EP0432601A1 - Fluides électrovisqueux à base de polyéthers dispersés - Google Patents

Fluides électrovisqueux à base de polyéthers dispersés Download PDF

Info

Publication number
EP0432601A1
EP0432601A1 EP90123063A EP90123063A EP0432601A1 EP 0432601 A1 EP0432601 A1 EP 0432601A1 EP 90123063 A EP90123063 A EP 90123063A EP 90123063 A EP90123063 A EP 90123063A EP 0432601 A1 EP0432601 A1 EP 0432601A1
Authority
EP
European Patent Office
Prior art keywords
electroviscous
weight
evf
component
viscosity
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
EP90123063A
Other languages
German (de)
English (en)
Other versions
EP0432601B1 (fr
Inventor
Udo Dr. Herrmann
Gunther Dr. Penners
Günter Dr. Oppermann
Roland Dr. Flindt
Hans-Horst Dr. Steinbach
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.)
Momentive Performance Materials GmbH
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
Priority claimed from DE19893941232 external-priority patent/DE3941232A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0432601A1 publication Critical patent/EP0432601A1/fr
Application granted granted Critical
Publication of EP0432601B1 publication Critical patent/EP0432601B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/001—Electrorheological fluids; smart fluids

Definitions

  • the invention relates to an electroviscous liquid, the viscosity of which is increased when a voltage is applied.
  • Electroviscous liquids are dispersions of finely divided, hydrophilic solids in hydrophobic and electrically non-conductive oils, whose viscosity changes very quickly and reversibly under the influence of a sufficiently strong electric field from the liquid to the plastic or solid state.
  • the viscosity reacts to both DC electrical fields and AC fields, whereby the current flow through the EVF should be very low. Therefore EVF can be used wherever the transmission of large forces with the help of low electrical power is required, e.g. in couplings, hydraulic valves, shock absorbers, vibrators or devices for positioning and fixing workpieces.
  • the abrasiveness and settling stability of the disperse phase play an important role in practical use.
  • the disperse phase should not sediment as far as possible, but in any case it should be easy to redisperse and should not cause any abrasion even under extreme mechanical stress.
  • the disperse phase consists of organic solids, such as Saccharides (DE 2 530 694), starch (EP 284 268 A2, US 3 970 573), polymers (EP 150 994 A1, DE 3 310 959 A1, GB 1 570 234, US 4 129 513), ion exchange resins (JP 92 278 / 1975, JP 32 221/1985, US 3 047 507), or silicone resins (DE 3 912 888 A1).
  • inorganic materials such as e.g.
  • Li hydrazine sulfate (US 4,772,407 A), zeolites (EP 265 252 A2), silica gel (DE 3,517,281 A1, DE 3,427,499 A1), and aluminum silicates (DE 3,536,934 A1) are used.
  • the electroviscous effect of the substances mentioned is due to the loading of the solids with water. Small amounts of water enable the migration of ions and thereby increase the ionic conductivity or the polarizability of the disperse particles, which is essential for the formation of the effect.
  • the electroviscous effect arises from the fact that the polarized particles of the disperse phase agglomerate in an external electrical field by means of dipole-dipole interactions.
  • Soot-filled bead polymers JP 016 093 or conductive polymers such as polypyrene or polyacetylene (JP 01 260 710) have also been used as replacements for the water-containing ones Phase discussed. However, such systems are expensive or complex to manufacture.
  • the above-mentioned EVF corresponding to the prior art are generally produced by dispersing a solid into a dispersion medium.
  • the viscosity of the resulting suspension depends on the shape and size, or the size distribution of the dispersed particles, and on the solids concentration and the dispersing action of any dispersing agents used. High volume-related solids contents with low viscosity are difficult to achieve.
  • solids which consist of particles with a spherical geometry, the volume fraction of the disperse phase and thus the electroviscous effect can be increased while maintaining the viscosity.
  • the object of the invention was to provide an anhydrous, non-abrasive, sedimentation-stable EVF with good electroviscous properties, which despite high volume fractions of the disperse phase is characterized by a low basic viscosity and low electrical conductivity.
  • the EVF according to the invention contains, dispersed in a non-conductive liquid in pure form or as a reaction product with other substances, 1 to 80% by weight, preferably 1 to 60% by weight, particularly preferably 20 to 60% by weight, of one Polyether.
  • the mixture of polyether and any additives, called template, which is dispersed into the non-conductive liquid during the EVF manufacturing process, should preferably be in liquid form.
