[go: up one dir, main page]

WO1986001512A1 - Preparation de derives liquides d'hydrates de carbone - Google Patents

Preparation de derives liquides d'hydrates de carbone Download PDF

Info

Publication number
WO1986001512A1
WO1986001512A1 PCT/GB1985/000388 GB8500388W WO8601512A1 WO 1986001512 A1 WO1986001512 A1 WO 1986001512A1 GB 8500388 W GB8500388 W GB 8500388W WO 8601512 A1 WO8601512 A1 WO 8601512A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyol
solvent
saccharide
catalyst
acid
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
PCT/GB1985/000388
Other languages
English (en)
Inventor
Richard Heywood Still
John Lawrence Stanford
John Leslie Cawse
Michael Joseph Donnelly
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.)
MANCHESTER INSTITUTE OF SCIENCE, University of
Original Assignee
MANCHESTER INSTITUTE OF SCIENCE, University of
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 MANCHESTER INSTITUTE OF SCIENCE, University of filed Critical MANCHESTER INSTITUTE OF SCIENCE, University of
Publication of WO1986001512A1 publication Critical patent/WO1986001512A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
    • C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic

Definitions

  • This invention relates to the preparation of liquid carbohydrate derivatives.
  • polyols are often based either on polyesters or polyethers with the latter having greater versatility. Most polyether polyols are at present based on oil-derived feedstocks, although polyols for certain limited applications have been prepared from natural products such as sucrose and sorbitol. Even these types of polyol however require oil-based chemicals to be used in- their preparation in order to convert the intractable carbohydrate into a liquid form. The conventional method of doing this involves chain-extending the hydroxyl groups of the carbohydrate with alkylene oxides such as propylene oxide and ethylene oxide.
  • alkylene oxides such as propylene oxide and ethylene oxide.
  • any polyols made from novel sources will have to possess similar characteristics to the oil-derived materials.
  • Some of the polyol characteristics which are required by the polyurethane industry include: low viscosity; high reactivity; miscibility with isocyanates; low volatility and low toxicity; and simplicity of manufacture.
  • RIM Reaction Injection Moulding
  • RRIM Reinforced Reaction Injection Moulding
  • the literature describes various simple glycosides (i.e. products obtained by reaction of a carbohydrate with an alcohol (the aglycon) having two or more hydroxyl groups).
  • glycosides are produced with aglycons of low molar mass and are generally obtained either in the form of amorphous solids with high softening points, or
  • glycosides are often highly polar and do not mix readily with diisocyanates.
  • chain extension is often accomplished by alkoxylation under pressure.
  • Table 1 gives some examples of short chain glycosides, prepared by the direct reaction between the carbohydrate and excess alcohol in the absence of an added solvent, and the subsequent steps necessary to convert them into useful products. The need for a two stage process to convert the glycosides to useful products is obviously disadvantageous as is the fact that the chain extension reaction is effected with oil derived products.
  • a method of producing a liquid glycoside comprising reacting a saccharide or polysaccharide with a long chain, substantially non-polar polyol in a solvent in the presence of an acid catalyst.
  • the product of this reaction comprises a saccharide moiety or oligomers thereof bonded at the C 1 -site to the long chain polyol which ensures that the original, polar saccharide or polysaccharide is converted to a liquid product miscible with isocyanates used for polyurethane formation.
  • the saccharide is preferably a mono or di-saccharide, preferred examples being D-glucose, L-glucose, galactose, sucrose, and lactose, although polysaccharides such as starch and simple alkyl glucosides such as methyl glucoside can also be used.
  • the saccharide may be used in pure form or may be provided by syrups such as glucose syrups, corn syrups or molasses.
  • Polyols for use in the method are preferably polymeric in nature and have a minimum molar mass of about 130 with a preferred maximum of about 2000.
  • the preferred polyols are of the general formula
  • R is H or lower alkyl (particularly methyl) m is 2 to 4 and n gives a maximum molar mass of about 2000.
  • PTHF is prepared from tetrahydrofuran which can be obtained from oat. hulls, corn cobs, or cellulose via the intermediate product furfural.
  • Castor oil is a triol obtained from the castor plant.
  • Catalysts useful for the reaction include mineral acids, organic acids and Lewis acids, preferred examples being HF, HCl (gaseous or concentrated aqueous), H 3 PO 4 , HClO 4 , H 2 SO 4 , HCOOH, p-toluene sulphonic acid, AICI 3 and BF 3 .
