WO2000022034A1 - Utilisation d'hydroxycarbonate, d'hydroxyoxycarbonate ou d'oxycarbonate d'aluminium comme charge dans une composition de caoutchouc - Google Patents
Utilisation d'hydroxycarbonate, d'hydroxyoxycarbonate ou d'oxycarbonate d'aluminium comme charge dans une composition de caoutchouc Download PDFInfo
- Publication number
- WO2000022034A1 WO2000022034A1 PCT/FR1999/002483 FR9902483W WO0022034A1 WO 2000022034 A1 WO2000022034 A1 WO 2000022034A1 FR 9902483 W FR9902483 W FR 9902483W WO 0022034 A1 WO0022034 A1 WO 0022034A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydroxycarbonate
- compound
- amorphous
- use according
- composition according
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Definitions
- the present invention relates to the use as a filler in rubber, hydroxycarbonate, hydroxyoxycarbonate or amorphous aluminum oxycarbonate compositions.
- the object of the invention is to provide a filler for the rubber compositions providing them with a very satisfactory compromise in properties, namely preferably:
- the subject of the present invention is the use as filler, in a rubber composition, of at least one compound (A) consisting of an amorphous aluminum hydroxycarbonate or an amorphous aluminum hydroxyoxycarbonate or an oxycarbonate d amorphous aluminum.
- said hydroxycarbonate, hydroxyoxycarbonate or oxycarbonate contains at least 0.01, in particular at least 0.04, mole of carbonate per mole of aluminum; it can contain at least 0.1 mole of carbonate per mole of aluminum. In general, its carbonate / aluminum molar ratio is at most 0.25, in particular at most 0.2.
- the carbonates present in hydroxycarbonate, hydroxyoxycarbonate or oxycarbonate, and which can be detected by infrared spectroscopy, are usually covalent.
- the compound (A) generally has a BET specific surface of between 40 and 150 m 2 / g, in particular between 45 and 95 m 2 / g; it can be between 50 and
- the BET surface is determined according to the BRUNAUER - EMMET method -
- This compound (A) preferably has a small proportion of reactive AI-OH surface functions.
- the compound (A) used is an amorphous aluminum hydroxycarbonate corresponding to the crude formula (I) as follows AI (OH) x (CO 3 ) y , zH 2 O (I) in which
- y can be at most equal to 0.2.
- the compound (A) preferably has the following property: it remains amorphous (its X-ray diffraction spectrum remains flat) after having been calcined (in air) for 2 hours at any temperature between 150 and 700 ° C or after having undergone a treatment consisting of rapid dehydration using a gas stream at 600 ° C, the contact time of the compound with this gas being 1 at 2 seconds.
- the compound (A) is generally formed of aggregates of elementary particles which are slightly or non-porous, for example substantially spherical, of size which can be between 15 and 25 nm.
- the compound (A) used is obtained from calcination (notably in air) at any temperature between 150 and 700 ° C, especially between 180 and 650 ° C, of a amorphous aluminum hydroxycarbonate (called starting amorphous aluminum hydroxycarbonate), in particular for 1 to 3 hours, for example for 2 hours.
- the starting amorphous aluminum hydroxycarbonate preferably has the following property: it remains amorphous after having undergone a treatment consisting of rapid dehydration using a gas stream at 600 ° C., the time contact of the compound with this gas being 1 to 2 seconds.
- the compound (A) used is derived from the rapid dehydration of an amorphous aluminum hydroxycarbonate (called starting amorphous aluminum hydroxycarbonate) using a stream of gas to a temperature between 500 and 700 ° C, in particular equal to 600 ° C, the contact time of this starting amorphous aluminum hydroxycarbonate with this gas being between a fraction of a second and 4 seconds, in particular between 1 and 2 seconds.
- the starting amorphous aluminum hydroxycarbonate preferably has the following property: it remains amorphous after having been calcined (in air) for 2 hours at any temperature between 150 and 700 ° C.
- the compound (A) used advantageously has a high dispersibility. This dispersibility is quantified using the measurement of the level of fines ( ⁇ f ), that is to say the proportion (by weight) of particles of size less than 0.3 ⁇ m, after deagglomeration at ultra- sounds, performed according to the test described below. In this test, the ability to disperse the compound is measured by a particle size measurement (by sedimentation), carried out on a suspension of the compound previously disaggregated by ultra-sonification.