  • the template can be chemically modified by adding suitable reagents before, during or after the dispersing step. This modification influences the consistency and, through the partial or complete implementation of the functional groups of the template, the conductivity of the disperse phase in the finished EVF.
  • a suitable dispersing agent is used for the dispersion.
  • the size of the dispersed particles in the EVF according to the invention is 0.05, preferably 0.1 to 200 ⁇ m.
  • the viscosity of the EVF at room temperature is between 0.5, preferably 3, and
  • a preferably liquid template is used for the disperse phase, which contains at least one of the following substances: (I): a linear or branched, optionally functionalized polyether, (II): the reaction product of (I) with mono- or oligofunctional compounds, such as additives such as polyols, aliphatic carboxylic acids or amines, alcohols, esters etc., in different stoichiometric ratios, (III): a mixture of (I) and / or (II) with other non-reactive additives, which in the finished EVF influence the electrical or mechanical properties of the disperse phase, such as conductivity and elastic behavior.
  • Additives (III) with plasticizer function in the sense of Invention are capped low molecular weight polyethers such as bismethylated trimethylpropane or the esters of phthalic acid.
  • linear polyethers examples are polyethylene glycols, polypropylene glycols, polybutylene glycols, statistical ethylene glycol-propylene glycol copolymers or else ethylene glycol-propylene glycol block polymers, such as those e.g. are sold by GAF under the trade name "Pluronic".
  • Branched polyethers are, for example, tris (polypropylene oxide) ⁇ -ol) glycidyl ether or other substances which are obtained by ethoxylation or propoxylation of higher-functionality hydroxy compounds, e.g. Pentaerythritol or 1,1,1-trimethylolpropane can be obtained.
  • the molecular weight of the polyglycols is between 62 and 1,000,000, preferably below 100,000, particularly preferably between 100 and 10,000.
  • the polyglycols can optionally contain functional end groups. Amines, allyl or vinyl groups, or carboxyl groups are examples of such functional end groups.
  • Polyethylene or polypropylene mono- or diamines can be obtained under the trade name "Jeffamin” from the company "TEXACO”. Examples of products containing acrylic groups are the esters of glycols with corresponding acids, e.g. Acrylic acid.
  • the substances mentioned under (II) include e.g. the polyesters common in polymethane chemistry, which are sold by BAYER AG under the trade name "Desmophen".
  • an additive (IV) for example crosslinking agent
  • a crosslinking agent for example crosslinking agent
  • emulsification of the template which by reaction with the functional end groups of the compounds (I), (II) and / or (III) leads to molecular weight build-up in the emulsion droplets, or also to a reduction in the number of functional end groups.
  • viscous or solid particles are formed, the spherical geometry of which is retained during and after the reaction.
  • crosslinkers examples are di- or multifunctional isocyanates with different structures, which are sold, for example, under the trade name "Desmodur” by BAYER AG.
  • Tri- or higher functional Glycol is particularly preferred to use tolylene diisocyanate as a crosslinker.
  • the so-called acetate, amine, benzamide, oxime and alkoxy crosslinkers commonly used in silicone chemistry can also be used for crosslinking.
  • the isocyanate crosslinking agent is preferably used in amounts such that 20 to 100%, preferably up to 80%, of the OH groups of the glycol are reacted. Radical crosslinking systems are suitable for the conversion of allyl or vinyl group-modified compounds of groups (I) to (III).
  • the EVF according to the invention contains the disperse phase (the reaction product from the initial charge and (IV)) to 10 to 85% by weight, but preferably to 40 to 70% by weight.
  • silicone oils such as polydimethylsiloxanes or also polysiloxanes with higher alkyl groups, fluorine-containing siloxanes and liquid methylphenylsiloxanes are used. These can be used alone or in combination of two or more types.
  • the solidification point of the dispersion media is preferably set below -30 ° C, the boiling point above 150 ° C.
  • the viscosity of the oils is between 3 and 300 mm2 / s at room temperature. In general, the low-viscosity oils with a viscosity of 3 to 20 mm2 / s are preferred because they achieve a lower basic viscosity of the EVF.
  • the oil should also have a density that approximately corresponds to the density of the disperse phase.
  • a density that approximately corresponds to the density of the disperse phase.
  • Fluorine-containing siloxanes of the general structure are particularly suitable for producing sedimentation-stable EVF:
