EP0000893A1 - Procédé pour la préparation de polyisocyanates et leur utilisation - Google Patents

Procédé pour la préparation de polyisocyanates et leur utilisation Download PDF

Info

Publication number
EP0000893A1
EP0000893A1 EP78100606A EP78100606A EP0000893A1 EP 0000893 A1 EP0000893 A1 EP 0000893A1 EP 78100606 A EP78100606 A EP 78100606A EP 78100606 A EP78100606 A EP 78100606A EP 0000893 A1 EP0000893 A1 EP 0000893A1
Authority
EP
European Patent Office
Prior art keywords
formula
isocyanate
polyisocyanates
diisocyanate
nco
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.)
Granted
Application number
EP78100606A
Other languages
German (de)
English (en)
Other versions
EP0000893B1 (fr
Inventor
Gerhard Dr. Grögler
Holger Dr. Meyborg
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP0000893A1 publication Critical patent/EP0000893A1/fr
Application granted granted Critical
Publication of EP0000893B1 publication Critical patent/EP0000893B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/70—Other substituted melamines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
    • C08G18/8058—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38 with compounds of C08G18/3819

Definitions

  • the present invention relates to the polyisocyanates according to claim 1, the process for their preparation according to claim 3 and their use according to claim 5.
  • the polyisocyanates according to the invention which can be obtained by the process according to the invention correspond to the general formula of claim 1, where X and Y have the meaning given there.
  • X is preferably a radical having isocyanate groups, as is the case by removing the in the sense of the isocyanate addition reaction, a more reactive isocyanate group can be obtained from an aromatic diisocyanate with isocyanate groups of different reactivity.
  • X particularly preferably represents a 3-isocyanato-4-methylphenyl or a 4- (o-isocyanato-benzyl) phenyl radical.
  • Y preferably represents a radical of the formula -NH-CO-NH-X, where X preferably has the last-mentioned preferred or in particular the last-mentioned particularly preferred meaning.
  • the compounds according to the invention are prepared by reacting amino-containing s-triazine derivatives of the formula mentioned in claim 3 with diisocyanates of the formula X-NCO, where X corresponds to the definition mentioned in claim 1 or preferably the last definitions made, and wherein Y 'is the in Claim 3 has the meaning given and preferably represents an H 2 N group.
  • Diisocyanates X-NCO suitable for the process according to the invention are any organic diisocyanates which, in the sense of the isocyanate addition reaction, have isocyanate groups of different reactivity and are otherwise inert under the conditions of the process according to the invention.
  • Aromatic diisocyanates corresponding to this definition are preferably used in the process according to the invention.
  • the preferred aromatic diisocyanates include, in particular, those in the molecular weight range 174-400 which, in addition to a free, ie sterically unimpeded aromatically bound isocyanate group have a further aromatically bound isocyanate group which is sterically hindered by at least one substituent in the o-position.
  • substituents which can lead to steric hindrance of the isocyanate group, are in particular C 1 -C S -alkyl-, C 6 -C 10 -aryl-, C 1 -C 8 -alkoxy-, C 1 -C 8 -thioethers- , C 1 -C 8 alkoxycarbonyl, chlorine, bromine or cyano groups.
  • aromatic diisocyanates in the process according to the invention in which aromatic diisocyanates with isocyanate groups of the same reactivity as, for example, 4,4'-diisocyanatodiphenyl-. methane or 2,6-diisocyanatotoluene are present if the proportion of such diisocyanates with isocyanate groups of the same reactivity does not exceed an upper limit of 50, preferably 40,% by weight, based on the total mixture.
  • the particularly preferred diisocyanates suitable for the process according to the invention include, for example, 2,4-diisocyanatotoluene, optionally in a mixture with up to 50% by weight, based on the total mixture of 2,6-diisocyanatotoluene, 2,4'-diisocyanatotoluene, optionally in a mixture with up to 50 wt .-% based on the total mixture of 4,4'-diisocyanatodiphenylmethane.
  • 2,4'-Diisocyanatodiphenylpropan 2,4'-Diisocyanatodiphenylsulfid, 2,4'-Diisocyanatodiphenyläther, 2,4'-Diisocyanatodiphenylsulfon, 2,4'- D iisocyanatodiphenylsulfodioxid, 3-methyl-4,4'-diisocyanatodiphenylmethane , 3-ethyl-4,4'-diisocyanatodiphenylmethane, 3-isopropyl-4,4'-diisocyanatodiphenylmethane, 3,5-dimethyl-4,4'-diisocyanatodiphenylmethane, 3,5-diethyl-4,4'-diisocyanatodiphenylmethane or 3,5-diisopropyl-4,4'-diisocyanatodip
  • S-triazine derivatives which have amino groups and are suitable for the process according to the invention and correspond to the above are Melamine, 6-chloro-2,4-diamino-s-triazine, benzoguanamine, acetoguanamine or caprinoguanamine. ! elamin is particularly preferred.
