EP0883630A1 - Verfahren zur oxidation von stärke - Google Patents

Verfahren zur oxidation von stärke

Info

Publication number
EP0883630A1
EP0883630A1 EP97905500A EP97905500A EP0883630A1 EP 0883630 A1 EP0883630 A1 EP 0883630A1 EP 97905500 A EP97905500 A EP 97905500A EP 97905500 A EP97905500 A EP 97905500A EP 0883630 A1 EP0883630 A1 EP 0883630A1
Authority
EP
European Patent Office
Prior art keywords
acylated
starch
polysaccharidc
process according
polysacchande
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.)
Ceased
Application number
EP97905500A
Other languages
English (en)
French (fr)
Inventor
Dogan Sahin Sivasligil
Theodoor Maximiliaan Slaghek
Dirk De Wit
Kornelis Fester Gotlieb
Reinier Joszef Johannes Jansen
Hans Van Overeem
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.)
Kemira Chemicals BV
Original Assignee
Kemira Chemicals BV
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 Kemira Chemicals BV filed Critical Kemira Chemicals BV
Publication of EP0883630A1 publication Critical patent/EP0883630A1/de
Ceased 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
    • 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

Definitions

  • the present invention relates to a process for reducing the viscosity of polysaccharides, especially starch, by oxidativc degradation without metal catalysts.
  • Starch is economically relevant both as a foodstuff and for non-food applications. Worldwide the annual starch production is about 26 million tons.
  • One of the largest non-food users of starch derivatives is the paper industry. In this field starch solutions with high starch content (25 wt.%) and low viscosities are much desired.
  • Important features of starch derivatives arc an improved initial wet strength of the paper sheet, a better printability, a better retention of cationic additives and applicability as glue. The demand for these starch derivatives is several million tons a year.
  • Starch has to be subjected to a viscosity-reducing treatment, before it can be used on an industrial scale.
  • the starch is generally treated oxidatively in an alkaline medium at increased temperature (40-60°C). This treatment takes 4-15 hours at about 60°C, for example in case hypochlorite is used as an oxidising agent together with sulphuric acid or phosphoric acid.
  • Disadvantages of this method are the amount of salt produced in addition to chlorine-containing derivatives, and a high proportion of short chain starch molecules.
  • the peroxysulphuric acid has to be prepared in situ from hydrogen peroxide and sulphuric acid, or else a salt of the acid has to be used, which has the disadvantage of generating salts as byproducts.
  • the reactivity of pcracetic acid is lower and results in longer reaction times.
  • An ob)ect of the im cntion is to ⁇ dc a piocess for reducing the v iscosity of starch and other polysaccharides with simple means, without the use of heav ⁇ metals and salt-producing agents, and without oiganic -product It is also an object to prov ide a v iscosity-ieducmg pioccss which allows the starch granule to remain intact, for easier working, di ving and handling of the product
  • This object is achiev ed b ⁇ means of a pioccss whcicin the polysacchande is oxidised using hydrogen peroxide in the picscncc of an acv latcd poly sacchande as an activator
  • any wholh of partially watci -soluble poh saccha ⁇ dc can be used These comprise firstly starch (c.g potato, corn. wa ⁇ v maize, tapioca, wheat, ⁇ cc and other starches) and fractions and deriv ativ es thcicof. such as aim lose, floe gels, ethox latcd starch and carboxymeth l starch Furthci moic.
  • the solubilitv of cellulose deriv ativ es and inulm and deriv ati es thereof and pentosans such as w lans can be impro ed or their viscosity can be reduced with the process of the inv ention
  • Carbohydrate deriv atives such as N-acylated, carbox latcd, carbow methylated, alkv latcd, hv droxyalkylatcd, hydrogenated and dehydrogenated dci n ativ es can also be treated according to the ention