  • the reaction is conducted in a solvent. It is important to note that attempts at direct reaction between carbohydrates and high molar mass polyols fail owing to incompatibility of the two reactants. This leads to a number of undesirable side reactions: for example, if an attempt is made to react polytetrahydrofuran with glucose using an acid catalyst, in the bulk state, the PTHF udergoes coupling, dehydration and depolymerisation reactions (giving THF), while the glucose reacts mainly with other glucose molecules to produce intractable unreactive oligosaccharides.
  • the solvent for the reaction is preferably a polar, aprotic solvent, preferred examples being dimethylformamide, tetramethyl urea, dimethyl acetamide, N-methyl pyrolidinone (NMP), dimethyl sulphoxide, and acetonitrile.
  • a method of producing a liquid glycoside comprising reacting together a polysaccharide rendered substantially non-hydrogen bonding by substituent groups and a polyol in a solvent in the presence of an acid catalyst.
  • the substituent groups on the polysaccharide are substantially non-polar.
  • Glycosides produced by the method described in the preceding paragraph comprise monomeric or oligomeric units derived from the polysaccharide chain (the monomeric or oligomeric units being substantially non-hydrogen bonding by virtue of their substituent groups) bonded to one of the polyol moieties which provide reactive sites for subsequent polymer formation.
  • the nature of the monomeric or oligomeric units i.e. non-hydrogen bonding ensures that the products are liquids which are miscible with isocyanates.
  • Suitable substituents for rendering the polysaccharide substantially non-hydrogen bonding are, for example, alkyl groups, ester groups, halogen atoms, nitro groups and phosphate groups. It should be noted that the use of substituents rendering the polysaccharide substantially non-hydrogen bonding is essential as attempts to prepare liquid glycosides from unsubstituted cellulose were unsuccessful.
  • Examples of substituted polysaccharides which may be used in the method of the second aspect of the invention are starch ethers, cellulose ethers, dextran ethers, and simple glucosides thereof (e.g. methyl, ethyl, butyl). Mixtures of these polysaccharides may be used.
  • glycosides produced in accordance with the second aspect of the invention are to a large extent derived from materials (i.e. the polysaccharide) obtained from renewable natural resources.
  • the polyols used in the method of the second aspect of the invention are, for preference, low molar mass polyols although it is possible to use long chain, substantially non-polar polyols as used in the method of the first aspect of the invention.
  • Particularly suitable polyols are monomeric alkylene glycols, particularly those having 2-4 carbon atoms, i.e. ethanediol, propanediol and butanediol. Low molecular weight triols, e.g. glycerol, are also suitable.
  • the solvents used for the method of the second aspect may be the cheaper aliphatic ketones (e.g. butanone); aromatic hydrocarbons and chlorinated hydrocarbons.
  • the selected carbohydrate (pretreated by enzymes, hydrolysis etc. if necessary) is dissolved in the selected solvent along with the required amount of polyol.
  • the reaction is carried out either in a stepwise or simultaneous addition manner using a total reactant concentration of 20 to 50% w/w.
  • the reaction mixture is warmed if necessary, preferably in a nitrogen atmosphere, to facilitate dissolution of the carbohydrate.
  • the selected acid catalyst is then added and reaction allowed to proceed at the selected temperature (typically in the range ambient to 150°C) for a specified time, which depends upon the degree of conversion required. The latter is dependent on the temperature, nature of acid and . solvent, and concentration of reactants.
  • the acid catalyst is then neutralised, the solvent and other volatiles removed by vacuum distillation and the resulting liquid carbohydrate polyol (i.e. the glycoside), filtered, if necessary, to removed unreacted carbohydrate.
  • carbohydrate polyol i.e. the glycoside
  • the precise ratio of carbohydrate to polyol used in the preparation depends on the required properties of the final liquid glycoside. These properties can be varied over a wide range by using different stoichiometric amounts of polyol and carbohydrate.
  • the glycosides produced by the method of the first and second aspects of the invention are polyols useful forpolymer formation.
  • they satisfy the requirements for polyurethane formation, namely low viscosity, high reactivity, low volatility, miscibility with iscocyanates and low toxicity.
  • the ability to use different starting polyols and carbohydrates means that the liquid glycosides produced can be tailored to meet the specific requirements of a polymer manufacturer.
  • polyurethanes can be produced ranging from flexible or semi-rigid foams to soft rubbers and tough glasses.
