WO1994010271A1 - Liquides electrovisqueux contenant de l'amidon - Google Patents

Liquides electrovisqueux contenant de l'amidon Download PDF

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Publication number
WO1994010271A1
WO1994010271A1 PCT/EP1993/002902 EP9302902W WO9410271A1 WO 1994010271 A1 WO1994010271 A1 WO 1994010271A1 EP 9302902 W EP9302902 W EP 9302902W WO 9410271 A1 WO9410271 A1 WO 9410271A1
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WO
WIPO (PCT)
Prior art keywords
esters
electroviscous
atoms
liquids
starch
Prior art date
Application number
PCT/EP1993/002902
Other languages
German (de)
English (en)
Inventor
Lutz Jeromin
Kurt Buick
Dieter Legel
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1994010271A1 publication Critical patent/WO1994010271A1/fr

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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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin

Definitions

  • the invention relates to electroviscous liquids which contain starch with a water content of 5 to 20% by weight and ester compounds, and to a process for the preparation of these electroviscous liquids.
  • the present invention furthermore relates to the use of esters of polyols with 2 to 6 hydroxyl groups and 2 to 32 C atoms and monocarboxylic acids with 2 to 32 C atoms as electrically non-conductive hydrophobic liquid in electroviscous liquids which contain starch contain a water content of 5 to 20% by weight as a solid.
  • Electroviscous liquids are dispersions of finely divided hydrophilic solids in electrically non-conductive hydrophobic liquids, the viscosities of which change very quickly and reversibly from the liquid to the plastic or solid state under the influence of a sufficiently strong electrical field.
  • the change in viscosity occurs both through constant electrical fields and through alternating fields, the current flow through the electroviscous liquids being very low in both cases. Therefore, electroviscous liquids can be used wherever the transmission of large forces with the aid of low electrical power is required, such as in hydraulic valves, vibration or shock absorbers and vibrators.
  • electroviscous liquids are desired which have a high temperature resistance and good chemical stability at temperatures of approximately -50.degree. C. to 150.degree. C. and also a good electroviscous effect. Since electroviscous liquids can come into contact with components, they should at the same time be inert to the material of the components, that is, they should not attack, swell or even dissolve them.
  • hydrophilic solids dispersions of barium titanates and water-laden, finely divided silicon dioxide (hydrophilic solids) with dibutyl sebacate (hydrophobic liquid) have an electroviscous effect.
  • the esters of short-chain monofunctional alcohols with sebacic acid are, however, relatively thermally unstable, since the first smoke development occurs at around 130 ° C.
  • the hydrophilic solids either contain heavy metals or are not biodegradable, so they must be disposed of.
  • electroviscous liquids which primarily contain activated silica gel as a hydrophobic solid.
  • a large number of compounds are described as hydrophobic, non-conductive liquids, such as mineral oil and dicarboxylic acid esters of mono- and / or polyhydric alcohols.
  • These electroviscous liquids contain water or a mixture of water and a water-soluble alcohol as mandatory components so that a sufficient electroviscous effect is observed. In order to stabilize these complex mixtures, dispersing agents must also be present.
  • These electroviscous liquids also contain a solid that is not biodegradable and must therefore be disposed of after use.
  • 2,417,850 describes a method for converting electrical pulses into mechanical forces, using a low-viscosity, non-conductive liquid such as mineral oil or olive oil.
  • the effect can be improved by adding finely divided material such as starch.
  • Particularly good results are achieved by a mixture of refined mineral oil and lanolin, in which a maximum of 20 volume% starch granules are dispersed.
  • Olive oil as the triglyceride of the unbranched glycerol, is not sufficiently resistant to hydrolysis.
  • the invention was based on the object of providing electroviscous liquids which have good chemical and thermal resistances and at the same time are readily biodegradable. Both the hydrophobic liquid and the hydrophilic solid should be biodegradable. In addition, the electroviscous liquids should remain stable over a longer period of time even without dispersants.