- the deagglomeration (or dispersion) under ultrasound is implemented using a BRANSON OSI sonicator (450 W), equipped with a probe with a diameter of 12 mm.
- the particle size measurement is carried out using a SEDIGRAPH particle size analyzer (sedimentation in the gravity field + scanning by X-ray beam).
- This rate of fines ( ⁇ f ), or rate of particles of size less than 0.3 ⁇ m, is all the higher the higher the compound has a high dispersibility.
- the compound (A) used has a level of fines ( ⁇ f ) of at least 80%, in particular at least 90%, or even at least 95% .
- the starting amorphous aluminum hydroxycarbonate preferably contains at least 0.01, in particular at least 0.04, mole of carbonate per mole of aluminum; it can contain at least 0.1 mole of carbonate per mole of aluminum.
- its carbonate / aluminum molar ratio is at most 0.25, in particular at most 0.2.
- the carbonates present in this starting amorphous aluminum hydroxycarbonate, and which can be detected by infrared spectroscopy, are usually covalent.
- This starting amorphous aluminum hydroxycarbonate generally has a BET specific surface of between 40 and 150 m 2 / g, in particular between 45 and 95 m 2 / g; it can be between 50 and 75 m 2 / g. It is generally formed of aggregates of elementary particles which are not very porous or not, for example substantially spherical, of size which can be between 15 and 25 nm. It preferably has a small proportion of reactive AI-OH surface functions.
- the starting amorphous aluminum hydroxycarbonate preferably corresponds to the following crude formula (I)
- y can be at most equal to 0.2.
- the starting amorphous aluminum hydroxycarbonate in particular when it corresponds to the crude formula (I) mentioned above, can be prepared by the following method.
- a precipitation reaction is carried out by introducing a gaseous mixture, containing carbon dioxide (CO 2 ), into a suspension of alkali metal aluminate, in particular sodium aluminate, contained in a reaction vessel.
- this suspension of sodium aluminate can have a concentration, expressed as Al 2 O 3 , of between 10 and 150 g / l, in particular between 20 and 100 g / l; this concentration is for example between 40 and 70 g / l.
- pH can vary for example between 11 and 13.5, especially between 12 and 13.
- the initial reaction temperature that is to say the temperature of the aluminate suspension at the start of the introduction of the gas mixture, is usually set at not more than 15 ° C .; it is for example between 5 and 15 ° C.
- the reaction is generally carried out with stirring.
- the gaseous mixture which is introduced into the reaction vessel preferably contains, in addition to carbon dioxide, air.
- This gas mixture can then contain 20 to 50%, in particular 30 to 40%, by volume of carbon dioxide, and 50 to 80%, in particular 60 to 70%, by volume of air.
- the pressure in the reaction vessel is maintained throughout the reaction, preferably between 1, 3 and 3.5 bars, for example between 1, 7 and 2.5 bars.
- the final reaction temperature should generally be at most 25 ° C; it is for example between 10 and 25 ° C. It is preferable to maintain cooling in the reaction chamber during carbonation.
- the duration of the reaction (carbonation) can be between 10 and 60 minutes, for example between 10 and 30 minutes.
- the pH of the reaction medium at the end of the reaction is generally between 9.5 and 10.5.
- the precipitate obtained is usually filtered and, optionally, washed, for example with water. Even if any type of filtration means can be used, a filter press is advantageously used.
- the product obtained is, optionally after resuspension (or repulping), dried, preferably by atomization, in particular using an APV type atomizer, with an inlet temperature of for example between 400 and 500 C. C and an outlet temperature of, for example, between 100 and 135 ° C.
- the amorphous aluminum hydroxycarbonate obtained can undergo a final grinding operation, using any suitable known device, in order to "break" the agglomerates / aggregates.
- the rubber compositions in which is used, as a filler (in particular a reinforcing filler), the hydroxycarbonate or the amorphous aluminum oxycarbonate are generally based on one or more elastomers. More particularly, among the suitable elastomers, mention may be made of elastomers having a glass transition temperature of between -150 and +20 ° C.
