WO2008043481A1 - Agent de glisse pour matériel de sport d'hiver - Google Patents

Agent de glisse pour matériel de sport d'hiver Download PDF

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Publication number
WO2008043481A1
WO2008043481A1 PCT/EP2007/008633 EP2007008633W WO2008043481A1 WO 2008043481 A1 WO2008043481 A1 WO 2008043481A1 EP 2007008633 W EP2007008633 W EP 2007008633W WO 2008043481 A1 WO2008043481 A1 WO 2008043481A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
nanocorundum
sports equipment
alkyl
trimethoxysilyl
Prior art date
Application number
PCT/EP2007/008633
Other languages
German (de)
English (en)
Inventor
Norbert Schmitt
Karin Maierhofer
Original Assignee
Clariant International Ltd
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 Clariant International Ltd filed Critical Clariant International Ltd
Publication of WO2008043481A1 publication Critical patent/WO2008043481A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G3/00—Ski waxes

Definitions

  • hydrophobized silica as an additive for improving the tribological properties in lubricants for winter sports equipment.
  • the invention thus relates to a lubricant for winter sports equipment containing nanocorundum, this nanocorner preferably being modified with a silane or siloxane on the surface.
  • the nanocorundum according to the present invention are nanoparticles consisting of pure aluminum oxide, the alumina being present for the most part in the rhombohedral ⁇ -modification (corundum). But there are also nanoparticles in question, which consist of 50 to 99.9 wt .-% Al 2 O 3 and 0.1 to 50 wt .-% of an oxide of the I or II. Main group of the Periodic Table. Also in these mixed oxides, the aluminum chloride is present for the most part in the rhombohedral ⁇ -modification.
  • the oxides according to the present invention preferably have a crystallite size of less than 1 ⁇ m, preferably less than 0.2 ⁇ m and particularly preferably between 0.001 and 0.09 ⁇ m. Particles of this size will be referred to below as nanoparticles.
  • Such nanoparticles can be prepared by different methods described below. These process descriptions refer to the production of pure alumina particles, but it goes without saying that in all these process variants in addition to Al-containing starting compounds and those compounds of elements of I. or II. Main group of the Periodic Table can be present to form mixed oxides. For this purpose, especially the chlorides, but also the oxides, oxychlorides, carbonates, sulfates or other suitable salts come into question. The amount of such oxide formers is such that the finished nanoparticles contain the aforementioned amounts of oxide MeO, if such mixed oxides are desired.
  • the preparation of the nanoparticles according to the invention starts from larger agglomerates which are subsequently deagglomerated to the desired particle size.
  • These agglomerates can be prepared by methods described below.
  • Such agglomerates can be prepared, for example, by various chemical syntheses. These are usually precipitation reactions (hydroxide precipitation, hydrolysis of organometallic compounds) with subsequent calcination. Crystallization seeds are often added to reduce the transition temperature to the ⁇ -alumina. The sols thus obtained are dried and thereby converted into a gel. The further calcination then takes place at temperatures between 35O 0 C and 650 0 C. For the conversion to ⁇ -Al 2 O 3 must then be annealed at temperatures around 1000 0 C. The processes are described in detail in DE 199 22 492.
  • the desired molecules are obtained from chemical reactions of a Precursorgases or by rapid cooling of a supersaturated gas.
  • the formation of the particles occurs either by collision or the constant equilibrium evaporation and condensation of molecular clusters.
  • the newly formed particles grow by further collision with product molecules (condensation) and / or particles (coagulation). If the coagulation rate is greater than that of the new growth or growth, agglomerates of spherical primary particles are formed.
  • Flame reactors represent a production variant based on this principle. Nanoparticles are produced here by the decomposition of Precursor molecules formed in the flame at 1500 0 C - 2500 0 C. As examples, the oxidations of TiCl 4 ; SICI 4 and Si 2 O (CH 3 ) 6 in methane / O 2 flames leading to TiO 2 and SiO 2 particles. When using AICI3 so far only the corresponding clay could be produced. Flame reactors are now used industrially for the synthesis of submicroparticles such as carbon black, pigment TiO 2 , silica and alumina.
  • Small particles can also be formed from drops with the help of centrifugal force, compressed air, sound, ultrasound and other methods.
  • the drops are then converted into powder by direct pyrolysis or by in situ reactions with other gases.
  • the spray and freeze drying should be mentioned.
