Catalytic carboxylation of cellulose fibers in a continuous process with multiple additions of catalyst, secondary oxidant and base to a moving slurry of cellulose fibers |
| KR101409213B1 (en) * | 2012-12-20 | 2014-06-19 | 대상 주식회사 | Method for decreasing sulfurous acid included in by-products of corn wet-milling |
| EP3205673B1 (en) * | 2016-02-12 | 2018-05-23 | Coöperatie Avebe U.A. | Oxidation of starch |
| EP3416740B1 (en) | 2016-02-19 | 2021-01-06 | Intercontinental Great Brands LLC | Processes to create multiple value streams from biomass sources |
| CN114751994B (en) * | 2022-03-18 | 2023-02-17 | 西南林业大学 | Acetylated oxidized starch and preparation method thereof, modified urea-formaldehyde resin adhesive and preparation method and application thereof |
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|---|---|---|---|---|
| BE443524A (en) * | 1940-07-01 | |||
| NL209345A (en) * | 1955-07-27 | |||
| EP0492000B1 (en) * | 1990-12-28 | 1997-04-09 | AUSIMONT S.p.A. | Process for increasing the bleaching efficiency of an inorganic persalt |
| US5362868A (en) * | 1993-06-18 | 1994-11-08 | Degussa Aktiengesellshaft | Thinning of granular starch |
-
1996
- 1996-02-29 NL NL1002494A patent/NL1002494C2/en not_active IP Right Cessation
-
1997
- 1997-02-28 SK SK1190-98A patent/SK119098A3/en unknown
- 1997-02-28 EA EA199800778A patent/EA000896B1/en not_active IP Right Cessation
- 1997-02-28 CA CA002247109A patent/CA2247109A1/en not_active Abandoned
- 1997-02-28 BR BR9707771-2A patent/BR9707771A/en not_active Application Discontinuation
- 1997-02-28 CN CN97192664A patent/CN1212708A/en active Pending
- 1997-02-28 JP JP9530836A patent/JP2000506197A/en active Pending
- 1997-02-28 CZ CZ982669A patent/CZ266998A3/en unknown
- 1997-02-28 KR KR1019980706715A patent/KR19990087307A/en not_active Withdrawn
- 1997-02-28 AU AU22354/97A patent/AU723782B2/en not_active Ceased
- 1997-02-28 WO PCT/NL1997/000098 patent/WO1997031951A1/en not_active Ceased
- 1997-02-28 IL IL12594297A patent/IL125942A0/en unknown
- 1997-02-28 TR TR1998/01653T patent/TR199801653T2/en unknown
- 1997-02-28 PL PL97328613A patent/PL328613A1/en unknown
- 1997-02-28 EP EP97905500A patent/EP0883630A1/en not_active Ceased
- 1997-02-28 HU HU9901784A patent/HUP9901784A3/en unknown
- 1997-02-28 ZA ZA9701785A patent/ZA971785B/en unknown
- 1997-02-28 NZ NZ331585A patent/NZ331585A/en unknown
- 1997-02-28 YU YU37298A patent/YU37298A/en unknown
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1998
- 1998-08-28 BG BG102731A patent/BG102731A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9901784A2 (en) | 1999-10-28 |
| WO1997031951A1 (en) | 1997-09-04 |
| KR19990087307A (en) | 1999-12-27 |
| AU2235497A (en) | 1997-09-16 |
| NL1002494C2 (en) | 1997-09-01 |
| IL125942A0 (en) | 1999-04-11 |
| ZA971785B (en) | 1997-09-29 |
| NZ331585A (en) | 2000-03-27 |
| AU723782B2 (en) | 2000-09-07 |
| TR199801653T2 (en) | 1998-12-21 |
| CN1212708A (en) | 1999-03-31 |
| BR9707771A (en) | 2000-01-04 |
| YU37298A (en) | 1999-09-27 |
| EA199800778A1 (en) | 1999-02-25 |
| BG102731A (en) | 1999-07-30 |
| PL328613A1 (en) | 1999-02-01 |
| EA000896B1 (en) | 2000-06-26 |
| CA2247109A1 (en) | 1997-09-04 |
| EP0883630A1 (en) | 1998-12-16 |
| HUP9901784A3 (en) | 1999-11-29 |
| CZ266998A3 (en) | 1999-03-17 |
| JP2000506197A (en) | 2000-05-23 |
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