EP3164208A1 - Procede de synthese d'allophane hybride - Google Patents
Procede de synthese d'allophane hybrideInfo
- Publication number
- EP3164208A1 EP3164208A1 EP15734346.8A EP15734346A EP3164208A1 EP 3164208 A1 EP3164208 A1 EP 3164208A1 EP 15734346 A EP15734346 A EP 15734346A EP 3164208 A1 EP3164208 A1 EP 3164208A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base
- aluminum
- reactor
- allophane
- medium
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
Definitions
- the present invention aims to provide a process for the preparation of hollow particles of allophane-type aluminosilicate hybrid core. More specifically, it proposes a process for synthesizing aluminosilicates of spherical and hollow form, and whose internal silicon atoms are at least 90% by number, and preferably at 100% by number, functionalized by a radical. hydrophobic hydrocarbon.
- Allophans are aluminosilicate spheres (OH ⁇ AhCbSiOH) and exist naturally in natural deposits, and are related to imogolites of the same formula and chemical anisotropy, but in the form of hollow filaments still called nanotubes.
- the outer surface of the allophanes is covered with Al-OH while their inner surface is covered with Si-OH.
- the inside of the spheres is filled with water and on the wall of the nanospheres are pores of 0.7 to 1 nm which allow the water to be exchanged with the outside.
- US Pat. No. 6,254,845 describes a process for preparing hollow spheres of amorphous aluminosilicate polymers.
- the method comprises blending a silicon-based compound at high speed with an aluminum compound to form a slurry comprising precursor particles and a salt in solution. The latter is then removed and the particles of the precursor subjected to a heat treatment to obtain the hollow spheres of expected luminosilicates.
- the document FR 2 845 515 describes the synthesis of so-called partially hybrid allophanes, insofar as the interior of the hollow spheres is covered with 50% by number of Si-OH and by 50% by number of SR with R being a methyl group or vinyl. It should be noted that the presence of non-hydrolysable groups on the inner surface has the consequence of generating an increase in the diameter of these partially hybrid spheres. Their diameter changes from 5 nm to 10 nm.
- the present invention is specifically intended to provide a method according to this expectation.
- the present invention relates to a process for preparing hollow particles of spherical aluminosilicates of the allophane and hybrid-core type comprising at least the steps of
- all the steps (a) to (d) are carried out consecutively within the same reactor.
- the material constituting said reactor is devoid of silanol group and free fluorine atom.
- the constituent material of the reactor is different from glass and teflon.
- the material constituting the reactor is selected from stainless steel, polypropylene, inert porcelains including those conforming to those used in industrial chemistry reactors.
- the silicon alkoxide is of formula RSi (OR ') 3 in which R' is a C 1 -C 2 alkyl group and R is a saturated or unsaturated C 1 -C 2 hydrocarbon group.
- OCKb methyltrimethoxysilane
- OCH 3 vinyltrimethoxysilane
- the inventors have found that the choice of a particular material for the reactor dedicated to the preparation of the aluminosilicate provides access to an aluminosilicate reproducing advantageously the allophane isotropy, while being hybrid heart.
- hybrid heart intends to qualify the fact that at least 90% by number of silicon atoms present on the internal face of said cavity are functionalized with a hydrocarbon radical.
- This functionalization rate control may in particular be carried out by thermogravimetric analysis called TGA technology coupled to spectrometry or ⁇ infra-red.
- the hollow particles of aluminosilicates obtained according to the invention are of course compatible with a wide variety of applications, in particular taking advantage of their internal cavity to convey or trap a wide variety of hydrophobic molecules of interest (cosmetic active agents , pharmaceuticals, plasticizers, pesticides, hormones ).
- a substance is said to be hydrophobic when it has a very weak or even a total lack of affinity for an aqueous medium. This lack of affinity also results in a very low or even a lack of aqueous solubility.
- a compound is said to be immiscible in water if less than 3%, preferably less than 2%, for example less than 1% by weight of this compound is in solubilized form in water.