- natural rubber polymers or copolymers derived from aliphatic or aromatic monomers, comprising at least one unsaturation (such as, in particular, ethylene, propylene, butadiene, isoprene, styrene), polybutylacrylate, or combinations thereof; mention may also be made of silicone elastomers and halogenated elastomers.
- the filler contained in said rubber compositions is formed at least in part, in particular in majority by weight, by compound (A) consisting of a hydroxycarbonate or hydroxyoxycarbonate or amorphous aluminum oxycarbonate.
- compound (A) consisting of a hydroxycarbonate or hydroxyoxycarbonate or amorphous aluminum oxycarbonate.
- Another compound such as precipitated silica, in particular very dispersible, can optionally be used as filler, but generally in the minority by weight relative to the compound (A).
- these compositions do not contain precipitated silica as filler and / or the filler is formed entirely of compound (A).
- the rubber compositions generally also comprise at least one coupling agent and / or at least one covering agent.
- the invention also relates to the finished articles based on the rubber compositions described above. Mention may be made, as finished articles, of the tire casings, in particular the sidewalls and the tire tread, the shoe soles, etc. The following examples illustrate the invention without, however, limiting its scope.
- a reactor having a volume of 100 liters is used, provided with a double jacket and equipped with a suitable stirring means for gas / liquid transfer, namely a Rushton turbine, and capable of working under pressure (the dissipated power required is about 4 kW / m 3 ).
- This suspension is cooled by means of the double jacket; its temperature is thus brought to 10 ° C. Then introduced into the reactor, under the Rushton turbine, a gas mixture having the following composition: Q (CO 2 ) 10 Nm 3 / h Q (air) 18.6 Nm 3 / h The pressure in the reactor is maintained at 2 bars.
- the reaction (carbonation) takes about 15 minutes.
- the final temperature of the reaction mixture is approximately 20 ° C.
- the end of the reaction can be monitored in particular using a pH probe.
- the final pH of the reaction mixture is 10.
- the precipitate formed is then filtered using a filter press and washed using deionized water, the amount of washing water used being of the order of 67 l / kg of solid (expressed as Al 2 O 3 ) dry.
- the product obtained after repulping in deionized water, is spray-dried, using an APV atomizer, with an inlet temperature of 450 ° C and an outlet temperature of 125 ° C.
- the product thus prepared is an amorphous aluminum hydroxycarbonate: its X-ray diffraction spectrum is flat. This product remains amorphous after being calcined for 2 hours in air at
- This product contains 0.1 mole of carbonate per mole of aluminum.
- Example 2 The aluminum hydroxycarbonate prepared in Example 1 is calcined in air for 2 hours at a temperature of 200 ° C.
- the compound then obtained, referenced HCA1 is amorphous.
- the carbonates present in this compound are covalent in nature.
- the HCA1 compound contains 0.09 mole of carbonate per mole of aluminum. Its particle size (Malvern) is 5.0 ⁇ m.
- the hydroxyoxycarbonate referenced HCA1 prepared in Example 2, undergoes a grinding operation using an air jet mill, in order to "break" the agglomerates / aggregates.
- the amorphous compound obtained is reference HCA2.
- the carbonates present in this compound are covalent in nature.
- the HCA2 compound contains 0.09 mole of carbonate per mole of aluminum. Its particle size (Malvern) is 1.25 ⁇ m.
- the aluminum hydroxycarbonate prepared in Example 1 is calcined in air for 2 hours at a temperature of 600 ° C.
- the amorphous compound obtained is referenced HCA3.
- the carbonates present in this compound are covalent in nature.
- the HCA3 compound contains 0.05 mole of carbonate per mole of aluminum. Its particle size (Malvern) is 0.95 ⁇ m.
- compositions are prepared by thermo-mechanically working the elastomers in an internal mixer (BANBURY type) with a volume equal to 1 liter, in two stages, with an average speed of the pallets of 80 revolutions / minute, until obtaining at a temperature of 160 ° C., these steps being followed by a finishing step carried out on an external mixer.
- BANBURY type internal mixer
- the compositions are prepared by thermo-mechanically working the elastomers in an internal mixer (BANBURY type) with a volume equal to 1 liter, in two stages, with an average speed of the pallets of 80 revolutions / minute, until obtaining at a temperature of 160 ° C., these steps being followed by a finishing step carried out on an external mixer.
