EP0254618B1 - Vorfabrizierter Inhibitor auf der Basis von Kautschukgummi für Komposittreibstoff mit Polyurethanbinder - Google Patents

Vorfabrizierter Inhibitor auf der Basis von Kautschukgummi für Komposittreibstoff mit Polyurethanbinder Download PDF

Info

Publication number
EP0254618B1
EP0254618B1 EP87401538A EP87401538A EP0254618B1 EP 0254618 B1 EP0254618 B1 EP 0254618B1 EP 87401538 A EP87401538 A EP 87401538A EP 87401538 A EP87401538 A EP 87401538A EP 0254618 B1 EP0254618 B1 EP 0254618B1
Authority
EP
European Patent Office
Prior art keywords
gum rubber
inhibitor
peroxide
butyl
rubber
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.)
Expired - Lifetime
Application number
EP87401538A
Other languages
English (en)
French (fr)
Other versions
EP0254618A1 (de
Inventor
Jacques Maucourt
Claude Combette
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.)
Safran Ceramics SA
Original Assignee
Societe Nationale des Poudres et Explosifs
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 Societe Nationale des Poudres et Explosifs filed Critical Societe Nationale des Poudres et Explosifs
Publication of EP0254618A1 publication Critical patent/EP0254618A1/de
Application granted granted Critical
Publication of EP0254618B1 publication Critical patent/EP0254618B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones

Definitions

  • the invention relates to a preformed inhibitor for composite propellant.
  • the invention relates more particularly to a preformed inhibitor having as matrix a rubber rubber to which a composite propellant with a polyurethane binder is directly adhered.
  • inhibitor any part which is placed on at least part of a propellant block to limit the combustion surface thereof.
  • the inhibitors of the present invention also play a role in protecting the structure of the craft.
  • inhibitor also designates parts of the inhibition of a block, such as for example the bottoms or the end faces, the other parts of the inhibition being able to be carried out with other inhibitory compositions.
  • the methods of the second group make it possible to manufacture free blocks or glued molded blocks.
  • the inhibitor is preformed directly in the structure of the self-propelled vehicle, the propellant then being poured into this structure.
  • the inhibitors of the present invention are used for carrying out the methods of the second group.
  • Inhibitors are already known having as matrix rubber rubbers. However, these inhibitors are used with a composite propellant based on polybutadiene with terminal carboxyl functions (PBCT), and do not adhere to the composite propellant based on polybutadiene with terminal hydroxyl functions (PBHT).
  • PBCT polybutadiene with terminal carboxyl functions
  • PBHT terminal hydroxyl functions
  • an inhibitor based on a gum rubber is known, the ethylene-propylene-diene-monomer elastomer, more commonly called EPDM for a composite propellant based on PBHT.
  • Patent FR-A-2 554 114 describes the use as an inhibitor of an EPDM gum rubber vulcanized with peroxides.
  • This rubber comprises fillers, in particular carbonizable organic fibers to ensure good resistance to the effect of erosion by the flow of hot gases.
  • Patent FR-A-2 495 133 describes the use of a gasifiable organic filler, in particular of oxamide, in an inhibitor based on rubber EPDM gum; the role of this oxygenated charge being to reduce the formation of slag during the degradation of the inhibitor.
  • adhesion of the inhibitor to the propellant is obtained by the presence of an adhesion layer also called "primary" deposited between the inhibitor and the propellant.
  • this adhesion layer is a major drawback.
  • the application of this adhesion layer to the inhibitor increases the duration and the manufacturing costs.
  • it can generate defects in the load obtained, for example, by trapping air bubbles. To avoid any defect and to obtain a uniform adhesion on all the block this application requires great care.
  • the object of the present invention is in particular to remedy these drawbacks by proposing a preformed inhibitor based on gum rubber to which a propellant with a polyurethane binder is directly adhered.
  • the invention provides a preformed inhibitor for a composite propellant block based on a polyurethane binder obtained from a polyol and a polyisocyanate.
  • This inhibitor comprises a rubber-based matrix, fillers, a rubber vulcanization system, and is characterized in that the rubber rubber is chosen from the group comprising ethylene-propylene-diene-monomer copolymers (called EPDM rubbers). and isoprene-isobutylene copolymers (called butyl rubbers), the vulcanization system of EPDM rubber being a system based on peroxide compounds, that of butyl rubber being a sulfur-based system comprising at least one vulcanization accelerator and devoid of vulcanization activator.
  • EPDM rubbers ethylene-propylene-diene-monomer copolymers
  • butyl rubbers isoprene-isobutylene copolymers
  • the vulcanization system of EPDM rubber being a system based on peroxide compounds
  • the composite propellants adhere directly to the inhibitors according to the invention, without the use of an adhesion or "primary" layer.
  • the inhibitor contains a bonding dopant.
  • the bonding dopant is oxamide, preferably present at a concentration of between 50 and 200 parts by weight per 100 parts of gum rubber.
  • the doping agent is diethylene glycol (DEG), preferably present at a concentration of between 1 and 5 parts by weight per 100 parts of gum rubber.
  • DEG diethylene glycol
  • butyl rubbers suitable for the invention mention may be made of the various known butyl rubbers, the percentage of unsaturation being indifferent, as well as halogenated butyl rubbers, such as chlorobutyl.
  • the sulfur vulcanization systems suitable for the invention are those containing sulfur, and vulcanization accelerators. Sulfur can be supplied by vulcanization accelerators.
  • a vulcanization accelerator suitable for the invention mention may be made of zinc salts and dithiocarbamic acid such as zinc dibutyldithiocarbamate, zinc diethyl dithiocarbamate or zinc ethylphenyl dithiocarbamate , or thiurams such as, mercaptobenzothiazole (MTB), benzothiazyl disulfide (MBTS), or guanidines or amines, or the like.
  • dithiocarbamic acid such as zinc dibutyldithiocarbamate, zinc diethyl dithiocarbamate or zinc ethylphenyl dithiocarbamate , or thiurams such as, mercaptobenzothiazole (MTB), benzothiazyl disulfide (MBTS), or guanidines or amines, or the like.
  • MTB mercaptobenzothiazole
  • MBTS benzothiazyl disulfide
  • the sulfur vulcanization systems suitable for the invention do not contain a vulcanization activator such as, for example, stearic acid, zinc oxide. These products have a detrimental effect on the propellant adhesion properties.
  • Vulcanization systems suitable for EPDM rubbers include one or more peroxide compounds such as, for example, dicumyl peroxide; 2,5 dimethyl 2,5 Bis peroxide; 2,5 dimethyl 2,5 dimethyl hexane peroxide; 2,5 dimethyl 2,5 bis (t-butyl) hexyne 3 peroxide; 1,3 bis (t-butylisopropyl) benzene peroxide; 1-1 bis (t-butyl) 3.3.5 trimethylcyclohexane peroxide and t-butylcumyl peroxide or the like.
  • peroxide compounds such as, for example, dicumyl peroxide; 2,5 dimethyl 2,5 Bis peroxide; 2,5 dimethyl 2,5 dimethyl hexane peroxide; 2,5 dimethyl 2,5 bis (t-butyl) hexyne 3 peroxide; 1,3 bis (t-butylisopropyl) benzene peroxide; 1-1 bis (t-butyl
  • the concentration of peroxide or sulfur vulcanization system is that indicated and recommended by the rubber manufacturers for their use.
  • fillers can be added to the rubber such as fillers which reinforce the mechanical properties.
  • At least part of these charges is an electrically conductive charge, such as, for example, carbon black.
  • an electrically conductive charge such as, for example, carbon black.
  • concentration by weight of this conductive filler is between 5 and 50 parts per 100 parts of gum rubber.
  • Polyurethane binder propellants are composite propellants comprising an inert binder, an oxidant, a fuel, ballistic additives, catalysts.
  • these compositions can contain an explosive such as tetramethylenetetranitramine, trimethylenetrinitramine, for example.
  • Propellants suitable for the invention have as an inert binder, a polyurethane obtained by reaction of a polyol with a polyisocyanate.
  • polybutadienes containing terminal hydroxyl functions PBHT
  • R45M and R45HT polyalkylene ether glycols
  • polypropylene glycols or polyethylene glycols polyalkylene ester glycols, or the like.
  • polyisocyanates suitable for the invention aromatic, aliphatic, arylaliphatic or alkylaromatic polyisocyanates can be used.
  • Difunctional isocyanates are preferred, such as, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, dimeryl diisocyanate or the like.
  • the inhibitors of the invention are prepared according to conventional methods of using rubbers.
  • the compositions are prepared in a mixer by first plasticizing the rubber compound at ambient temperature, then by introducing fillers such as carbon black, oxamide. After homogenization of the assembly, the various additives such as adhesion doping agents and antioxidant agents are always introduced at ambient temperature. Finally, the vulcanizing agents are mixed with the composition.
  • composition is calendered in the form of a sheet with an average thickness of 5 millimeters.
  • These sheets are then cut to the desired dimensions and placed in a mold where they are shaped and vulcanized under pressure, at a temperature of the order of 160 ° C. and a duration of 30 to 60 minutes.
  • the number of sheets deposited depends on the thickness of the part to be produced.
  • vulcanization temperature and duration are given for information only and are determined, in a manner well known to those skilled in the art, by measuring a mechanical property to determine the optimum degree of vulcanization suitable for rubber application. For example, shear strength can be monitored using a cone rheometer.
  • the part thus formed is placed either in a mold when it is desired to make free blocks, or in the structure of a machine when the propellant charge is of the "molded-glued" type.
  • the propellant is then poured into the mold or structure, and crosslinked by heat treatment according to a process well known to those skilled in the art.
  • the surface of the rubber part is sanded, dusted and dried before the propellant is poured.
  • the propellant used in Examples 1 to 6 has the following composition:
  • the inhibitor is based on butyl gum rubber and has the following composition expressed in parts by weight per 100 parts of gum rubber (phr).
  • Example 1 A composition identical to that of Example 1 is produced, but by replacing the isoprene-isobutylene copolymer (Butyl 065) with an isoprene-isobutylene copolymer also marketed by ESSO under the name Butyl 365 containing 2.25 moles of isoprene per 100 moles of isobutylene.
  • the inhibitor has the composition of that of Example 2 in which a bonding dopant, diethylene glycol, has been added in a proportion of 2 phr.
  • composition of the inhibitor is as follows:
  • composition of the inhibitor is as follows:
  • a test is carried out with the same composition as for Example 5 but without adding oxamide, and replacing the dicumyl peroxide with 2,5-dimethyl 2,5 Bis peroxide.
  • Examples 5 and 6 show the effect of oxamide on the characteristics of the bonding.
  • Example 7 was carried out with a propellant of the following composition:
  • composition of the inhibitor tested is as follows:
  • Examples 8 and 9 are comparative examples not falling within the scope of the present invention.
  • composition of the inhibitor which is based on butyl gum rubber, differs from that of Example 1 in that a vulcanization activator is added in the following weight proportions:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (9)