  • the acylated carbohydiatc used as a catah st can be any oligo- or poly ⁇ sacchande which is wholh or pai tiallv acv latcd It was found that only a small amount of acylated carbohy drate is ncccssai v to cnsuic an efficient reaction It is often sufficient if for each 700 anl diogkicosc (oi othci monosaccharide) units, one acylated monosaccharide unit is picscnt Picfciahh at least one and especially at least four monoacv latcd monosacchandc units ai c picscnt for each 100 units In particular an av erage of 0 06-0 2 acv latcd monosacchandc units is present m the total of non-acylated and acylated polysaccharidc.
  • acylated comprises alkanoylatcd (formylated, acetylatcd, propionylatcd, etc.), bcnzoylated, sulphatated, phosphory latcd etc..
  • the acylated carbohydrate can simply be obtained by treatment of a carbo- hydrate with an acylating agent such as acetic anhydride using standard methods.
  • acylated carbohydrates are commcrciallv available, such as acetyl starch having a DS of about 2.5% or 8%.
  • An advantage of the use of an acylated carbohydrate is that the oxidation reaction proceeds smoothly and no undesired by-products arc formed; the acylated polysaccharidc or its oxidation product can be part of the treated polysaccharidc product without any inconvenience.
  • the acylated carbohydrate can advantageously be a derivative of the same carbohydrate to be treated.
  • the treatment of starch can suitable be performed using acetylated starch as the activator.
  • the acv latcd carbohydrate can be prepared in situ, e.g. by acylation with the corresponding carboxylic anhydride at pH 8-9.5 in a concentrated solution or suspension of the carbohydrate. The acylation may then be followed by the oxidation, but oxidation may also be started during acylation.
  • the amount of hydrogen peroxide to be used is entirely dependent on the desired degree of oxidation.
  • An amount of 1 wt.% is sufficient in general for achieving an effective viscosity degree.
  • the hydrogen peroxide can be added at once, but it has been found that better products arc obtained when the hydrogen peroxide is added gradually or in portions, for example over a period from 5 minutes to 3 hours.
  • the reaction can be performed at room temperature, but preferably at increased temperature, generally from 20 to 90°C. in particular from 40°C to 5°C below the pasting temperature, which pasting temperature is at about 65°C for most starch types. This results in a viscosity-reduced product still having a granular structure.
  • the reaction time is from several minutes to several hours at that temperature, depending on the particular polysaccharidc and the desired degree of viscosity reduction.
  • the polysaccharidc is preferably treated at a relatively high concentration. such as 10-55 wt.%, in particular 33-50 % by weight.
  • the treatment is carried out under neutral to alkaline conditions, i.e. at a pH between 5 and 12, especially between 8 and 11, in particular between 9 and 1 1 .
  • the treatment can advantageously be carried out in two or more stages, i.e. addition of peroxide at neutral pH (5-8.5) and subsequent reaction at alkaline pH (8.5-1 1 ).
  • the acylation can be performed under slightly alkaline conditions (pH 7.5-9.5), during or after acylation peroxide is added with some pH decrease (e.g. pH 6-8.5) and oxidation is completed at higher pH (8.5-11 ).
  • the product obtained by the process of the invention is essentially free of chlorine (as salt or covalcntly bound), i.e. not abov e natural abundance ( ⁇ 20 ppm) and of transition metals.
  • the carboxyl content is preferably between 0.2 and 5, especially between 0.5 and 3 wt.%.
  • the viscosity is preferably below 4000 Brabender units (at 25 w.t% dry substance and at 40°C) and in particular below 1000 Brabender units.
  • Viskograph E The results arc given below in Brabender units at 40°C; V" means viscosity at 5 wt.%.
  • Table 1 summarises the results of the product after 3 hours and after 6 hours. The result of the treatment using only hydrogen peroxide after 3 hours is also given for comparison.