- the vulcanization of the formulations is adapted to the vulcanization kinetics of the corresponding mixtures.
- compositions of Example 6 The properties of the compositions are set out below, the measurements having been carried out (on the vulcanized formulations), as in the case of the compositions of Example 6 below, according to the following standards and / or methods:
- a Monsanto 100 S rheometer corresponds to the time during which the control of the mixture is possible.
- the rubber mixture hardens from Ts2 (start of vulcanization).
- T90 corresponds to the time after which 90% of the vulcanization has been carried out.
- the modules x% correspond to the stress measured at x% of tensile deformation.
- the value considered is determined 15 seconds after the application of the force.
- test conditions are as follows:
- the test pieces are of rectangular shape (length 6 mm, width 4 mm, thickness 2.5 mm approximately).
- a sinusoidal deformation of increasing amplitude is applied at a constant frequency of 5 Hz.
- G ', G "and tan ⁇ are evaluated.
- ⁇ G' refers to the difference between the module G ' measured at a shear deformation of 0.001 and the modulus G 'measured at a shear deformation of 1 and tan ⁇ max corresponds to the maximum of the tangent of the loss angle as a function of the deformation.
- test pieces are of rectangular shape (length 10 mm, width 6 mm, thickness 2.5 mm approximately).
- a sinusoidal deformation with a constant amplitude of 10 microns, is applied at a constant frequency of 10 Hz.
- E ', E "and tan ⁇ are evaluated as a function of temperature.
- the scanning speed in temperature is 0.5 ° C / Below, tan ⁇ max (T) corresponds to the maximum of the tangent of the loss angle as a function of temperature.
- the UV A resistance to aging is evaluated in tension, on samples which have remained for 100 hours in a UV apparatus AT ATLAS CON at a temperature of 60 ° C. In these two cases, the results are expressed in stress and strain at break, and are norms compared to the value of the stress and the strain before aging.
- composition 1 exhibits an advantageous compromise in properties compared with the reference composition (composition R).
- composition 1 With a Mooney viscosity and a vulcanization kinetics comparable to those of the reference composition, composition 1 leads to a strengthening in terms of more marked modulus. With composition 1, there is a clear drop in the amplitude of the fall in modulus (Payne effect), also manifested by a drop in the tangent maximum ⁇ as a function of the deformation.
- Composition 1 also offers greater resistance to thermal aging and UV aging than that of the reference composition.
- compositions are prepared by thermo-mechanically working the elastomers in an internal mixer (BANBURY type) with a volume equal to 1 liter, in two stages, with an average speed of the pallets of 80 revolutions / minute, until obtaining at a temperature of 160 ° C., these steps being followed by a finishing step carried out on an external mixer.
- BANBURY type internal mixer
- the compositions are prepared by thermo-mechanically working the elastomers in an internal mixer (BANBURY type) with a volume equal to 1 liter, in two stages, with an average speed of the pallets of 80 revolutions / minute, until obtaining at a temperature of 160 ° C., these steps being followed by a finishing step carried out on an external mixer.
- the vulcanization of the formulations is adapted to the vulcanization kinetics of the corresponding mixtures.
- compositions are set out below, the measurements having been carried out (on the vulcanized formulations) according to the standards and / or methods described in Example 5.
- Table 5 The properties of the compositions are set out below, the measurements having been carried out (on the vulcanized formulations) according to the standards and / or methods described in Example 5.
- compositions 2 and 3 according to the invention exhibit an advantageous compromise of properties compared to the reference composition (composition R).
- composition R the reference composition
- composition 2 and especially composition 3 lead to a strengthening in terms of more pronounced modulus at 100% deformation.
- compositions 2 and 3 there is a clear drop in the amplitude of the fall in modulus (Payne effect), also manifested by a drop in the maximum tangent ⁇ as a function of the deformation. The Payne effect and the energy dissipation are therefore lower with the compositions according to the invention compared to the reference composition.