  • liquid glycosides with high carbohydrate contents such as those obtained by the alcoholysis of ethyl cellulose or a simple saccharide with a low molar mass polyol
  • glasses can be produced which are dimensionally stable upto 140°C.
  • the glycosides are suitable for RIM,RRIM, and other processes such as casting and low-pressure dispensing.
  • polystyrene resin The number of hydroxyl groups which a polyol possesses is clearly instrumental in determining whether a polyurethane prepared from the polyol is linear or cross-linked.
  • Polyol glycosides prepared from a mono-saccharide in accordance with the first aspect of the invention possess at least five hydroxyl groups (Formula I) but the number of these
  • R polyol skeleton derived from e.g. PTHF, castor oil.
  • R' H or a second saccharide unit.
  • a liquid glycoside produced by the method of the first aspect of the invention may be reacted In excess with diisocyanate under mild conditions to produce an essentially linear polymer whereas the same glycoside in the presence of an excess of diisocyanate and at higher cure temperatur'es add longer reaction times will produce a cross-linked polymer.
  • glycosides obtained by the method of the second aspect of the invention are of the formula II:
  • second aspect of the invention have fewer hydroxyl groups per saccharide unit and so will tend to produce linear polymers on reaction with difunctional reagents since the most accessible hydroxyl groups will be at the hydrolysed sites.
  • Example 5 illustrates a method in accordance with the
  • reducing content was measured by means of quantitative Fehlings anlysis involving gravimetric determination of cuprous oxide.
  • the hydroxyl equivalent weight was determined by acetylation using the method of Sorenson and Campbell in which the polyol is refluxed for 3 hours with acetic anhydride/pyridine mixture. It was also necessary to determine the equivalent weight of the polyols towards isocyanate.
  • the polyol was mixed with diisocyanate in bulk using varying weight ratios, the mixtures were cured and the Tg of the polymer determined. The ratio at which a maximum in Tg was observed was taken as the effective equivalent weight of the polyol.
  • Residual solvent levels in the polyol glycosides were determined by gas-liquid chromatography. The glucose conversion was calculated from the reducing end group concentration of the solution immediately prior to catalyst neutralisation and is quoted relative to the reducing power of glucose.
  • Example 1 Preparation of polytetrahydrofuan 670 monoglucoside.
  • the resin was removed by filtration and washed with NMP which was returned to the filtrate.
  • the majority of the NMP was removed from the filtrate by rotary film evaporation under vacuum.
  • the recovered NMP may be utilised in further reactions without adverse effects.
  • the slurry so produced was filtered hot (50°C) to yield the polyol glucoside as a clear brown liquid and the unconverted carbohydrate as a brown paste.
  • Example 1 The reactants were heated to 130°C and held for 40 minutes at this temperature. The product was obtained as an amber liquid by the procedure described in Example 1. It had the following properties:
  • Example 5 Preparation of a Liquid glucoside from Ethyl Cellulose and Ethane Diol 99% Ethane diol (80g) and dry butanone (800cm 3 ) were placed in a 2L flanged reaction vessel equipped with a nitrogen inlet, stirrer and condenser. Ethyl cellulose (150g) (previously dried at 105°), having an ethoxyl content of 47.5 - 49% was added with stirring. When the mixture became homongeneous heating was commenced and when refluxing occurred perchloric acid (5.3cm 3 , S.G. 1.54), was added. Heating under reflux conditions was continued for 11 ⁇ 2 hours.
  • Poly tetrahydrofuran 2035 monoglucoside (11.3g) (prepared by the method described in Example 1) was reacted with diphenyl methane diisocyanate MDI (1.1g) at 50°C for ten minutes. The reacting mixture was then poured into a flat mould and cured at 100°C for 24 hours. The resulting opaque dark amber rubber had a Tg of -76.5°C when measured by differential scanning calorimetry (DSC) at a heating rate of 20°C min -1 on a Dupont 990 Thermal Analyser.
  • DSC differential scanning calorimetry
  • Poly tetrahydrofuran 629 monoglucoside (35.0g), ethane diol (8.75g) and MDI (45.97g) were reacted together at 50°C and then cured at 105°C for 21 hours.
  • the resulting polymer was a pale yellow, semi-rigid tough solid. Torsion pendulum studies showed this material to have a higher modulus over the temperature range (-20-140°C) than a polymer from
  • Example 5 (60.24g) was stirred under vacuum for 30 minutes at 80°C. MDI (45.18g) was then added and stirring continued under vacuum for 10 minutes. The clear amber reaction mixture was then poured into a flat mould and cured at 150°C for 2 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Polyethers (AREA)