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)
EP97905500A 1996-02-29 1997-02-28 Verfahren zur oxidation von stärke Ceased EP0883630A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1002494A NL1002494C2 (nl) 1996-02-29 1996-02-29 Werkwijze voor het oxideren van zetmeel.
NL1002494 1996-02-29
PCT/NL1997/000098 WO1997031951A1 (en) 1996-02-29 1997-02-28 Process for oxidising starch

Publications (1)

Publication Number Publication Date
EP0883630A1 true EP0883630A1 (de) 1998-12-16

Family

ID=19762420

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97905500A Ceased EP0883630A1 (de) 1996-02-29 1997-02-28 Verfahren zur oxidation von stärke

Country Status (20)

Country Link
EP (1) EP0883630A1 (de)
JP (1) JP2000506197A (de)
KR (1) KR19990087307A (de)
CN (1) CN1212708A (de)
AU (1) AU723782B2 (de)
BG (1) BG102731A (de)
BR (1) BR9707771A (de)
CA (1) CA2247109A1 (de)
CZ (1) CZ266998A3 (de)
EA (1) EA000896B1 (de)
HU (1) HUP9901784A3 (de)
IL (1) IL125942A0 (de)
NL (1) NL1002494C2 (de)
NZ (1) NZ331585A (de)
PL (1) PL328613A1 (de)
SK (1) SK119098A3 (de)
TR (1) TR199801653T2 (de)
WO (1) WO1997031951A1 (de)
YU (1) YU37298A (de)
ZA (1) ZA971785B (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007085C2 (nl) * 1997-09-19 1999-03-22 Inst Voor Agrotech Onderzoek Werkwijze voor de oxidatie van koolhydraten.
NL1010660C2 (nl) * 1998-11-26 2000-05-30 Inst Voor Agrotech Onderzoek Werkwijze voor het oxideren van zetmeel.
DE19953589B4 (de) 1999-11-08 2005-05-25 Sca Hygiene Products Gmbh Polysaccharid mit funktionellen Gruppen, Verfahren zu dessen Herstellung und daraus hergestellte Produkte
KR100371866B1 (ko) * 2000-06-24 2003-02-11 주식회사 삼양제넥스 종이 표면 사이징용 변성전분 및 그것의 제조방법
DE10241040B4 (de) * 2001-09-04 2004-11-18 Heppe Gmbh Biotechnologische Systeme Und Materialien Werkstoffe aus modifizierten Polysacchariden und Verfahren zu ihrer Herstellung
CN101177459B (zh) * 2007-11-30 2010-05-19 四川大学 高羰基含量氧化淀粉及其制备方法
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 (ko) * 2012-12-20 2014-06-19 대상 주식회사 옥수수 습식가공 부산물에 함유된 아황산의 저감방법
EP3205673B1 (de) * 2016-02-12 2018-05-23 Coöperatie Avebe U.A. Oxidation von stärke
CN108883400B (zh) 2016-02-19 2021-09-17 洲际大品牌有限责任公司 由生物质源形成多值料流的方法
CN114751994B (zh) * 2022-03-18 2023-02-17 西南林业大学 一种乙酰化氧化淀粉及其制备方法、一种改性脲醛树脂胶黏剂及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE443524A (de) * 1940-07-01
NL113890C (de) * 1955-07-27
EP0492000B1 (de) * 1990-12-28 1997-04-09 AUSIMONT S.p.A. Verfahren zur Erhöhung der Bleichwirksamkeit von anorganischen Persalzen
US5362868A (en) * 1993-06-18 1994-11-08 Degussa Aktiengesellshaft Thinning of granular starch

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9731951A1 *

Also Published As

Publication number Publication date
AU723782B2 (en) 2000-09-07
SK119098A3 (en) 1999-06-11
BG102731A (en) 1999-07-30
TR199801653T2 (xx) 1998-12-21
NZ331585A (en) 2000-03-27
HUP9901784A2 (hu) 1999-10-28
KR19990087307A (ko) 1999-12-27
PL328613A1 (en) 1999-02-01
WO1997031951A1 (en) 1997-09-04
CN1212708A (zh) 1999-03-31
EA199800778A1 (ru) 1999-02-25
EA000896B1 (ru) 2000-06-26
CZ266998A3 (cs) 1999-03-17
IL125942A0 (en) 1999-04-11
HUP9901784A3 (en) 1999-11-29
ZA971785B (en) 1997-09-29
CA2247109A1 (en) 1997-09-04
NL1002494C2 (nl) 1997-09-01
BR9707771A (pt) 2000-01-04
YU37298A (sh) 1999-09-27
JP2000506197A (ja) 2000-05-23
AU2235497A (en) 1997-09-16

Similar Documents

Publication Publication Date Title
US4675394A (en) Polysaccharide derivatives containing aldehyde groups, their preparation from the corresponding acetals and use as paper additives
US4731162A (en) Polysaccharide derivatives containing aldehyde groups for use as paper additives
US6586588B1 (en) Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US6872821B2 (en) Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US4663448A (en) Aldehyde-containing heterpolysaccharides, a process for their preparation, and the use thereof
US4749800A (en) Polysaccharide esters containing acetal and aldehyde groups
US3652542A (en) Process for preparing etherified depolymerized starch product compatible with polyvinyl alcohol
US8936820B2 (en) Process for the manufacture of oxidized starch, oxidized starch and its use
EP0883630A1 (de) Verfahren zur oxidation von stärke
WO1996038484A1 (en) Oxidized polymeric carbohydrate ethers for use as sequestering agent, and methods for the preparation thereof
DE60005141T2 (de) Oxidation von Polysacchariden mit Niroxylverbindungen
US4801699A (en) Polysaccharide esters containing acetal and aldehyde groups
Tupa et al. Preparation and characterization of modified starches obtained in acetic anhydride/tartaric acid medium
US4048435A (en) Method for the preparation of highly substituted granular starches
US4387221A (en) Alkyl- and alkenyl-sulfosuccinate starchhalf-esters, a method for the preparation thereof
JP2001049591A (ja) 繊維素材及びその製造方法
CN101365725A (zh) 淀粉改性的方法
US3767604A (en) Compatible mixtures of modified starch and polyvinyl alcohol
RU2160805C2 (ru) Отделочный агент
NL1004738C2 (nl) Fructaan-polycarbonzuur.
JP6675852B2 (ja) アニオン変性セルロースナノファイバーの製造方法
MXPA98007046A (en) Process to oxidate almi
US6265570B1 (en) Cold water soluble starch aldehydes and the method of preparation thereof
CA1237124A (en) Starch, gum, and cellulose derivatives containing aldehyde groups; their preparation from the corresponding acetals and use as paper additives
Ott et al. Modification of starch

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: 19980828

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20000616

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20001202