  • the present invention relates to electroviscous liquids comprising a) starch with a water content of 5 to 20% by weight as a hydrophilic solid and b) esters of branched, aliphatic polyols with 2 to 6 hydroxyl groups and with 2 to 32 C atoms and Monocarboxylic acids with 2 to 32 carbon atoms as a hydrophobic liquid.
  • esters contained in the electroviscous liquids according to the invention are known compounds and can be prepared by relevant organic chemistry methods, such as by acid or base-catalyzed reaction of the polyols with monocarboxylic acids.
  • these are esters which are prepared by practically complete esterification, ie full esters which have maximally small residual hydroxyl or acid numbers, preferably below 6.
  • Aliphatic, aromatic and cyclic monocarboxylic acids come into consideration as the acid component of the esters.
  • the aliphatic monocarboxylic acids can be saturated and / or unsaturated. Aliphatic monocarboxylic acids and of these the saturated representatives are preferred. Aliphatic, saturated monocarboxylic acids having 6 to 24 carbon atoms are very particularly preferred.
  • straight-chain saturated monocarboxylic acids are the fatty acids caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pal itic acid, stearic acid and / or behenic acid.
  • the fatty acids can also be a technical mixture, as is the case with the pressure splitting of natural fats and oils.
  • the aliphatic saturated monocarboxylic acids can also be branched, such as the alpha-branched carboxylic acids which are accessible by oxidation of alpha-branched primary alcohols prepared by the Guerbet process.
  • Examples of these branched saturated monocarboxylic acids are 2-n-butyl-n-octanoic acid, 2-n-heptyl-n-undecanoic acid, 2-n-octyl-n-dodecanoic acid and in particular 2-n-hexyl-n-decanoic acid. right (isopalmitic acid).
  • the Guerbet process according to which saturated primary alcohols are converted into defined ⁇ -branched primary alcohols by boiling in the presence of catalytic amounts of alkali metal hydroxide and heavy metal salts, is described, for example, by EF Pratt, DG Kubler in J. Am. Chem. Soc. 76 (1954), pages 52-56.
  • the polyol components of the esters are derived from branched, aliphatic polyols having 2 to 6 hydroxyl groups and 2 to 32 C atoms.
  • these branched, aliphatic polyols particular preference is given to those which, in the vicinity of the carbon having the primary hydroxyl groups, have a tertiary carbon atom (that is to say a carbon atom which has no hydrogen atom).
  • Suitable examples of these are trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, neopentylglycol, dipentaerythritol and / or mixtures thereof.
  • mixtures of aliphatic, saturated branched diols and aliphatic saturated branched polyols having 3 to 6 hydroxyl groups are used as the polyol component.
  • Mixtures of neopentyl glycol and trimethylolpropane, pentaerythritol and / or dipentaerythritol are preferred. It is preferred that neopentyl glycol is present in the mixture in a molar ratio of 5: 1 to 1: 5, preferably 1: 2 to 1: 4, with triethylolpropane, pentaerythritol and / or dipentaerythritol.
  • esters of fully aliphatic, saturated, branched polyols having 3 to 6 hydroxyl groups preferably trimethylolpropane, pentaerythritol and / or dipentaerythritol, are used.
  • Tri ethylolpropane esters of caprylic and / or capric acid are very particularly preferred.
  • the starches contained in the electroviscous liquids according to the invention can be conventional starches such as are obtainable from potatoes, corn, wheat etc. or else modified starches as can be obtained by pre-gelatinization, partial degradation or chemical derivatization.
  • Soluble starches which are also referred to as “thin-boiling” starches, and are preferably converted into low-molecular starch fragments by partial degradation, are preferred in the sense of the invention.
  • Such partial degradation can be oxidative, enzymatic or acid-catalyzed (see Handbook of Water-Soluble Gu s and Resins, Editor: Robert, L. Davidson, 1980 by Mc Graw-Hill, Inc., pages 22-30 to 22 -34).
  • Soluble starches for iodometry which are generally prepared by acid-catalyzed degradation (see Ullman's Encyclopedia of Industrial Chemistry, 4th revised and expanded), are particularly preferred for the purposes of the invention Edition, Verlag Chemie, Weinheim, Deerfield, Basel, 1982, Volume 22, pages 174-176 and already cited manual).