Abstract

Procédés de production de glycosides liquides. Un procédé consiste à faire réagir un saccharide ou polysaccharide avec un polyol sensiblement non-polaire dans un solvant en présence d'un catalyseur acide. Un autre procédé consiste à faire réagir, en présence d'un catalyseur acide, un polyol avec un polysaccharide rendu sensiblement inerte à l'hydrogène par des groupes de substituants.
PCT/GB1985/000388 1984-08-30 1985-08-30 Preparation de derives liquides d'hydrates de carbone Ceased WO1986001512A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848421884A GB8421884D0 (en) 1984-08-30 1984-08-30 Liquid carbohydrate derivatives
GB8421884 1984-08-30

Publications (1)

Publication Number Publication Date
WO1986001512A1 true WO1986001512A1 (fr) 1986-03-13

Family

ID=10566013

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1985/000388 Ceased WO1986001512A1 (fr) 1984-08-30 1985-08-30 Preparation de derives liquides d'hydrates de carbone

Country Status (4)

Country Link
EP (1) EP0221080A1 (fr)
JP (1) JPS62500108A (fr)
GB (1) GB8421884D0 (fr)
WO (1) WO1986001512A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442371A3 (en) * 1990-02-16 1992-02-26 Basf Aktiengesellschaft Bisglycosides
FR2898810A1 (fr) * 2006-03-24 2007-09-28 Seppic Sa Nouveau procede d'amelioration de la tolerance oculaire de compositions moussantes et/ou detergentes a usage cutane
FR2936803A1 (fr) * 2008-10-06 2010-04-09 Arkema France Copolymere a blocs issu de matieres renouvelables et procede de fabrication d'un tel copolymere a blocs.
US8119582B2 (en) * 2006-04-28 2012-02-21 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Method for improving the foaming properties of cleansing and/or foaming formulations for topical use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346558A (en) * 1965-11-19 1967-10-10 Staley Mfg Co A E Continuous process for preparing polyol gly cosides
EP0038009A1 (fr) * 1980-04-11 1981-10-21 BASF Aktiengesellschaft Procédé de préparation de polymères contenant des groupes hydroxyle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346558A (en) * 1965-11-19 1967-10-10 Staley Mfg Co A E Continuous process for preparing polyol gly cosides
EP0038009A1 (fr) * 1980-04-11 1981-10-21 BASF Aktiengesellschaft Procédé de préparation de polymères contenant des groupes hydroxyle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Industrial & Engineering Chemistry Product Research and Development, Volume 8, Nr. 3, September 1969 F.H. OTEY et al.: "Urethane Plastics based on Starch and Starch-Derived Glycosides", see pages 267-274 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442371A3 (en) * 1990-02-16 1992-02-26 Basf Aktiengesellschaft Bisglycosides
US5126441A (en) * 1990-02-16 1992-06-30 Basf Aktiengesellschaft Bisglycosides
FR2898810A1 (fr) * 2006-03-24 2007-09-28 Seppic Sa Nouveau procede d'amelioration de la tolerance oculaire de compositions moussantes et/ou detergentes a usage cutane
WO2007110526A3 (fr) * 2006-03-24 2007-11-15 Seppic Sa Nouveau procédé d'amélioration de la tolérance oculaire de compositions moussantes et/ou détergentes à usage cutané
US7902135B2 (en) 2006-03-24 2011-03-08 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Method of improving the ocular tolerance of foaming and/or detergent compositions for skin use
US8119582B2 (en) * 2006-04-28 2012-02-21 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Method for improving the foaming properties of cleansing and/or foaming formulations for topical use
FR2936803A1 (fr) * 2008-10-06 2010-04-09 Arkema France Copolymere a blocs issu de matieres renouvelables et procede de fabrication d'un tel copolymere a blocs.
WO2010040944A3 (fr) * 2008-10-06 2010-06-10 Arkema France Copolymere a blocs issu de matieres renouvelables et procede de fabrication d'un tel copolymere a blocs
US8231950B2 (en) 2008-10-06 2012-07-31 Arkema France Block copolymer derived from renewable materials and method for making such block copolymer
EP3196226A1 (fr) * 2008-10-06 2017-07-26 Arkema France Copolymère à blocs issu de matières renouvelables et procédé de fabrication d'un tel copolymère à blocs
EP3660076A1 (fr) * 2008-10-06 2020-06-03 Arkema France Copolymère à blocs issu de matières renouvelables et procédé de fabrication d'un tel copolymère à blocs