  • the reaction partners are used in such quantitative ratios that at least 2 isocyanate groups of the diisocyanate are present in the reaction mixture for each amino group of the s-triazine derivative, this quantity indication in the case of the use of the above-mentioned mixtures exclusively relating to the diisocyanate with NCO- Groups of different reactivity relates.
  • the s-triazine derivative is stirred in an excess of the initially introduced diisocyanate, and the solution or dispersion formed in the process is then heated to 60-180 ° C., preferably 100-160 ° C., optionally with the addition of known urethanization catalysts, such as zinc acetylacetonate, until the Isocyanate content of the reaction mixture shows the calculated waste.
  • known urethanization catalysts such as zinc acetylacetonate
  • the process products according to the invention can be obtained in pure form by filtration and washing, for example with an inert solvent such as acetone, chloroform or petroleum ether.
  • an inert solvent such as acetone, chloroform or petroleum ether.
  • the way of working described represents the is by far the preferred procedure, since when using an NCO / NH 2 equivalent ratio of ⁇ 2: 1, for example in the presence of inert solvents, generally no process products according to the invention but rather highly crosslinked reaction products are obtained. (The use of non-polar diluents such as mineral spirits or aromatic hydrocarbons which do not dissolve the process products would be possible, however, is generally superfluous).
  • the excess of the diisocyanate component is chosen so that 5-8 NCO equivalents, based on all diisocyanates of the diisocyanate component, are present in the reaction mixture for each H2N equivalent of the s-triazine polyamine, preferably 3-10.
  • the new compounds according to the invention are sparingly to insoluble in practically all common organic solvents, with the exception, for example, of highly polar solvents such as dimethylformamide or dimethyl sulfoxide.
  • the new compounds have a high melting point and decompose in the melt. They are suitable as an isocyanate component in powder coatings based on polyurethane and in particular as active fillers in the production of polyurethane plastics by the isocyanate polyaddition process known per se.
  • the compounds according to the invention are preferably dispersed in the isocyanate component used for the production of the polyurethane plastic.
  • Such dispersions of the process products according to the invention in organic polyisocyanates are then processed in a manner known per se using polyhydroxy polyethers and / or polyhydroxy polyesters, if appropriate in combination with chain extenders known per se, to give polyurethane plastics, in particular polyurethane elastomers, which then, thanks to the use of the compounds according to the invention, are improved by improved heat Stability, improved tear propagation resistance, improved elongation at break and improved tensile strength.
  • the last-mentioned dispersions are reacted with the polyether polyols or polyester polyols known per se in polyurethane chemistry to form prepolymers containing NCO groups, in such proportions that the unmodified diisocyanate in the resulting NCO prepolymers originating isocyanate groups as well as the isocyanate groups of the compounds according to the invention are present.
  • NCO prepolymers are then reacted with chain extenders, for example a diamine of the type exemplified in Example 10, to give the high molecular weight polyurethane polyurea, the amount of chain extender either being chosen such that for all isocyanate groups of the prepolymer including the isocyanate groups of the dispersed compounds according to the invention
  • chain extenders for example a diamine of the type exemplified in Example 10
  • chain extenders for example a diamine of the type exemplified in Example 10
  • the amount of chain extender either being chosen such that for all isocyanate groups of the prepolymer including the isocyanate groups of the dispersed compounds according to the invention
  • an isocyanate-reactive group of the chain extender is available or so that, in a first approximation Isocyanate-reactive groups of the chain extender are only available for the isocyanate groups of the prepolymer, which do not originate from the compounds according to the invention, a subsequent chemical
  • the triisocyanate reacts only slowly in the cold (RT) with aliphatic amines such as di-n-butylamine.
  • the NCO value can therefore only be determined at RT after a longer reaction time:
  • the solids content of the prepolymer is 8.4% and its viscosity is 4500 cP (25 ° C).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP78100606A 1977-08-19 1978-08-07 Procédé pour la préparation de polyisocyanates et leur utilisation Expired EP0000893B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772737402 DE2737402A1 (de) 1977-08-19 1977-08-19 Polyisocyanate, ein verfahren zu ihrer herstellung und ihre verwendung
DE2737402 1977-08-19