  • Suitable dispersants for the disperse phase are surfactants which are soluble in the dispersion medium and which, e.g. are derived from amines, imidazolines, oxazolines, alcohols, glycol or sorbitol.
  • Polymers soluble in the dispersion medium can also be used. Suitable are e.g. Polymers which contain 0.1 to 10% by weight of N and / or OH, and 25 to 83% by weight of C4-C24-alkyl groups and have a molecular weight in the range from 5000 to 1,000,000.
  • the N- and / or OH-containing compounds in these polymers can e.g.
  • Amine, amide, imide, nitrile, 5- to 6-membered N-containing heterocyclic rings, or an alcohol, and the C4-C24-alkyl groups are esters of acrylic or methacrylic acid.
  • N and OH-containing compounds mentioned are N, N-dimethylaminoethyl methacrylate, tert-butylacrylamide, maleimide, acrylonitrile, N-vinylpyrrolidone, vinylpyridine and 2-hydroxyethyl methacrylate.
  • the abovementioned polymeric dispersants generally have the advantage over the low molecular weight surfactants that the dispersions prepared with them are more stable with regard to the settling behavior.
  • Polysiloxane-polyether copolymers as are available, for example, under the trade name "Tegopren” from GOLDSCHMIDT AG in Essen (FRG), are preferably used for the dispersion in silicone oil.
  • Particularly preferred dispersants from this class are polysiloxane polyethers with an ethylene oxide-propylene oxide weight ratio of approximately 1: 1.
  • Such one Product, with an ethylene oxide-propylene oxide weight ratio of 49:51, is sold by GOLDSCHMIDT under the name "Tegopren 5830".
  • the reaction products of hydroxy-functional polysiloxanes with a wide variety of silanes are dispersants for the preparation of the EVF according to the invention.
  • Particularly preferred dispersants from this class of substances are the reaction products of a hydroxy-functional polysiloxane with aminosilanes.
  • the dispersant should be present in the EVF in amounts of 0.1 to 4% by weight, preferably 0.5 to 3% by weight.
  • EVF which is produced with silicone oil
  • silicone oil it applies that they are stable in settling, physiologically indifferent (non-toxic), and are very compatible with elastomeric materials, in particular with rubber.
  • they are heat and cold resistant within an unusually wide temperature range and have only a slight pressure dependence of the viscosity.
  • the electroviscous dispersions according to the invention have a high dielectric strength. It should be emphasized as a further advantage that the EVFs described are settling-stable and not abrasive and have low basic viscosities despite high volume fractions of the disperse phase.
  • the initial charge is mixed with the reactive additive or the crosslinking agent.
  • the mixture is dispersed in a liquid phase containing the dispersant.
  • shear homogenizers, high-pressure homogenizers or ultrasound can be used for this purpose.
  • the dispersion should be carried out so that the particle size does not exceed 200 ⁇ m, preferably 100 ⁇ m.
  • the product is allowed to react for a relatively long time at a suitable temperature which, depending on the reactivity of the crosslinking agent, is typically in a range from 0 ° C., preferably 15 ° C. to 150 ° C.
  • the crosslinking agent is only mixed into the dispersion after the dispersion process.
  • the template is sprayed with or without surfactant or additive (IV) into a fine powder, and the resulting powder is subsequently dispersed into the liquid phase.
  • the electrode area of the inner rotating cylinder with a diameter of 50 mm is approx. 78 cm2, the gap between the electrodes is 0.50 mm.
  • the shear load can be set to a maximum of 2640 s ⁇ 1.
  • the measuring range of the shear stress of the viscometer is a maximum of 750 Pa.
  • the EVF can be excited with both DC and AC voltage.
  • the EVF is preferably tested with AC voltage and with dynamic shear stress. This gives well-reproducible flow curves.
  • a constant shear rate of 0 ⁇ D ⁇ 2640 s ⁇ 1 is set and the dependence of the shear stress ⁇ on the electrical field strength E is measured effective current of 4 mA and a frequency between 50 and 550 Hz. Preferably, however, is measured at 50 Hz, because then the total current at lowest, and therefore the required electrical power is lowest.
  • Flow curves corresponding to FIG. 1 are obtained. It can be seen that the shear stress ⁇ initially increases parabolically with small field strengths and linearly with larger field strengths. The slope S of the linear part of the curve can be seen in the figure and is given in Pa.m / kV.
  • comparison approaches 1 to 3 correspond to the prior art. They are based on Examples 6, 7 and 9 of DE 3 536 934 A1. The liquids described in these examples are distinguished by particularly good electroviscous properties.
  • Examples 1 to 12 are EVFs according to the invention.