- compositions 2 and 3 finally offer resistance to thermal aging and to UV aging comparable to or even greater than that of the reference composition.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000575934A JP2002527557A (ja) | 1998-10-13 | 1999-10-13 | アルミニウムヒドロキシカーボネート、ヒドロキシオキシカーボネート又はオキシカーボネートの、ゴム組成物における充填剤としての使用 |
EP99949046A EP1141106B1 (fr) | 1998-10-13 | 1999-10-13 | Utilisation d'hydroxycarbonate, d'hydroxyoxycarbonate ou d'oxycarbonate d'aluminium comme charge dans une composition de caoutchouc |
BR9914409-3A BR9914409A (pt) | 1998-10-13 | 1999-10-13 | Utilização de pelo menos um composto consistindo em um hidroxicabornato, um hidroxicarbonato, ou um oxicarbonato de alumìnio, composição de borracha, e, artigo acabado |
CA002346511A CA2346511C (fr) | 1998-10-13 | 1999-10-13 | Utilisation d'hydroxycarbonate, d'hydroxyoxycarbonate ou d'oxycarbonate d'aluminium comme charge dans une composition de caoutchouc |
US09/807,315 US6512038B1 (en) | 1998-10-13 | 1999-10-13 | Use of aluminum hydroxycarbonate, hydroxyoxycarbonate or oxycarbonate as filler in a rubber composition |
AU62068/99A AU764171B2 (en) | 1998-10-13 | 1999-10-13 | Use of aluminium hydroxycarbonate, hydroxyoxycarbonate or oxycarbonate as filler in a rubber composition |
DE69909513T DE69909513T2 (de) | 1998-10-13 | 1999-10-13 | Verwendung von aluminiumhydroxycarbonat, aluminiumhydroxyoxycarbonat oder aluminiumoxycarbonat als füllstoff in kautschukzusammensetzungen |
KR1020017004588A KR20010080110A (ko) | 1998-10-13 | 1999-10-13 | 고무 조성물에서 충전재로서, 알루미늄히드록시카보네이트, 히드록시옥시카보네이트 또는옥시카보네이트의 용도 |
AT99949046T ATE244737T1 (de) | 1998-10-13 | 1999-10-13 | Verwendung von aluminiumhydroxycarbonat, aluminiumhydroxyoxycarbonat oder aluminiumoxycarbonat als füllstoff in kautschukzusammensetzungen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9813175A FR2784386B1 (fr) | 1998-10-13 | 1998-10-13 | Utilisation d'hydroxycarbonate, d'hydroxyoxycarbonate ou d'oxycarbonate d'aluminium comme charge dans une composition de caoutchouc |
FR98/13175 | 1998-10-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000022034A1 true WO2000022034A1 (fr) | 2000-04-20 |
Family
ID=9531804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/002483 WO2000022034A1 (fr) | 1998-10-13 | 1999-10-13 | Utilisation d'hydroxycarbonate, d'hydroxyoxycarbonate ou d'oxycarbonate d'aluminium comme charge dans une composition de caoutchouc |
Country Status (14)
Country | Link |
---|---|
US (1) | US6512038B1 (fr) |
EP (1) | EP1141106B1 (fr) |
JP (1) | JP2002527557A (fr) |
KR (1) | KR20010080110A (fr) |
CN (1) | CN1323329A (fr) |
AT (1) | ATE244737T1 (fr) |
AU (1) | AU764171B2 (fr) |
BR (1) | BR9914409A (fr) |
CA (1) | CA2346511C (fr) |
DE (1) | DE69909513T2 (fr) |
ES (1) | ES2203183T3 (fr) |
FR (1) | FR2784386B1 (fr) |
WO (1) | WO2000022034A1 (fr) |
ZA (1) | ZA200102633B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7335284B2 (en) | 2001-05-01 | 2008-02-26 | Adamant Technologies Sa | Modular electrochemical cell |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2893032A1 (fr) * | 2005-11-04 | 2007-05-11 | Dgtec Soc Par Actions Simplifi | Polymere presentant une tenue au feu et un retard a la propagation de la flamme fortement ameliores. |
US7960463B2 (en) * | 2007-12-31 | 2011-06-14 | Bridgestone Corporation | Tire treads including aluminum hydroxycarbonate |