- the precursor of the aluminum used during step (a) is chosen from aluminum perchlorate A1 (C10 4 ) 3> aluminum nitrate A1 (N0 3 ) 3 or aluminum chloride AICI3, and preferably is aluminum perchlorate A1 (C1C ⁇ 4) 3.
- the molar ratio Al / Si of step (a) is between 1.5 and 2.5.
- the aluminum concentration of the aqueous solution in step (a) may be from 0.01 to 1 mol.L -1 and preferably from 0.05 to 0.1 mol.L -1.
- the silicon alkoxide or the mixture of silicon alkoxides hydrolyzed in step (b) corresponds to the formula R-Si (OR ') 3 in which R' is a linear alkyl or alkenyl group or branched C 1 -C 6 , or a phenyl group, said group R possibly being able to carry a substituent chosen from -OH, -NH 2 , -COOH, a phenyl group or a halogen atom, and R is a linear alkyl group or branched to C1-C12.
- R ' is methyl, ethyl, propyl, butyl or vinyl and even more preferably R is methyl or vinyl.
- R is a methyl, ethyl or propyl group and, even more preferably, R is a methyl group.
- the preferred silicon alkoxides are methyltrimethoxysilane (OCH 3 ) 3 SiCH and vinyltrimethoxysilane
- the base / aluminum molar ratio (ratio between the concentration of added base and the amount of aluminum initially present) still means that the hydrolysis ratio is a synthesis parameter well known to those skilled in the art which can be determined at all. along the reaction from pH.
- the base added in step (b) may be selected from sodium hydroxide, potassium hydroxide or lithium hydroxide and, preferably, said base is sodium hydroxide. Its concentration may be between 0.1 and 3 mol L "1.
- the addition of the base is advantageously carried out at a rate of between 50 and 300 mL.1T 1, and preferably, between 100 and 280 ml / hr.
- the mixture thus obtained is stirred at room temperature, that is to say at a temperature likely to vary from 18 to 25 ° C until the medium becomes completely clear.
- This clarity can in particular be controlled by spectroscopy. It corresponds to 95% to 100% of visible transmission measured by UV-visible spectrometry in a 1 cm cell on the entire visible spectrum. This clarity can be obtained after 8 to 12 hours of agitation.
- This stirring time is indeed likely to vary according to the chemical nature of the silicon alkoxide retained for the process.
- step (d) can be carried out at a temperature between 70 and 150 ° C. and preferably between 80 and 100 ° C., either in an autoclave, in an oven or at reflux.
- the duration of the heating step (d) is between 4 and 8 days.
- the method of the invention may further comprise a step (e) washing or concentration of the solution obtained at the end of step (d).
- the washing step serves to remove from the reaction medium the by-products formed in the previous steps, such as residual ions from the base used in step (b) or the alcohols from the hydrolysis of alkoxide.
- Step (d) can therefore be carried out by dialysis, either by concentration and preferably by ultrafiltration.
- the hollow particles of hybrid aluminosilicates thus purified can be recovered according to conventional techniques.
- Another subject of the invention relates to the allophane-type hybrid spherical hollow-shaped particles as such that can be obtained according to the process of the invention, and simultaneously comprising a hydrophilic external surface and a hydrophobic internal surface at 100.degree. %.
- the presence of an internal cavity in these spheres can also be characterized by S AXS analysis.
- S AXS analysis by comparing the signal obtained by diffusion of X-rays to a homogeneous electron density model, it can be deduced that the hybrid allophanes have a wall of the order of 5 to 7 ⁇ thick and therefore a hydrophobic cavity with a size of between 2.5 and 5 nm.
- the particles according to the invention are particularly advantageous as vehicles or for the trapping of molecules of interest and in particular hydrophobic.
- Another aspect of the invention relates to the use of spherical hollow aluminosilicate hollow particles according to the claims for vehicle purposes or trapping at least one molecule of hydrophobic interest.
- a substance is said to be hydrophobic when it has a very weak or even a total lack of affinity for an aqueous medium. This lack of affinity also results in a very low or even a lack of aqueous solubility.
- a compound is said to be immiscible in water if less than 3%, preferably less than 2%, for example less than 1% by weight of this compound is in solubilized form in water.