  • Such starches are commercially available as finely divided powders. Starches with low average particle diameters are particularly suitable, preferably below 100 ⁇ m and in particular in the range from 0.1 to 50 ⁇ m, since the stability of the electroviscous liquids is higher, the smaller the particle diameter.
  • the starches naturally have a water content that varies depending on their origin. If desired, such starches with the natural water content, provided it is between 5 and 20% by weight, can be used. According to the invention, however, the water content is preferably set precisely. For this purpose, the starches are first dried to free them of water and then treated with water-laden air to the desired water content. For the electroviscous liquids according to the invention, it has been shown that starches with a water content of about 15% by weight have particularly good electroviscous effects.
  • the electroviscous liquids contain the water-laden starches in a mass ratio to the esters of at least 30:70 to 70:30, preferably 40:60 to 60:40.
  • the electroviscous liquids can contain the dispersants known from the prior art, such as those of US Pat. No. 3,047,507.
  • the electroviscous liquids preferably do not contain such a dispersant.
  • Another object of the present invention is a process for the production of electroviscous liquids, which is characterized in that starch is first treated by treatment with humid air with a water content of 5 to 20% by weight, based on water-laden starch, loaded and then mixed with esters of branched, aliphatic polyols with 2 to 6 hydroxyl groups and with 2 to 32 C atoms and monocarboxylic acids with 2 to 32 C atoms and the mixture was finally converted into a finely divided dispersion by means of conventional homogenizers.
  • the starch is preferably dried first before it is treated with humid air. This eliminates the natural water content of the starches, so that the subsequent water treatment leads to starches with a defined water load. These water-laden starches are dispersed into the esters of the type described. A homogeneous, finely divided dispersion is obtained if shear homogenizers, high-pressure homogenizers or ultrasound are used after the dispersion.
  • electroviscous liquids according to the invention show good electro-reactivities and are very well tolerated with elastomeric materials, in particular with fluororubbers, are stable over a long period of time, and are thermally stable and very readily biodegradable.
  • the present invention furthermore relates to the use of esters of branched, aliphatic polyols with 2 to 6 hydroxyl groups and with 2 to 32 C atoms and monocarboxylic acids with 2 to 32 C atoms as electrically non-conductive hydrophobic liquid in electroviscous liquids, contain the starch with a water content of 5 to 20% by weight as a hydrophilic solid. Details of the esters and their amounts can be found in the description above. Examples
  • a commercially available soluble starch for analysis by Riedel de Haen, catalog number 33615, catalog: Laborchemischen 1992, page 1127; Loss on drying (105 ° C) ax. 10%; Sulfate ash max. 0.5%, pH (2%, 20 ° C) 6.0 -7.5) was dried at 105 ° C in a drying cabinet for 10 hours.
  • the dried starch was then cooled with the exclusion of air and weighed and then exposed to moist air until the water content of 8, 10, 12 or 15% by weight was reached by absorption of water from the air.
  • the starch loaded with water was dispersed into the respective ester (see below) using a laboratory stirrer.
  • the laboratory stirrer was equipped with a toothed washer (diameter 50 mm). At a stirrer speed of 2000 per minute, the dispersion process took about 30 minutes.
  • esters were used to prepare the electroviscous liquids according to the invention:
  • Tri ethylolpropane tricaprylate (acid number SZ according to DGF-CV2 ⁇ 0.2)
  • the electroviscous liquids each contained 50% by weight of water-moist starch.
  • the rotating body and the associated cup were of slightly conical design with the same inclination of the cone, so that the gap width s between the rotating body and cup could be varied easily and quickly by axially displacing the rotating body.
  • the measurement records Mrj (U) deliver via the relationships specific to the measuring apparatus
  • Gap distance s 1.2 mm
  • the electroviscous behavior of the liquids is better, the larger S and the smaller are good and EQ.
  • the specified electrical voltages and currents (direct current) characterize the electrical power.
  • Electroviscous liquid Test temperature 20 ° C; Shear rate 3931 / s, gap width 12,
  • Electroviscous liquid Test temperature 20 ° C; Shear rate 3931 / s, gap width 12,