  • Table I lists the electroviscous properties of the EVF I to 11 according to the invention and the comparative samples at different temperatures.
  • EVF 2 to 4 shows the relationship between some properties (electro-viscous effect S, threshold value of the electric field strength E o and viscosity V at a rotational speed of the rotor of 1,000 rpm) of the EVF described in Examples 1 to 5 and the Amount of hydroxyl groups reacted with isocyanate at a measuring temperature of 25 ° C.
  • the arrows on the ordinate represent typical values for an EVF according to Comparative Example 2. It should be particularly emphasized that many EVF according to the invention are characterized by very good electroviscous effects despite their low viscosity and low threshold field strength.
  • the EVF was produced in accordance with the procedure given in Example 1. However, no crosslinker was added, so that the conversion of the hydroxyl groups of the glycol is 0 mol%.
  • the dispersant (b) 0.6 g of the dispersant (b) are dissolved in 20 g of the dispersion medium (a). 17.5 g of the glycol (a) are mixed with 7.61 g of the crosslinking agent (a). In the case of a quantitative reaction, this amount of crosslinker leads to the stoichiometric conversion of the hydroxyl groups in the glycol and thus corresponds to an OH conversion of 100 mol%.
  • the mixture is emulsified into the dispersant solution immediately after the preparation according to Example 1. The samples were subsequently reacted for 48 hours at room temperature.
  • the dispersant (b) 0.6 g of the dispersant (b) are dissolved in 20 g of the dispersion medium (a). 17.5 g of the trifunctional glycol (b) are mixed with 6.79 g of the crosslinker (a). In the case of a quantitative reaction, this amount of crosslinker leads to the stoichiometric conversion of the hydroxyl groups in the glycol and thus corresponds to an OH conversion of 100 mol%.
  • the mixture is emulsified into the dispersant solution immediately after the preparation according to Example 1. Subsequently, the samples were fully reacted at 90 ° C. for 8 hours.
  • dispersant (b) 0.5 g of the dispersant (b) are dissolved in 20 g of the dispersion medium (a). 15.0 g of the bifunctional glycol (a) are mixed with 4.14 g of the crosslinker (b). In the case of a quantitative reaction, this amount of crosslinker leads to an OH conversion of 75 mol%.
  • the mixture is emulsified into the dispersant solution immediately after the preparation according to Example 1. Subsequently, the samples were left to react for 48 hours at room temperature.
  • the dispersant (b) 0.6 g of the dispersant (b) are dissolved in 20 g of the dispersion medium (b). 17.5 g of the trifunctional glycol (b) are mixed with 6.79 g of the crosslinker (a). In the case of a quantitative reaction, this amount of crosslinker leads to the stoichiometric conversion of the hydroxyl groups in the glycol and thus corresponds to an OH conversion of 100 mol%.
  • the mixture is emulsified into the dispersant solution immediately after the preparation according to Example 1. The samples were subsequently fully reacted at 90 ° C. for 8 hours.
  • Example 6 of patent DE 3 536 934 A1 50 parts by weight of an erionite (composition: 62% by weight SiO2, 18% by weight Al2O3, 10% by weight Na2O) in 50 parts by weight of a polydimethylsiloxane -Silicone oil with a viscosity of 5 mm2 / s (at 25 ° C) dispersed.
  • the moisture content of the erionite according to DIN 55 921 was 6% by weight.
  • 2.5 parts by weight of the dispersant 1 (amino-functional siloxane) described in the patent were used as the dispersant.
  • Example 7 of patent DE 3 536 934 A1 40 parts by weight of an Al silicate (composition: 75% by weight SiO2, 9% by weight Al2O3, 7% by weight Na2O) were converted into 60 parts by weight a polydimethylsiloxane silicone oil with a viscosity of 5 mm2 / s (at 25 ° C) dispersed.
  • the moisture of the Al silicate according to DIN 55 921 was 6% by weight. 6 parts by weight of the dispersant 1 described in the patent were used as the dispersant.
  • Example 9 of patent DE 3 536 934 A1 50 parts by weight of a zeolite Y (Na form) (composition: 58% by weight SiO2, 20% by weight Al2O3, 12% by weight Na2O) were added in 50 Part by weight of a polydimethylsiloxane silicone oil with a viscosity of 5 mm2 / s (at 25 ° C) dispersed.
  • the moisture of the zeolite Y according to DIN 55 921 was 6% by weight.
  • 2.5 parts by weight of the dispersant 1 described in the patent were used as the dispersant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)
EP90123063A 1989-12-14 1990-12-01 Fluides électrovisqueux à base de polyéthers dispersés Expired - Lifetime EP0432601B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19893941232 DE3941232A1 (de) 1989-12-14 1989-12-14 Elektroviskose fluessigkeiten auf basis von polyglykolen und aminofunktionellen polyethern
DE3941232 1989-12-14
DE4026880 1990-08-25
DE4026880 1990-08-25