  1. Vorgeformter Inhibitor für Propergole mit Polyurethanbindemittel, der enthält:
    - Eine Matrix auf der Basis eines Elastomerkautschuks,
    - mindestens einen Füllstoff,
    - ein System zur Vulkanisation des Elastomerkautschuks,
    dadurch gekennzeichnet, daß
    a) der Elastomerkautschuk unter Copolymeren aus Ethylen-Propylen-Dien-Monomeren (EPDM) und Copolymeren aus Isopren-Isobuten (Butyl) ausgewählt ist,
    b) das System zur Vulkanisation des Elastomerkautschuks
    - ein System auf der Basis von Peroxidverbindungen ist, wenn der Elastomerkautschuk ein EPDM-Copolymer ist,
    - ein System auf der Basis von Schwefel ist, das mindestens einen Vulkanisationsbeschleuniger enthält und frei von Vulkanisationsaktivatoren ist, wenn der Elastomerkautschuk ein Butyl-Copolymer ist,
    und
    c) der Inhibitor ferner enthält:
    - Oxamid, wenn der Elastomerkautschuk ein EPDM-Copolymer ist,
    - Diethylenglycol, wenn der Elastomerkautschuk ein Butyl-Copolymer ist.
  2. Inhibitor nach Anspruch 1, dadurch gekennzeichnet, daß die Konzentration an Oxamid 50 bis 200 Gewichtsteile auf 100 Gewichtsteile des EPDM-Elastomerkautschuks beträgt.
  3. Inhibitor nach Anspruch 1, dadurch gekennzeichnet, daß die Konzentration an Diethylenglycol 1 bis 5 Gewichtsteile auf 100 Gewichtsteile des Butyl-Elastomerkautschuks beträgt.
  4. Inhibitor nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß mindestens ein Füllstoff ein elektrisch leitender Füllstoff ist.
  5. Inhibitor nach Anspruch 4, dadurch gekennzeichnet, daß die Konzentration des elektrisch leitenden Füllstoffs 5 bis 50 Gewichtsteile auf 100 Gewichtsteile des Elastomerkautschuks beträgt.
  6. Inhibitor nach einem der Ansprüche 1, 2, 4 oder 5, dadurch gekennzeichnet, daß das System zur Vulkanisation des EPDM-Kautschuks mindestens eine Peroxidverbindung enthält, die unter Dicumylperoxid, 2,5-Dimethyl-2,5-dimethylhexanperoxid, 2,5-Dimethyl-2,5-bis(t-butyl)-hexinperoxid, 1,3-Bis(t-butylisopropyl)-benzolperoxid, t-Butylcumylperoxid und 1,1-Bis(t-butyl)-3,3,5-trimethylcyclohexanperoxid ausgewählt ist.
  7. Inhibitor nach einem der Ansprüche 1, 3, 4 und 5, dadurch gekennzeichnet, daß das System zur Vulkanisation des Butyl-Elastomerkautschuks Schwefel und einen Vulkanisationsbeschleuniger enthält.
  8. Inhibitor nach einem der vorhergehenden Ansprüche, auf dem direkt, ohne Einschaltung einer Zwischenschicht eines Klebemittels, ein Propergol mit Polyurethanbindemittel haftet.
  9. Inhibitor, auf dem direkt ein Propergol mit Polyurethanbindemittel haftet, nach Anspruch 8, wobei das Polyurethanbindemittel durch Vernetzung eines Polybutadiens mit endständigen Hydroxygruppen (PBHT) mit einem Polyisocyanat erhalten ist.
EP87401538A 1986-07-21 1987-07-02 Vorfabrizierter Inhibitor auf der Basis von Kautschukgummi für Komposittreibstoff mit Polyurethanbinder Expired - Lifetime EP0254618B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8610520A FR2601669B1 (fr) 1986-07-21 1986-07-21 Inhibiteur preforme a base de caoutchouc gomme pour propergol composite a liant polyurethanne
FR8610520 1986-07-21