Abstract

L'invention concerne des liquides électrovisqueux qui contiennent de l'amidon avec une teneur en eau comprise entre 5 et 20 % en poids et des composés esters, ainsi qu'un procédé de fabrication desdits liquides électrovisqueux. L'invention concerne en outre l'utilisation d'esters de polyoles aliphatiques ramifiés ayant entre 2 et 6 groupes hydroxyle et entre 2 et 32 atomes de C et d'acides monocarboxyliques ayant entre 2 et 32 atomes de C comme liquide hydrophobe non électroconducteur dans des liquides électrovisqueux de ce type. Ces liquides électrovisqueux présentent une bonne réactivité électrique, ne précipitent pas facilement, sont compatibles avec différents matériaux et sont surtout très facilement biodégradables.
PCT/EP1993/002902 1992-10-28 1993-10-20 Liquides electrovisqueux contenant de l'amidon WO1994010271A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4236405.1 1992-10-28
DE19924236405 DE4236405A1 (de) 1992-10-28 1992-10-28 Elektroviskose Flüssigkeiten mit Stärke

Publications (1)

Publication Number Publication Date
WO1994010271A1 true WO1994010271A1 (fr) 1994-05-11

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WO (1) WO1994010271A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19533800A1 (de) * 1995-09-13 1997-04-10 Berger Werner Prof Dr Rer Nat Verfahren zur Herstellung einer thermoplastischen Polymermischung auf der Basis von Stärke

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417850A (en) * 1942-04-14 1947-03-25 Willis M Winslow Method and means for translating electrical impulses into mechanical force
US3047507A (en) * 1960-04-04 1962-07-31 Wefco Inc Field responsive force transmitting compositions
FR1553235A (fr) * 1968-01-03 1969-01-10
FR2277871A1 (fr) * 1974-07-09 1976-02-06 United Kingdom Government Composition de fluide pouvant repondre a l'influence d'un champ electrique
US3970573A (en) * 1975-08-25 1976-07-20 Westhaver James W Electroviscous fluids
EP0342041A1 (fr) * 1988-05-12 1989-11-15 Toa Nenryo Kogyo Kabushiki Kaisha Fluides électrorhéologiques
WO1993013187A1 (fr) * 1992-01-04 1993-07-08 Henkel Kommanditgesellschaft Auf Aktien Liquides electrovisqueux

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417850A (en) * 1942-04-14 1947-03-25 Willis M Winslow Method and means for translating electrical impulses into mechanical force
US3047507A (en) * 1960-04-04 1962-07-31 Wefco Inc Field responsive force transmitting compositions
FR1553235A (fr) * 1968-01-03 1969-01-10
FR2277871A1 (fr) * 1974-07-09 1976-02-06 United Kingdom Government Composition de fluide pouvant repondre a l'influence d'un champ electrique
US3970573A (en) * 1975-08-25 1976-07-20 Westhaver James W Electroviscous fluids
EP0342041A1 (fr) * 1988-05-12 1989-11-15 Toa Nenryo Kogyo Kabushiki Kaisha Fluides électrorhéologiques
WO1993013187A1 (fr) * 1992-01-04 1993-07-08 Henkel Kommanditgesellschaft Auf Aktien Liquides electrovisqueux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ELVERS ET AL.: "ULLMANS ENCYCLOPÄDIE DER TECHNISCHEN CHEMIE,4.NEUBEARB. UND ERWEITERTE AUFLAGE.", 1982, VERLAG CHEMIE, WEINHEIM(DE),DEERFIELD(FLORIDA,VS),BASEL(CH) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19533800A1 (de) * 1995-09-13 1997-04-10 Berger Werner Prof Dr Rer Nat Verfahren zur Herstellung einer thermoplastischen Polymermischung auf der Basis von Stärke

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