Publications (2)

Publication Number Publication Date
EP0432601A1 true EP0432601A1 (fr) 1991-06-19
EP0432601B1 EP0432601B1 (fr) 1996-05-15

Family

ID=25887955

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90123063A Expired - Lifetime EP0432601B1 (fr) 1989-12-14 1990-12-01 Fluides électrovisqueux à base de polyéthers dispersés

Country Status (5)

Country Link
EP (1) EP0432601B1 (fr)
JP (1) JPH03255193A (fr)
AT (1) ATE138092T1 (fr)
DE (1) DE59010326D1 (fr)
ES (1) ES2087113T3 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472991A1 (fr) * 1990-08-25 1992-03-04 Bayer Ag Fluides électrovisceuses à base de dispersions de polymères avec une phase dispersée contenant des électrolytes
WO1992022623A1 (fr) * 1991-06-14 1992-12-23 Bayer Aktiengesellschaft Fluide electrovisqueux a base d'acrylates de polyether utilises comme phase dispersee
EP0521638A1 (fr) * 1991-06-29 1993-01-07 Dow Corning Limited Fluide électrorheologique comprenant un polysiloxane contenant un groupe fluorohexylalcoyle
EP0529166A1 (fr) * 1991-08-29 1993-03-03 Nippon Shokubai Co., Ltd. Fluides électrorhéologiques
WO1993006199A1 (fr) * 1991-09-19 1993-04-01 Bayer Aktiengesellschaft Liquide electrovisqueux
WO1993007244A1 (fr) * 1991-10-10 1993-04-15 The Lubrizol Corporation Fluides electrorheologiques renfermant des polyanilines
WO1993007243A1 (fr) * 1991-10-10 1993-04-15 The Lubrizol Corporation Fluides electrorheologiques renfermant des polymeres electroniquement conducteurs
EP0543377A1 (fr) * 1991-11-20 1993-05-26 Dow Corning Toray Silicone Company, Limited Fluide électrovisqueuse
EP0636683A1 (fr) * 1993-07-30 1995-02-01 Nippon Shokubai Co., Ltd. Fluide électrorhéologique
FR2712600A1 (fr) * 1993-11-18 1995-05-24 Rhone Poulenc Chimie Fluide électrorhéologique anhydre.
US5595680A (en) * 1991-10-10 1997-01-21 The Lubrizol Corporation Electrorheological fluids containing polyanilines
US5843331A (en) * 1995-11-13 1998-12-01 The Lubrizol Corporation Polymeric materials to self-regulate the level of polar activators in electrorheological fluids
US6065572A (en) * 1995-11-13 2000-05-23 The Lubrizol Corporation Polymeric materials to self-regulate the level of polar activators in electrorheological fluids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021191811A (ja) * 2020-06-05 2021-12-16 日立Astemo株式会社 電気粘性流体およびシリンダ装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219751A2 (fr) * 1985-10-17 1987-04-29 Bayer Ag Fluides électrovisqueux
EP0284268A2 (fr) * 1987-03-24 1988-09-28 Er Fluid Developments Limited Fluides électro-rhéologiques/fluides sensibles à un champ électrique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01266191A (ja) * 1988-04-19 1989-10-24 Bridgestone Corp 電気粘性液体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219751A2 (fr) * 1985-10-17 1987-04-29 Bayer Ag Fluides électrovisqueux
EP0284268A2 (fr) * 1987-03-24 1988-09-28 Er Fluid Developments Limited Fluides électro-rhéologiques/fluides sensibles à un champ électrique