Also Published As

Publication number Publication date
GB8421884D0 (en) 1984-10-03
JPS62500108A (ja) 1987-01-16
EP0221080A1 (fr) 1987-05-13

Similar Documents

Publication Publication Date Title
Vaidya et al. Polyester polyols for polyurethanes from pet waste: Kinetics of polycondensation
Beldi et al. Characterization of cyclic and non-cyclic poly-(ether-urethane) s bio-based sugar diols by a combination of MALDI-TOF and NMR
EP0342781B1 (fr) Polyuréthane et son procédé de préparation
JPH031331B2 (fr)
Donnelly et al. The conversion of polysaccharides into polyurethanes: a review
US3277076A (en) Polyether polyol useful as intermediate in preparation of polyurethane foam
JP2025041741A (ja) ブドウ糖含有糖類組成物を用いたポリオール組成物及びそれを含むポリウレタンフォーム
KR102437096B1 (ko) 알킬렌 옥사이드가 부가된 폴리올 조성물 및 이를 이용한 계면활성제
WO1986002635A1 (fr) Formation de polyols
WO1986001512A1 (fr) Preparation de derives liquides d'hydrates de carbone
US3337476A (en) Crystalline poly(propylene glycol)
US20240279264A1 (en) Catalytic polymerization and depolymerization of 1,6-anhydrosugars
Bar-Nir et al. Synthesis and structural characterization of 3-O-ethylene glycol functionalized cellulose derivatives
US3706726A (en) Polyurethane resins prepared from alkoxylated glucose derivatives
WO1993016977A1 (fr) Preparation et purification de poly(tetramethylene ether) formal glycols et de poly(oxybutylene formal)glycols
JP7208050B2 (ja) 土木建築材料
JP2005307083A (ja) リサイクル性ポリウレタンおよびその製造法
US6395859B1 (en) Hydrolyzable, energetic thermoplastic elastomers and methods of preparation thereof
JP5363737B2 (ja) ポリウレタン誘導体、その製造方法およびこれからなる生体適合性材料
EP4151662A1 (fr) Polyrotaxane ayant un groupe qui comporte une chaîne formée en ayant une molécule circulaire ayant un motif de répétition de propylénoxy
CN116144013B (zh) 一种端四烯基聚醚粘合剂及其合成方法
CN111574705A (zh) 一种双固化型硝酸酯聚醚及其合成方法
KR102632974B1 (ko) 무수당 알코올-알킬렌 글리콜 또는 무수당 알코올-알킬렌 글리콜 조성물을 포함하는 사슬 연장제 조성물 및 이를 이용하여 사슬 연장된 폴리우레탄, 및 이 사슬 연장된 폴리우레탄을 포함하는 접착제
CN116284744A (zh) 一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法
Al Souki et al. Synthesis and Post‐Functionalization of New Polyurethanes From Glycerol Monoether

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): GB JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1985904271

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1985904271

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1985904271

Country of ref document: EP