Publications (2)

Publication Number Publication Date
EP0254618A1 EP0254618A1 (de) 1988-01-27
EP0254618B1 true EP0254618B1 (de) 1991-04-17

Family

ID=9337573

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87401538A Expired - Lifetime EP0254618B1 (de) 1986-07-21 1987-07-02 Vorfabrizierter Inhibitor auf der Basis von Kautschukgummi für Komposittreibstoff mit Polyurethanbinder

Country Status (4)

Country Link
EP (1) EP0254618B1 (de)
DE (1) DE3769391D1 (de)
FR (1) FR2601669B1 (de)
NO (1) NO164412C (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2365420B (en) * 1988-05-11 2002-05-29 Royal Ordnance Plc Explosive compositions
US5069133A (en) * 1990-08-31 1991-12-03 Olin Corporation Elastomer-containing casings for propellants
GB2310427B (en) * 1996-02-22 2000-06-28 John Douglas Michael Wraige Energetic compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932242A (en) * 1957-11-21 1976-01-13 Bartley Charles E Solid propellant with butyl rubber binder
US3399087A (en) * 1962-06-08 1968-08-27 Aerojet General Co Castable propellant compositions containing isoolefin-diolefin copolymers
US3973397A (en) * 1973-08-14 1976-08-10 Imperial Metal Industries (Kynoch) Limited Rocket motor with ablative insulating casing liner
FR2332967A1 (fr) * 1975-11-28 1977-06-24 Poudres & Explosifs Ste Nale Materiau de liaison comportant un catalyseur de polymerisation d'un propergol a liant polybutadiene
FR2495133A1 (fr) * 1980-11-28 1982-06-04 Poudres & Explosifs Ste Nale Revetement inhibiteur pour propergols solides a combustion frontale comportant des charges organiques gazeifiables, bloc de propergol solide revetu dudit inhibiteur et procede d'obtention
FR2554114B3 (fr) * 1983-10-28 1985-12-27 Hercules Inc Materiaux d'isolation elastomeres exempts d'amiante pour les parois internes des moteurs-fusees