- the invention furthermore aims at a particle according to the invention containing at least one molecule of hydrophobic interest, chosen for example from therapeutic, phytosanitary, surfactant, insecticidal, dyestuff or marker agents. .
- a fresh sodium hydroxide solution (5.33 g of NaOH in 1333 ml of DI water) is then added to the dropping funnel. The addition is at a rate of 250 mL per minute.
- the reaction medium is clear after 1 ⁇ 4 hour.
- the reaction mixture is stirred for 12 hours at room temperature before being heated for 5 days at 90 ° C. in a container. polypropylene or stainless steel. After cooling to room temperature, the reaction medium is washed (diaf ltré) and concentrated by ultrafiltration on a lOkD membrane.
- the yield is 76% (average measurement over three batches: two in a polypropylene bottle and one in a stainless steel container).
- Example 2 The procedure used is that of Example 1 except that 50 ml of EtOH were added to the aqueous medium to achieve the "solubility / dispersion" of (OMe) 3 -ivinyl.
- the yield compared to ⁇ introduced aluminum is 67% (obtained on three lots: 2 in a stainless steel container and 1 in a polypropylene container.
- the zeta potential is + 37mV.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1456382A FR3023181B1 (fr) | 2014-07-03 | 2014-07-03 | Procede de synthese d’allophane hybride |
PCT/EP2015/065128 WO2016001373A1 (fr) | 2014-07-03 | 2015-07-02 | Procede de synthese d'allophane hybride |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3164208A1 true EP3164208A1 (fr) | 2017-05-10 |
Family
ID=51610295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15734346.8A Ceased EP3164208A1 (fr) | 2014-07-03 | 2015-07-02 | Procede de synthese d'allophane hybride |
Country Status (4)
Country | Link |
---|---|
US (1) | US10512892B2 (fr) |
EP (1) | EP3164208A1 (fr) |
FR (1) | FR3023181B1 (fr) |
WO (1) | WO2016001373A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109569504B (zh) * | 2018-12-20 | 2021-06-08 | 中国科学院广州地球化学研究所 | 一种用于吸附有机气体的水铝英石材料及其制备方法 |
FR3136932A1 (fr) | 2022-06-27 | 2023-12-29 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Utilisation de polymères d’aluminosilicate à titre d’ingrédient actif contre les microorganismes phytopathogènes |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1574954A (en) * | 1977-03-28 | 1980-09-10 | Nat Res Dev | Synthetic imogolite |
DE69518909T2 (de) * | 1994-10-31 | 2001-04-05 | Kodak Pathe Paris | Neues, polymeres, leitfähiges Aluminiumsilikat-Material, Element mit diesem Material, und Verfahren zur Herstellung desselben |
FR2740465A1 (fr) * | 1995-10-25 | 1997-04-30 | Kodak Pathe | Composition antistatique et produit photographique contenant une couche de cette composition |
JP3200623B2 (ja) | 1997-02-25 | 2001-08-20 | 経済産業省産業技術総合研究所長 | 中空球状ケイ酸塩クラスターの製造方法 |
FR2767128B1 (fr) * | 1997-08-08 | 1999-09-10 | Eastman Kodak Co | Nouveau polymere inorganique a base d'aluminium et de silicium |
US6099894A (en) * | 1998-07-27 | 2000-08-08 | Frisby Technologies, Inc. | Gel-coated microcapsules |
FR2802912B1 (fr) * | 1999-12-27 | 2002-02-15 | Eastman Kodak Co | Procede pour preparer un polymere d'aluminosilicate |
JP4830078B2 (ja) | 2000-11-28 | 2011-12-07 | 独立行政法人産業技術総合研究所 | メタン分子の保持方法およびイモゴライトが充填された耐圧容器 |
FR2842515B1 (fr) * | 2002-07-18 | 2004-10-01 | Eastman Kodak Co | Procede pour preparer un polymere d'aluminosilicate hybride et polymere obtenu par ce procede |
FR2842541B1 (fr) * | 2002-07-18 | 2004-10-01 | Eastman Kodak Co | Materiau destine a la formation d'images par impression par jet d'encre |
JP4122917B2 (ja) | 2002-10-04 | 2008-07-23 | 富士電機機器制御株式会社 | 回路しゃ断器の接点開閉機構 |