Publications (2)

Publication Number Publication Date
EP0000893A1 true EP0000893A1 (fr) 1979-03-07
EP0000893B1 EP0000893B1 (fr) 1980-09-17

Family

ID=6016781

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100606A Expired EP0000893B1 (fr) 1977-08-19 1978-08-07 Procédé pour la préparation de polyisocyanates et leur utilisation

Country Status (4)

Country Link
US (2) US4255570A (fr)
EP (1) EP0000893B1 (fr)
DE (2) DE2737402A1 (fr)
IT (1) IT1106886B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0053327A1 (fr) * 1980-12-02 1982-06-09 Bayer Ag Procédé de préparation de composés contenant des unités de s-triazine et des groupes isocyanate ou des groupes réagissant sur un isocyanate et leur utilisation comme charge réactive lors de la préparation de polyuréthanes
EP0056153A3 (en) * 1981-01-08 1982-10-27 Bayer Ag Process for producing compounds having s-triazine units and epoxy groups, and their uses as incorporable filling materials in the production of polyurethane plastic materials
EP0419965A3 (en) * 1989-09-27 1992-01-15 Bayer Ag Polyisocyanates for lacquers, a process for their preparation and their use

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931487A (en) * 1988-03-04 1990-06-05 Dow Chemical Company Chain extenders for polyurethanes
DE4022663C2 (de) * 1990-07-17 1999-11-04 Bayer Ag Verfahren zur Herstellung von Polyurethanformkörpern
TW242644B (fr) * 1992-10-30 1995-03-11 Ppg Industries Inc
US6235858B1 (en) 1992-10-30 2001-05-22 Ppg Industries Ohio, Inc. Aminoplast curable film-forming compositions providing films having resistance to acid etching
JP2672031B2 (ja) 1992-10-30 1997-11-05 ピーピージー インダストリーズ，インコーポレイテッド 耐酸エッチング性を有する塗膜を与えるアミノプラスト硬化可能な塗膜形成組成物
US6103816A (en) * 1992-10-30 2000-08-15 Ppg Industries Ohio, Inc. Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1943635A1 (de) * 1969-08-28 1971-03-11 Bayer Ag s-Triazinyl-isocyanate
FR2243936A1 (en) * 1973-09-17 1975-04-11 Aries Robert N-s-triazinyl urea herbicides - prepd from 2-amino triazine and alkyl isocyanate or carbamoyl halide
DE2436740A1 (de) * 1974-07-30 1976-02-12 Bayer Ag Verfahren zur herstellung von polyharnstoffen
DE2032547B2 (de) * 1970-07-01 1976-06-16 Bayer Ag, 5090 Leverkusen Herstellung von harnstoffgruppen aufweisenden polyisocyanaten und deren verwendung
DE2507682A1 (de) * 1975-02-22 1976-09-02 Bayer Ag Isocyanate
DE2653408A1 (de) * 1975-11-26 1977-06-08 Shell Int Research Triazin-harnstoff-verbindungen, verfahren zu ihrer herstellung und diese verbindungen als verdickungsmittel enthaltende schmierfette

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2838511A (en) * 1955-10-31 1958-06-10 Du Pont Preparation of triaryl isocyanates
BE617033A (fr) 1961-04-28
US3210339A (en) * 1962-08-01 1965-10-05 Dentsche Gold Und Silber Schei Diamino-s-triazine derivatives

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1943635A1 (de) * 1969-08-28 1971-03-11 Bayer Ag s-Triazinyl-isocyanate
DE2032547B2 (de) * 1970-07-01 1976-06-16 Bayer Ag, 5090 Leverkusen Herstellung von harnstoffgruppen aufweisenden polyisocyanaten und deren verwendung
FR2243936A1 (en) * 1973-09-17 1975-04-11 Aries Robert N-s-triazinyl urea herbicides - prepd from 2-amino triazine and alkyl isocyanate or carbamoyl halide
DE2436740A1 (de) * 1974-07-30 1976-02-12 Bayer Ag Verfahren zur herstellung von polyharnstoffen
DE2507682A1 (de) * 1975-02-22 1976-09-02 Bayer Ag Isocyanate
DE2653408A1 (de) * 1975-11-26 1977-06-08 Shell Int Research Triazin-harnstoff-verbindungen, verfahren zu ihrer herstellung und diese verbindungen als verdickungsmittel enthaltende schmierfette