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5268118A (en) * 1990-08-25 1993-12-07 Bayer Aktiengesellschaft Electroviscous liquids based on polymer dispersions with an electrolyte-containing disperse phase
EP0472991A1 (fr) * 1990-08-25 1992-03-04 Bayer Ag Fluides électrovisceuses à base de dispersions de polymères avec une phase dispersée contenant des électrolytes
WO1992022623A1 (fr) * 1991-06-14 1992-12-23 Bayer Aktiengesellschaft Fluide electrovisqueux a base d'acrylates de polyether utilises comme phase dispersee
US5462687A (en) * 1991-06-14 1995-10-31 Bayer Aktiengesellschaft Electroviscous fluid based on polyether acrylates as disperse phase
EP0521638A1 (fr) * 1991-06-29 1993-01-07 Dow Corning Limited Fluide électrorheologique comprenant un polysiloxane contenant un groupe fluorohexylalcoyle
EP0529166A1 (fr) * 1991-08-29 1993-03-03 Nippon Shokubai Co., Ltd. Fluides électrorhéologiques
WO1993006199A1 (fr) * 1991-09-19 1993-04-01 Bayer Aktiengesellschaft Liquide electrovisqueux
WO1993007243A1 (fr) * 1991-10-10 1993-04-15 The Lubrizol Corporation Fluides electrorheologiques renfermant des polymeres electroniquement conducteurs
US5435932A (en) * 1991-10-10 1995-07-25 The Lubrizol Corporation Electrorheological fluids containing eletronically conductive polymers
US5437806A (en) * 1991-10-10 1995-08-01 The Lubrizol Corporation Electrorheological fluids containing polyanilines
WO1993007244A1 (fr) * 1991-10-10 1993-04-15 The Lubrizol Corporation Fluides electrorheologiques renfermant des polyanilines
US5595680A (en) * 1991-10-10 1997-01-21 The Lubrizol Corporation Electrorheological fluids containing polyanilines
EP0543377A1 (fr) * 1991-11-20 1993-05-26 Dow Corning Toray Silicone Company, Limited Fluide électrovisqueuse
EP0636683A1 (fr) * 1993-07-30 1995-02-01 Nippon Shokubai Co., Ltd. Fluide électrorhéologique
FR2712600A1 (fr) * 1993-11-18 1995-05-24 Rhone Poulenc Chimie Fluide électrorhéologique anhydre.
US5843331A (en) * 1995-11-13 1998-12-01 The Lubrizol Corporation Polymeric materials to self-regulate the level of polar activators in electrorheological fluids
US6065572A (en) * 1995-11-13 2000-05-23 The Lubrizol Corporation Polymeric materials to self-regulate the level of polar activators in electrorheological fluids

Also Published As

Publication number Publication date
ATE138092T1 (de) 1996-06-15
DE59010326D1 (de) 1996-06-20
EP0432601B1 (fr) 1996-05-15
ES2087113T3 (es) 1996-07-16
JPH03255193A (ja) 1991-11-14

Similar Documents

Publication Publication Date Title
EP0472991B1 (fr) Fluides électrovisceuses à base de dispersions de polymères avec une phase dispersée contenant des électrolytes
EP0219751B1 (fr) Fluides électrovisqueux
EP0432601B1 (fr) Fluides électrovisqueux à base de polyéthers dispersés
EP0170939B1 (fr) Fluides électrovisqueux
DE69214856T2 (de) Aus der Emulsion gelierte Silikon-Entschäumer
EP0201827B1 (fr) Fluides électrovisqueux
US9902919B2 (en) Electrorheological compositions
DE69202620T2 (de) Silikon-Entschäumerzusammensetzung.
EP1400581B1 (fr) Fluides électrorhéologiques
EP0023533B1 (fr) Agent pour le traitement anti-moussant de milieux liquides
DE69214962T2 (de) Elektroviskose flüssigkeit
DE19632430C1 (de) Verfahren zur Herstellung von nicht-wäßrigen Dispersionen und deren Verwendung
DE69102660T2 (de) Elektrorheologische Flüssigkeiten auf der Basis von Silicon-ionomer-Partikeln.
DE4119670A1 (de) Elektroviskose fluessigkeit auf basis von polyetheracrylaten als disperse phase
EP2016117B1 (fr) Dispersion stable a la sédimentation, procédé de production et son utilisation
DE3912888C2 (fr)
DE69916548T2 (de) Schwingungsdämpfende Zusammensetzung
DE69206764T2 (de) Elektroviskose Flüssigkeit
DE3941232A1 (de) Elektroviskose fluessigkeiten auf basis von polyglykolen und aminofunktionellen polyethern
DE69107406T2 (de) Elektroviskose-Flüssigkeit.
DE69819994T2 (de) Polyfluoroalkyl-Siloxane
EP0583763A2 (fr) Fluide électrorhéologique à lase de silicate lamellaire synthétique
JPH01304188A (ja) 電気粘性液体
JPH06172772A (ja) 電気粘性流体
JPH04161497A (ja) 電気粘性液体

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: 19901201

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19920703

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 138092

Country of ref document: AT

Date of ref document: 19960615

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

REF Corresponds to:

Ref document number: 59010326

Country of ref document: DE

Date of ref document: 19960620

REG Reference to a national code

Ref country code: ES

Ref legal event code: BA2A

Ref document number: 2087113

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2087113

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19960618

ET Fr: translation filed
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: CH

Ref legal event code: PUE

Owner name: BAYER AG TRANSFER- GE BAYER SILICONES GMBH & CO. K

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

NLS Nl: assignments of ep-patents

Owner name: GE BAYER SILICONES GMBH & CO. KG

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

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

Ref country code: ES

Payment date: 20011122

Year of fee payment: 12

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

Ref country code: GB

Payment date: 20011205

Year of fee payment: 12

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

Ref country code: BE

Payment date: 20011212

Year of fee payment: 12

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

Ref country code: FR

Payment date: 20011219

Year of fee payment: 12

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

Ref country code: NL

Payment date: 20011221

Year of fee payment: 12

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

Ref country code: AT

Payment date: 20011228

Year of fee payment: 12

Ref country code: SE

Payment date: 20011228

Year of fee payment: 12

Ref country code: CH

Payment date: 20011228

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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 NON-PAYMENT OF DUE FEES

Effective date: 20021201

Ref country code: AT

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

Effective date: 20021201

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

Ref country code: SE

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

Effective date: 20021202

Ref country code: ES

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

Effective date: 20021202

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: 20021231

Ref country code: CH

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

Effective date: 20021231

Ref country code: BE

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

Effective date: 20021231

BERE Be: lapsed

Owner name: *GE BAYER SILICONES G.M.B.H. & CO. K.G.

Effective date: 20021231

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: 20030701

GBPC Gb: european patent ceased through non-payment of renewal fee
EUG Se: european patent has lapsed
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: 20030701

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

Ref country code: FR

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

Effective date: 20030901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021202

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051201

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

Ref country code: DE

Payment date: 20100224

Year of fee payment: 20

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20101201