Also Published As

Publication number Publication date
NO872985L (no) 1988-01-22
NO164412B (no) 1990-06-25
NO164412C (no) 1990-10-03
DE3769391D1 (de) 1991-05-23
EP0254618A1 (de) 1988-01-27
FR2601669A1 (fr) 1988-01-22
FR2601669B1 (fr) 1991-08-30
NO872985D0 (no) 1987-07-17

Similar Documents

Publication Publication Date Title
RU2081887C1 (ru) Динамически частично вулканизованная пероксидами термопластичная эластомерная композиция и способ ее получения
RU2103287C1 (ru) Динамически частично (полностью) сшитая перекисью термопластичная эластомерная композиция (варианты)
WO1994000289A1 (en) Puncture sealant formulation
CN1059536A (zh) 含聚丁烯-1的动态的部分交联热塑性弹性体
JPS62177042A (ja) ゴムブレンドの作成
US5053450A (en) Elastomer compositions
FR3084669A1 (fr) Composition auto-cicatrisante
JPH0350252A (ja) ポリオレフィン系熱可塑性エラストマー組成物の製造方法
US4575522A (en) Rubber composition for geothermal application
FR2894252A1 (fr) Composition reticulee comprenant un copolymere coeur ecorce, son procede d'obtention et ses utilisations
EP1050548A1 (de) Thermoplastische Zusammensetzung und Verfahren zur Herstellung derselben
FR2749018A1 (fr) Elastomere reticule a transformation thermoplastique, son procede de fabrication et ses utilisations
EP0617077B1 (de) Zusammensetzung bestehend aus einem ungesättigten Elastomer und einem Weichmacher aus der Familie der Polyphenylmethanen
EP0254618A1 (de) Vorfabrizierter Inhibitor auf der Basis von Kautschukgummi für Komposittreibstoff mit Polyurethanbinder
CN1234793C (zh) 固体型压敏粘合剂组合物和使用该组合物的压敏粘合剂片材
EP0659860B1 (de) Klebende elastomere Matrix und deren Anwendung
EP1053285A1 (de) Zinkoxid dispersion
CA2224500A1 (fr) Compositions a base de polymere thermoplastique fluore et d'elastomere nitrile
CN113999519A (zh) 一种聚氨酯改性天然橡胶及其制备方法
CN114702760A (zh) 一种汽车雨刮胶条及其制备方法
EP2969557B1 (de) Kunststoffelastomerverbund, schwingungsdämpfendes teil damit und verfahren zur herstellung des verbundstoffes
EP0384822B1 (de) Thermoplastisches Elastomer aus Äthylen-alpha-Olefin-Copolymer und Polynorbornen
JPH0240691B2 (de)
EP4617312A1 (de) Thermoplastische elastomerzusammensetzung und artikel damit, z.b. ein rohr
FR2554114A1 (fr) Materiaux d'isolation elastomeres exempts d'amiante pour les parois internes des moteurs-fusees

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE GB IT LI NL

17P Request for examination filed

Effective date: 19880222

17Q First examination report despatched

Effective date: 19890728

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE GB IT LI NL

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3769391

Country of ref document: DE

Date of ref document: 19910523

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

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: SNPE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: SNPE

Free format text: SOCIETE NATIONALE DES POUDRES ET EXPLOSIFS#12, QUAI HENRI IV#PARIS 4E (FR) -TRANSFER TO- SNPE#12, QUAI HENRI IV#75181 PARIS CEDEX 04 (FR)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: SNPE MATERIAUX ENERGETIQUES

Free format text: SNPE#12, QUAI HENRI IV#75181 PARIS CEDEX 04 (FR) -TRANSFER TO- SNPE MATERIAUX ENERGETIQUES#12, QUAI HENRI IV#75004 PARIS (FR)

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

NLS Nl: assignments of ep-patents

Owner name: SNPE MATERIAUX ENERGETIQUES S.A.

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

Ref country code: NL

Payment date: 20050728

Year of fee payment: 19

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

Ref country code: CH

Payment date: 20050922

Year of fee payment: 19

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

Ref country code: DE

Payment date: 20050927

Year of fee payment: 19

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

Ref country code: GB

Payment date: 20060628

Year of fee payment: 20

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

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

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

Ref country code: IT

Payment date: 20060731

Year of fee payment: 20

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070201

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070201

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070201

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20070701