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0053327A1 (fr) * 1980-12-02 1982-06-09 Bayer Ag Procédé de préparation de composés contenant des unités de s-triazine et des groupes isocyanate ou des groupes réagissant sur un isocyanate et leur utilisation comme charge réactive lors de la préparation de polyuréthanes
EP0056153A3 (en) * 1981-01-08 1982-10-27 Bayer Ag Process for producing compounds having s-triazine units and epoxy groups, and their uses as incorporable filling materials in the production of polyurethane plastic materials
EP0419965A3 (en) * 1989-09-27 1992-01-15 Bayer Ag Polyisocyanates for lacquers, a process for their preparation and their use

Also Published As

Publication number Publication date
US4255570A (en) 1981-03-10
DE2737402A1 (de) 1979-02-22
DE2860170D1 (en) 1980-12-18
IT1106886B (it) 1985-11-18
US4348512A (en) 1982-09-07
EP0000893B1 (fr) 1980-09-17
IT7850756A0 (it) 1978-08-17

Similar Documents

Publication Publication Date Title
EP0417603B1 (fr) Procédé de préparation de polyisocyanates contenant des groupes urétidinedione
DE2560419C2 (de) Formteile aus Polyurethan
DE2625399C3 (fr)
EP0220641B1 (fr) p,p'-Méthylène-bis-anilines substituées
DE10111337A1 (de) Verfahren zur Herstellung von MDI, insbesondere von 2.4'-MDI
DE4238046A1 (de) Neue Bis-(4-substituierte-2,6-diisopropyl-phenyl)-carbodiimide, ein Verfahren zu ihrer Herstellung und ihre Verwendung sowie die zu ihrer Herstellung verwendbaren 4-substituierten 2,6-Diisopropyl-phenylisocyanate
EP0000893B1 (fr) Procédé pour la préparation de polyisocyanates et leur utilisation
EP0062823B1 (fr) Procédé de production de polyisocyanates aromatiques porteurs de groupes urée et/ou de groupes biuret et leur utilisation comme composant isocyanate dans la fabrication de polyuréthannes
DE2318170A1 (de) Heterocyclische diisocyanate
DE2066059C2 (de) Verfahren zur Herstellung von Cyanformamidylisocyanaten
EP0148462B1 (fr) Procédé pour la préparation in situ de diisocyanates contenant des groupes urée dans des polyols, des dispersions ou des solutions selon ce procédé et leur utilisation
DE1695543A1 (de) Isocyanurat enthaltende Polyisocyanate und Verfahren zum Herstellen derselben
EP0071839B1 (fr) Diisocyanates aromatiques contenant des groupes sulphonamido N,N-disubstitués, leur méthode de préparation et leur emploi pour la préparation de polyuréthanes
DE19504530A1 (de) Blockierte Polyisocyanate, Verfahren zu ihrer Herstellung und daraus hergestellte Lacke und Beschichtungssysteme
EP0013923A1 (fr) Suspensions d'isocyanates à groupes urée dans des prépolymères d'isocyanates, procédé pour leur préparation et leur utilisation dans la préparation de matières plastiques de polyuréthane à haut poids moléculaire
DE3781758T2 (de) Harnstoffmodifizierte isocyanate.
EP0777647B1 (fr) 4,4'-methylen-bis-(3-chloro-2,6-dialkylphenylisocyanates) et systemes de polyurethanne les contenant
EP0084802A1 (fr) Diisocyanates et leur méthode de préparation
DE2141698A1 (de) Sterisch gehinderte sekundäre Diamine als Härter für Polyurethane
DE2912074C2 (fr)
AT390788B (de) Neue diblockierte triisocyanatverbindungen, ein verfahren zu ihrer herstellung und ihre verwendung
DE3437632A1 (de) Verfahren zur herstellung hoehermolekularer aminoverbindungen mit vermindertem monomeramingehalt, sowie deren verwendung
EP0053327B1 (fr) Procédé de préparation de composés contenant des unités de s-triazine et des groupes isocyanate ou des groupes réagissant sur un isocyanate et leur utilisation comme charge réactive lors de la préparation de polyuréthanes
EP0307757A2 (fr) Procédé de fabrication de polyuréthanes à caractères cristaux-liquides et diisocyanates appropriés pour la mise en oeuvre de ce procédé
DE19545757A1 (de) 4,4'-(Phenylendiisopropyl)-bis(2,6-dialkylphenylisocyanate)

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
AK Designated contracting states

Designated state(s): BE DE FR GB

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 2860170

Country of ref document: DE

Date of ref document: 19801218

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19910724

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19910729

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910805

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910828

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19920807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19920831

BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19920831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19920807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT