EP1633789A1 - Vinyle-polybutadienes hydrogenes de type caoutchouc - Google Patents

Vinyle-polybutadienes hydrogenes de type caoutchouc

Info

Publication number
EP1633789A1
EP1633789A1 EP04733789A EP04733789A EP1633789A1 EP 1633789 A1 EP1633789 A1 EP 1633789A1 EP 04733789 A EP04733789 A EP 04733789A EP 04733789 A EP04733789 A EP 04733789A EP 1633789 A1 EP1633789 A1 EP 1633789A1
Authority
EP
European Patent Office
Prior art keywords
vinyl
hydrogenation
units
formula
polybutadienes
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Withdrawn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
EP04733789A
Other languages
German (de)
English (en)
Inventor
Cristina Stere
Werner Obrecht
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP1633789A1 publication Critical patent/EP1633789A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation

Definitions

  • Hydrogenated polybutadienes with a high vinyl content of 85 to 100% are known from European patent application EP-A 0 024 315.
  • the hydrogenated vinyl-polybutadienes described there are distinguished by a high ozone resistance, but have the disadvantage that the elasticity of the products at lower temperatures leaves something to be desired due to the higher glass transition temperatures and melting enthalpies.
  • US Pat. No. 4,025,478 discloses hot melt adhesive preparations based on hydrogenated vinyl polybutadiene, the vinyl content of which is 50 to 95%, the vinyl content being able to be adjusted to a double bond content of less than 15%, preferably less than 10%, by hydrogenation.
  • the hydrogenated vinyl polybutadienes must have a Mooney viscosity of ⁇ 10.
  • lubricant compositions which, inter alia, contain a hydrogenated polybutadiene as a component in a smaller amount, the has a weight in the range of 20,000 to 300,000 and has a vinyl content of 65 to 85%. The degree of hydrogenation of these products is 75 to 100%.
  • the hydrogenated vinyl polybutadienes should have a certain molecular weight range which is generally from 30,000 to 200,000.
  • these molecular weights or the associated Mooney viscosities are too low to obtain tires or tire components with good physical properties.
  • the present invention therefore relates to hydrogenated vinyl polybutadienes with degrees of hydrogenation of 20 to 100%, Mooney viscosities in the range from 10 to 150 Mooney units (ML 1 + 4/100 ° C.), glass transition temperatures (T g ) of ⁇ - 57 ° C and enthalpy of fusion ( ⁇ H) ⁇ 30 J / g, which have a microstructure of
  • Preferred according to the invention are hydrogenated vinyl polybuatienes which have a degree of hydrogenation of 20 to 100% and Mooney viscosities in the range from 10 to 150, glass transition temperatures of ⁇ -80 ° C. and melting enthalpies of 0 to 30 J / g and have a microstructure of
  • the molecular weight ratio M w / M n has values in the range from 1 to 20, preferably 1 to 10.
  • the hydrogenated vinyl polybutadienes according to the invention of the above-mentioned specification are obtained in a known manner by hydrogenation of corresponding vinyl polybutadienes which have a vinyl content of 40 to 64, preferably 45 to 60% by weight and a 1,4-butenyl content of 36 to 60, preferably 40 to 55% by weight.
  • the suitable selection of the initiators for the polymerization, of the solvent, of the molecular weight regulator and of the reagents for adjusting the vinyl content can give vinyl-polybutadienes which have the aforementioned vinyl content and butenyl content and a glass transition temperature of ⁇ -80 ° C., preferably ⁇ -90 ° C, enthalpies of fusion from 0 to 40 J / g, preferably 0 to 30 J / g and Mooney viscosities ML1 + 4 (100 ° C) from 10 to 150 Mooney units, preferably 10 to 120 Mooney units.
  • the polymerization reaction is carried out under inert conditions (exclusion of water, oxygen and carbon dioxide) in order to avoid deactivation of the initiator and / or of the living polymers.
  • the polymerization is stopped by additives such as water, alcohols, phenols and / or acids.
  • additives such as water, alcohols, phenols and / or acids.
  • the polymerization is preferably not stopped, since the amount of hydrogenation catalyst required can be minimized in this way.
  • Unreacted monomer is removed from the reaction mixture before the hydrogenation reaction.
  • the hydrogenation is carried out “in situ”, it is preferred not to use water vapor for this, but rather to “flash” unreacted butadiene without first cooling the reaction mixture.
  • the hydrogenation of the vinyl polybutadiene obtained was also carried out in a known manner using the known hydrogenation catalysts.
  • the catalysts are known to the person skilled in the art and are described for example in US-A 3113986, US-A 3333024, US-A 3700633, US-A 4107236, US-A 3700633, US-A 3595942, 4028485, 3135716, 3150209, 3496154, 3498960, 4145298, 4238202, 3231635, 3265765, 3322856, 5030779, 3541064, 3644588, FR-A 1581146, 2393608, WO-A 9314130.
  • the hydrogenation is preferably carried out with a nickel salt in combination with an aluminum alkyl (see here e.g. EP-A 1 258 498).
  • Ni-n-octanoate Ni-acetylacetonate, Ni-2-ethylhexanoate and / or Ni-versatate.
  • Aluminum alkyls are, for example: triisobutyl aluminum, trimethyl aluminum, Triethyl aluminum and / or tri-n-propyl aluminum. Triethyl aluminum and Ni-n-octanoate are preferred.
  • the hydrogenation is carried out at temperatures of approximately 50 to 120 ° C. and a hydrogenation pressure of approximately 1 atm to 100 atm.
  • the hydrogenation catalyst - in the present case nickel salt in combination with an aluminum alkyl - is removed from the hydrogenation solution by treating the hydrogenation solution with a suitable complexing agent and an oxidizing agent.
  • the nickel formed during the hydrogenation of the vinyl polybutadiene is oxidized and brought into a soluble form with the complexing agent.
  • the resulting nickel complex is then washed out of the hydrogenation solution with water.
  • Nitrilotriacetic acid, ethylenediaminetetraacetic acid, oxalic acid and or or citric acid, preferably citric acid, are suitable as complexing agents for the nickel formed.
  • the amount of complexing agents is approximately 0.01 g to 3 g, based on 100 g of polymer.
  • the amount of nickel remaining in the polymer depends, among other things. on the amount of catalyst used, the concentration of the polymer solution, the oxidizing agent and the type and amount of the complexing agent.
  • Both air and pure oxygen can serve as the oxidizing agent.
  • additives such as anti-aging agents or vulcanization aids or stretching oils
  • the known additives are used in the usual amounts for this.
  • the amount of the additives depends on the intended use of the hydrogenated vinyl-polybutadienes obtained.
  • BR polybutadiene
  • SBR Styrene / butadiene rubber
  • DR butyl rubber
  • EPM and EPDM hydrogenated nitrile rubber
  • HNBR hydrogenated nitrile rubber
  • CR polychloroprene
  • NBR nitrile rubber
  • BVM Ethylene / vinyl acetate copolymers
  • CM and CSM chlorinated or chlorosulfonated polyethylene
  • the respective mixing ratio of the rubbers to one another can easily be determined by preliminary tests and depends on the later intended use of the hydrogenated vinyl-polybutadienes according to the invention.
  • Another object of the present invention is the use of the hydrogenated vinyl polybutadienes according to the invention with the physical properties and microstructure described above for the production of moldings of all kinds, in particular for the production of tires and tire components such as tire treads and tire sidewalls.
  • technical rubber articles e.g. Hoses and sealing rings are made from the elastic, hydrogenated vinyl polybutadienes according to the invention.
  • the hydrogenated vinyl polybutadienes according to the invention can also be mixed with thermoplastics or thermosets, for example to increase the impact resistance of these polymers.
  • the thermoplastics used for this are: styrene / acrylonitrile copolymers, polybutylene terephthalate, polyethylene terephthalate; Polyoxymethylene, polystyrene, polycarbonate and polyvinyl chloride.
  • the following thermosets can be used: Unsaturated polyester resins, epoxy resins as well as phenol / formaldehyde and melamine / formaldehyde resins.
  • thermoplastics to the hydrogenated vinyl polybutadienes used also depends on the later intended use of these thermoplastics. It can therefore easily be determined by appropriate preliminary tests. - ⁇ -
  • the polymerization of butadiene is carried out using n-butyllithium as the polymerization catalyst and cyclohexane as the solvent.
  • the vinyl contents are adjusted by adding tetramethylethylenediamine (TMEDA) and t-butoxyethoxyethane (BEE) and by varying the polymerization temperature.
  • TMEDA tetramethylethylenediamine
  • BEE t-butoxyethoxyethane
  • the polymerizations were carried out in a 1.7 liter steel reactor. For this purpose, 2/3 of the empty reactor was filled with dry cyclohexane under protective gas. Then butadiene was metered in and a butadiene concentration of 12 to 13% by weight in cyclohexane was set.
  • the vinyl content, the degree of hydrogenation and the remaining microstructure were determined by ⁇ -NMR spectroscopy in CDC1 3 .
  • Tg glass transition temperature
  • the vinyl content depends on the polymerization temperature and the molar ratio Bu-Li / TMEDA (Tab. 1) and the molar ratio BuLi / BEE (Tab. 2).
  • BuLi is the polymerization catalyst
  • c) the vinyl content is determined by ⁇ -NMR
  • b) polymerization temperature b) polymerization temperature.
  • Tg is the glass temperature determined by DSC.
  • the hydrogenation of vinyl polybutadiene was carried out using a hydrogenation catalyst based on Ni octanoate [Ni (Oct) 2 ] and triethyl aluminum (TEA).
  • the hydrogenation catalyst was preformed from Ni (Oct) 2 and TEA in a 25 ml Schlenck vessel under argon.
  • the Schlenk vessel was filled with 2-5 ml of dry cyclohexane, then 0.7-1.0 ml of TEA was added (corresponding to the amount of polymer present in the reactor).
  • a 10% solution of Ni (Oct) 2 in cyclohexane was added dropwise at about 15 ° C. while stirring and cooling.
  • the catalyst solution was freshly prepared in each case and used immediately after the preparation.
  • the vinyl polybutadiene was isolated from the solution, as described above, after the end of the polymerization, an aliquot was characterized and the remaining amount of the vinyl polybutadiene was dissolved and hydrogenated in cyclohexane.
  • Vulkanox BKF A solution of Vulkanox BKF is added to the samples, as described for the production of vinyl-polybutadiene samples, ethanol precipitated, dried and characterized.
  • the hydrogenation was complete after about 2 hours, recognizable from the fact that the polymer solution no longer absorbed hydrogen.
  • the amount of residual hydrogen remaining in the reactor and in the polymer solution was removed by introducing argon to a pressure of 3 bar and then releasing the pressure, this procedure being repeated three times.
  • the degrees of hydrogenation were determined by H-NMR.
  • the samples were also characterized by means of DSC in order to determine glass transition temperatures (Tg), melting temperatures (Tm) and melting enthalpies (DH).
  • BuLi is the polymerization catalyst
  • the vinyl content is determined by -NMR c) polymerization temperature.
  • Tg (DSC) is the glass temperature determined with DSC.
  • the catalyst is preformed in a separate Schlenck vessel.
  • TEA is introduced as a 5 M solution in cyclohexane, then Ni (Oct) 2 is added dropwise within 1 A hour.
  • Ni (Oct) 2 is added dropwise within 1 A hour.
  • the preformed catalyst is then added to the hydrogenation reactor.
  • the hydrogenation catalyst is produced in the hydrogenation reactor without separate preforming.
  • the catalyst components TEA, Ni (Oct) 2 are gradually added directly to the hydrogenation reactor after every 10 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Vinyle-polybutadiènes hydrogénés présentant des degrés d'hydrogénation de 20 à 100 %, des viscosités de Mooney de l'ordre de 10 à 150 unités Mooney (ML 1+4/100 DEG C), des températures de transition vitreuse (Tg) de = -57 DEG C, des enthalpies de fusion (<H) = 30 J/g et une microstructure avec (a) 0 à 44 % en poids d'unités 1,2-vinyle-butadiène de formule (I), (b) 20 à 64 % en poids d'unités 1,2-butylène de formule (II), (c) 0 à 60 % en poids d'unités 1,4-buténylène de formule (III) et (d) 0 à 60 % en poids d'unités 1,4-butylène de formule (IV). Lesdits vinyle-polybutadiènes hydrogénés conviennent parfaitement à la fabrication de corps moulés en caoutchouc de toute sorte, en particulier à la fabrication d'articles techniques en caoutchouc, ainsi que de pneus et de constituants de pneus. Les corps moulés en caoutchouc fabriqués à l'aide de vinyle-polybutadiènes hydrogénés selon la présente invention possèdent une bonne résistance au vieillissement et une bonne élasticité à basse température.
EP04733789A 2003-05-30 2004-05-19 Vinyle-polybutadienes hydrogenes de type caoutchouc Withdrawn EP1633789A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10324304A DE10324304A1 (de) 2003-05-30 2003-05-30 Kautschukartige hydrierte Vinyl-Polybutadiene
PCT/EP2004/005385 WO2004106386A1 (fr) 2003-05-30 2004-05-19 Vinyle-polybutadienes hydrogenes de type caoutchouc

Publications (1)

Publication Number Publication Date
EP1633789A1 true EP1633789A1 (fr) 2006-03-15

Family

ID=33441440

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04733789A Withdrawn EP1633789A1 (fr) 2003-05-30 2004-05-19 Vinyle-polybutadienes hydrogenes de type caoutchouc

Country Status (9)

Country Link
US (1) US7176262B2 (fr)
EP (1) EP1633789A1 (fr)
CN (1) CN100577690C (fr)
BR (1) BRPI0410882B1 (fr)
CA (1) CA2524667A1 (fr)
DE (1) DE10324304A1 (fr)
MX (1) MXPA05012945A (fr)
TW (1) TW200508260A (fr)
WO (1) WO2004106386A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005044453A1 (de) 2005-09-17 2007-03-22 Lanxess Deutschland Gmbh Peroxidisch vernetzte hydrierte Vinylpolybutadiene sowie deren Verwendung zur Herstellung von technischen Gummiartikeln mit gutem Rückverformungsverhalten über einen breiten Temperaturbereich
DE102005054091A1 (de) * 2005-11-12 2007-05-16 Lanxess Deutschland Gmbh Schwefelvernetzte hydrierte Vinylpolybutadiene sowie deren Verwendung zur Herstellung von technischen Gummiartikeln mit guten Rückverformungsverhalten über einen breiten Temperaturbereich
DE102005061473A1 (de) * 2005-12-22 2007-07-05 Lanxess Deutschland Gmbh Hochgefüllte Kautschukmischungen und Vulkanisate auf Basis von hydrierten Vinylpolybutadienen
DE102006031317A1 (de) * 2006-07-01 2008-01-03 Lanxess Deutschland Gmbh Schichtartig aufgebaute Vulkanisate auf Basis von hydriertem Vinylpolybutadien
US20130172493A1 (en) * 2011-12-30 2013-07-04 Exxonmobil Research And Engineering Company Process for making dendritic polyolefins from telechelic polycyclic olefins
RU2538955C1 (ru) * 2013-07-09 2015-01-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" Способ получения гидрированных производных 1,2-полибутадиенов
RU2538956C1 (ru) * 2013-07-09 2015-01-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" Способ получения гидрированных 1,2-полибутадиенов
RU2539182C1 (ru) * 2013-10-25 2015-01-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" Способ получения гидрированных 1,2-полибутадиенов
TWI653245B (zh) * 2013-12-30 2019-03-11 Arlanxeo Deutschland Gmbh 含有苯酚之氫化腈橡膠
US10428203B2 (en) 2014-09-08 2019-10-01 Sumitomo Rubber Industries, Ltd. Pneumatic tire
JP6716942B2 (ja) 2016-02-18 2020-07-01 住友ゴム工業株式会社 空気入りタイヤ及び空気入りタイヤの製造方法
JP6805502B2 (ja) * 2016-02-18 2020-12-23 住友ゴム工業株式会社 空気入りタイヤ
JP6972534B2 (ja) 2016-10-31 2021-11-24 住友ゴム工業株式会社 混練機投入用ポリマー
JP6862787B2 (ja) 2016-11-22 2021-04-21 住友ゴム工業株式会社 空気入りタイヤ
EP3378877B1 (fr) * 2017-02-28 2019-06-19 Evonik Oil Additives GmbH Polybutadiènes hydrogénés utiles en tant qu'additifs de lubrification
US20230303734A1 (en) 2020-09-28 2023-09-28 Arlanxeo Deutschland Gmbh Partially hydrogenated diene polymers
US12006436B2 (en) * 2020-11-13 2024-06-11 The Goodyear Tire & Rubber Company Rubber composition and a tire
WO2023129959A1 (fr) * 2021-12-29 2023-07-06 Bridgestone Corporation Polymères de polybutadiène hydrogéné et compositions de caoutchouc les incorporant

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600311A (en) * 1968-09-03 1971-08-17 Petrolite Corp Hydrocarbon systems containing branched alkyline polymers
FR2219219B1 (fr) * 1973-02-22 1976-06-11 Inst Francais Du Petrole
FR2293484A1 (fr) * 1974-12-03 1976-07-02 Inst Francais Du Petrole Utilisation de polybutadienes hydrogenes et epoxydes comme additifs multifonctionnels pour huiles lubrifiantes et compositions lubrifiantes obtenues
US4025478A (en) * 1975-02-07 1977-05-24 Phillips Petroleum Company Hot melt adhesive
US4187360A (en) * 1975-07-18 1980-02-05 Phillips Petroleum Company Heat-shrinkable or heat-expandable products from hydrogenated polybutadiene
AU538067B2 (en) 1979-08-20 1984-07-26 Firestone Tire And Rubber Co., The Hydrogenated polybutadiene
US4238202A (en) 1979-08-31 1980-12-09 Phillips Petroleum Company Hydrocarbon fuels with carburetor detergent properties
US4445562A (en) * 1981-05-07 1984-05-01 The Firestone Tire & Rubber Company Sealant compositions having, as an essential component, hydrogenated polybutadiene as network polymer
US5030779A (en) 1989-06-08 1991-07-09 Shell Oil Company Hydrogenation catalyst and hydrogenation process wherein said catalyst is used
US5393843A (en) * 1992-08-31 1995-02-28 Shell Oil Company Butadiene polymers having terminal functional groups
KR100463298B1 (ko) 2000-10-25 2004-12-23 아사히 가세이 가부시키가이샤 수소 첨가 중합체

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004106386A1 *

Also Published As

Publication number Publication date
WO2004106386A1 (fr) 2004-12-09
DE10324304A1 (de) 2004-12-16
US20040242797A1 (en) 2004-12-02
CA2524667A1 (fr) 2004-12-09
CN1798772A (zh) 2006-07-05
BRPI0410882A (pt) 2006-07-04
BRPI0410882B1 (pt) 2014-01-14
US7176262B2 (en) 2007-02-13
CN100577690C (zh) 2010-01-06
MXPA05012945A (es) 2006-02-28
US20050197466A9 (en) 2005-09-08
TW200508260A (en) 2005-03-01

Similar Documents

Publication Publication Date Title
EP1633789A1 (fr) Vinyle-polybutadienes hydrogenes de type caoutchouc
DE69004712T2 (de) Verfahren zur Herstellung von Polybutadien mit verbesserter Verarbeitkeit.
DE1420647A1 (de) Verfahren und Katalysator zum Polymerisieren von Dienen mit konjugierten Doppelbindungen
DE3309821A1 (de) Verfahren zur modifizierung eines ungesaettigten polymerkautschuks
DE2833721A1 (de) Verfahren zur polymerisation und copolymerisation von diolefinen und katalysator hierfuer
DE10052183A1 (de) Katalysatorzusammensetzung zur Hydrierung von Synthesekautschuken auf der Grundlage konjugierter Diene
EP2181000A1 (fr) Polymères nanostructurés à base de diènes conjugués
DE3103202A1 (de) Polybutadiene und ihre herstellung
DE3033175C2 (de) Polybutadienkautschukzusammensetzungen
DE10315274A1 (de) Verfahren zur Herstellung eines modifizierten Polymerkautschuks
DE2460009A1 (de) Polymerisationsverfahren und dadurch hergestelltes polymerisat
EP0312928A1 (fr) Copolymères ramifiés et leur procédé de préparation
DE3938927A1 (de) Lineare, alternierende-blockcopolymere
DE1620927A1 (de) Verfahren zur Herstellung von hohem cis-1,4-Polybutadien
DE1595184B1 (de) Verfahren zur Polymerisation eines konjugierten Diens
DE1495444A1 (de) Polymerisationskatalysatoren
DE69300540T2 (de) Färbungsverhinderung bei Titanium-katalysierten, hydrierten Dienpolymeren.
DE1770970C3 (de) Verfahren zur katalytischen Hydrierung von Kohlenwasserstoffpolymerisaten
DE68907044T2 (de) Additionsprodukte aus einem aminoalkohol und nitrilkautschuk.
DE10253147B4 (de) Verfahren zur Herstellung eines Polymerkautschuks und ölgestreckter Polymerkautschuk
EP1319673A1 (fr) Polymères modifiés par des groupes fonctionnalisés
DE2735178A1 (de) Polymere
DE10242942A1 (de) Hochverzweigte Dien-Polymere
DE1921017B2 (de) Verfahren zur Herstellung von kautschukartigen Polymeren
DD236321A1 (de) Verfahren zur selektiven butadienpolymerisation aus c tief 4 fraktion

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: 20051230

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LANXESS DEUTSCHLAND GMBH

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20161201