FR2998560B1 (fr) * | 2012-11-23 | 2016-01-29 | Commissariat Energie Atomique | Procede de fabrication de nanotubes hybrides d'imogolite |
-
2014
- 2014-07-03 FR FR1456382A patent/FR3023181B1/fr active Active
-
2015
- 2015-07-02 US US15/323,512 patent/US10512892B2/en active Active
- 2015-07-02 EP EP15734346.8A patent/EP3164208A1/fr not_active Ceased
- 2015-07-02 WO PCT/EP2015/065128 patent/WO2016001373A1/fr active Application Filing
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2016001373A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20170128909A1 (en) | 2017-05-11 |
WO2016001373A1 (fr) | 2016-01-07 |
FR3023181A1 (fr) | 2016-01-08 |
FR3023181B1 (fr) | 2019-07-12 |
US10512892B2 (en) | 2019-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0547924B1 (fr) | Composition à base d'oxyde cérique, préparation et utilisation | |
EP2228127A1 (fr) | Procédé de préparation de particules de silice poreuses, lesdites particules et leurs utilisations | |
FR2721615A1 (fr) | Procédé de préparation de particules d'oxyde métallique organophiles. | |
FR2627773A1 (fr) | Particules fines de polyorganosilsesquioxane et procede de production de ces particules | |
FR3016303A1 (fr) | Procede de fabrication de microcapsules a double paroi, microcapsules preparees par ce procede et leur utilisation | |
FR3023181B1 (fr) | Procede de synthese d’allophane hybride | |
EP2806958B1 (fr) | Décontamination par hydrogels d'échantillons aqueux contenant des nanoparticules | |
EP2408786B1 (fr) | Nouveaux composes silanes porteurs d'une chaine carbonee cyclique comprenant une fonction alcyne pour fonctionnaliser des supports solides et immobiliser sur ces supports des molecules biologiques | |
CA2360830A1 (fr) | Sol organique et compose solide a base d'oxyde de titane et d'un compose amphiphile et procedes de preparation | |
FR2842515A1 (fr) | Procede pour preparer un polymere d'aluminosilicate hybride et polymere obtenu par ce procede | |
EP2922787B1 (fr) | Procédé de fabrication de nanotubes hybrides d'imogolite | |
EP3164209B1 (fr) | Application d'aluminosilicates hybrides | |
EP3538258B1 (fr) | Suspension colloïdale de nanoparticules de fluorure d'element alcalino-terreux fonctionnalisees | |
EP2567940B1 (fr) | Procédé de préparation d'argiles ayant de nouvelles propriétés physicochimiques | |
FR3023180A1 (fr) | Utilisation d’aluminosilicates a des fins de marquage | |
FR2840822A1 (fr) | Capsules minerales mesoporeuses par emulsion | |
EP2976299B1 (fr) | Procédé de fabrication de nanotubes d'imogolite à base de germanium | |
EP3164383B1 (fr) | Procédé de préparation de dithiocarbamates métalliques | |
EP2578581A1 (fr) | Nouveaux complexes de terres rares et matériaux hybrides organiques luminescents | |
FR3112540A1 (fr) | Procédé de préparation d'un gel d'alumine haute dispersibilité | |
FR3001454A1 (fr) | Procede de preparation d'un materiau hybride mgo/organique, ledit materiau et ses utilisations | |
WO2016076692A2 (fr) | Surfactant dérivé du quinolinium pour la modification d'argile | |
WO2006058995A2 (fr) | Oxyde poreux mesostructure multifonctionnalise | |
FR2700164A1 (fr) | Procédé d'hydrolyse d'esters carboxyliques alpha-substitués alpha-chiraux. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
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 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170203 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: THILL, ANTOINE Inventor name: PONCELET, OLIVIER |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20180831 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R003 |
|
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: 20191108 |