CN107144502B (zh) * | 2017-06-29 | 2019-12-20 | 中策橡胶集团有限公司 | 一种白炭黑在胶料中分散性的表征方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0097330A1 (fr) * | 1982-06-18 | 1984-01-04 | Kyowa Chemical Industry Co., Ltd. | Procédé de réticulation d'une composition réticulable halogénée de caoutchouc |
US4492682A (en) * | 1982-01-29 | 1985-01-08 | Rhone-Poulenc Specialites Chimiques | Preparation of ultrapure boehmites and/or pseudo-boehmites |
EP0807603A2 (fr) * | 1996-05-16 | 1997-11-19 | Sumitomo Chemical Company Limited | Hydroxyde d'aluminium, procédé de sa production et son utilisation |
EP0810258A1 (fr) * | 1996-05-28 | 1997-12-03 | Compagnie Generale Des Etablissements Michelin-Michelin & Cie | Composition de caoutchouc diénique à base d'alumine en tant que charge renforçante et son utilisation pour la fabrication d'enveloppes de pneumatiques |
-
1998
- 1998-10-13 FR FR9813175A patent/FR2784386B1/fr not_active Expired - Fee Related
-
1999
- 1999-10-13 CA CA002346511A patent/CA2346511C/fr not_active Expired - Fee Related
- 1999-10-13 WO PCT/FR1999/002483 patent/WO2000022034A1/fr active IP Right Grant
- 1999-10-13 BR BR9914409-3A patent/BR9914409A/pt not_active IP Right Cessation
- 1999-10-13 US US09/807,315 patent/US6512038B1/en not_active Expired - Lifetime
- 1999-10-13 CN CN99812122A patent/CN1323329A/zh active Pending
- 1999-10-13 DE DE69909513T patent/DE69909513T2/de not_active Expired - Lifetime
- 1999-10-13 ES ES99949046T patent/ES2203183T3/es not_active Expired - Lifetime
- 1999-10-13 AU AU62068/99A patent/AU764171B2/en not_active Ceased
- 1999-10-13 JP JP2000575934A patent/JP2002527557A/ja not_active Ceased
- 1999-10-13 AT AT99949046T patent/ATE244737T1/de not_active IP Right Cessation
- 1999-10-13 EP EP99949046A patent/EP1141106B1/fr not_active Expired - Lifetime
- 1999-10-13 KR KR1020017004588A patent/KR20010080110A/ko active IP Right Grant
-
2001
- 2001-03-30 ZA ZA200102633A patent/ZA200102633B/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4492682A (en) * | 1982-01-29 | 1985-01-08 | Rhone-Poulenc Specialites Chimiques | Preparation of ultrapure boehmites and/or pseudo-boehmites |
EP0097330A1 (fr) * | 1982-06-18 | 1984-01-04 | Kyowa Chemical Industry Co., Ltd. | Procédé de réticulation d'une composition réticulable halogénée de caoutchouc |
EP0807603A2 (fr) * | 1996-05-16 | 1997-11-19 | Sumitomo Chemical Company Limited | Hydroxyde d'aluminium, procédé de sa production et son utilisation |
EP0810258A1 (fr) * | 1996-05-28 | 1997-12-03 | Compagnie Generale Des Etablissements Michelin-Michelin & Cie | Composition de caoutchouc diénique à base d'alumine en tant que charge renforçante et son utilisation pour la fabrication d'enveloppes de pneumatiques |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7335284B2 (en) | 2001-05-01 | 2008-02-26 | Adamant Technologies Sa | Modular electrochemical cell |
Also Published As
Publication number | Publication date |
---|---|
DE69909513D1 (de) | 2003-08-14 |
BR9914409A (pt) | 2001-06-26 |
AU764171B2 (en) | 2003-08-14 |
ZA200102633B (en) | 2002-01-18 |
AU6206899A (en) | 2000-05-01 |
US6512038B1 (en) | 2003-01-28 |
FR2784386B1 (fr) | 2000-11-10 |
EP1141106B1 (fr) | 2003-07-09 |
DE69909513T2 (de) | 2004-06-03 |
FR2784386A1 (fr) | 2000-04-14 |
JP2002527557A (ja) | 2002-08-27 |
CN1323329A (zh) | 2001-11-21 |
EP1141106A1 (fr) | 2001-10-10 |
ATE244737T1 (de) | 2003-07-15 |
ES2203183T3 (es) | 2004-04-01 |
KR20010080110A (ko) | 2001-08-22 |
CA2346511C (fr) | 2006-11-28 |
CA2346511A1 (fr) | 2000-04-20 |
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