  • precursor drops are transported through a high temperature field (flame, oven), resulting in rapid evaporation of the volatile component or initiating the decomposition reaction to the desired product.
  • the desired particles are collected in filters.
  • the production of BaTiO 3 from an aqueous solution of barium acetate and titanium lactate can be mentioned here.
  • the nanoparticles must be released. This is preferably done by grinding or by treatment with ultrasound. According to the invention, this deagglomeration takes place in the presence of a solvent.
  • the nanocorund remains as a small particle. If, according to the preferred variant, the nanocorund is to be coated on the surface with a silane or siloxane, this coating agent is added during or after the grinding to the suspension of the nanocorundum, the first variant being preferred. By adding such a coating agent during the milling process, the resulting active and reactive surfaces of the nanocorundum are saturated by chemical reaction or by physical attachment and thus prevents reagglomeration of the nanoparticles.
  • agglomerates are used which, as described in Ber. DKG 74 (1997) no. 11/12, pp. 719-722, as previously described.
  • the starting point here is aluminum chlorohydrate, which has the formula Al 2 (OH) x Cl y, where x is a number from 2.5 to 5.5 and y is a number from 3.5 to 0.5 and the sum of x and y is always 6 amounts to.
  • This aluminum chlorohydrate is mixed with crystallization seeds as an aqueous solution, then dried and then subjected to a thermal treatment (calcination).
  • aqueous solutions Preference is given to starting from about 50% aqueous solutions, as they are commercially available. Such a solution is mixed with nuclei which promote the formation of the ⁇ -modification of Al 2 O 3 . In particular, such nuclei cause a lowering of the temperature for the formation of the ⁇ -modification in the subsequent thermal treatment.
  • nuclei As germs are preferably in question finely disperse corundum, diaspore or hematite. Particular preference is given to using finely divided ⁇ -Al 2 O 3 nuclei having an average particle size of less than 0.1 ⁇ m. In general, 2 to 3 wt .-% of germs based on the resulting alumina from.
  • this starting solution still contains oxide formers in order to generate the oxides MeO in the nanocorundum.
  • the chlorides of the elements of the I. and II. Main group of the Periodic Table, in particular the chlorides of the elements Ca and Mg, but also other soluble or dispersible salts such as oxides, oxychlorides, carbonates or sulfates.
  • the amount of oxide generator is such that the finished nanoparticles contain 0.01 to 50 wt .-% of the oxide MeO.
  • the oxides of the I. and II. Main group may be present as a separate phase in addition to the alumina or with this real mixed oxides such as spinels, etc. form.
  • the term "mixed oxides" in the context of this invention should be understood to include both types.
  • This suspension of aluminum chlorohydrate, germs and optionally oxide formers is then evaporated to dryness and subjected to a thermal treatment (calcination).
  • This calcination is carried out in suitable devices, for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
  • suitable devices for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
  • the temperature for the calcination should not exceed 1400 ° C.
  • the lower temperature limit depends on the desired yield of nanocrystalline mixed oxide, the desired residual chlorine content and the content of germs.
  • the formation of the nanoparticles begins at about 500 0 C, but to keep the chlorine content low and the yield of nanoparticles high, but you will work preferably at 700 to 1100 0 C, in particular at 1000 to 1100 ° C.
  • agglomerates accumulate in the form of nearly spherical nanoparticles. These particles consist of Al 2 O 3 and optionally MeO. The content of MeO acts as an inhibitor of crystal growth and keeps the crystallite size small.
  • the agglomerates are preferably comminuted by wet grinding in a solvent, for example in an attritor mill, bead mill or stirred mill.
  • a solvent for example in an attritor mill, bead mill or stirred mill.
  • nanoparticles which have a crystallite size of less than 1 .mu.m, preferably less than 0.2 .mu.m, more preferably between 0.001 and 0.9 microns.
  • a suspension of nanoparticles with a d90 value of approximately 50 nm is obtained.
  • Another possibility for deagglomeration is sonication.
  • coating agents which is a preferred variant of this invention, such as e.g. Silanes or siloxanes there are two possibilities.
  • deagglomeration can be carried out in the presence of the coating agent, for example by adding the coating agent to the mill during milling.
  • Suitable solvents for the deagglomeration are both water and conventional solvents, preferably those which are also taken in the paint industry, such as C- ⁇ -C 4 alcohols, in particular methanol, ethanol or isopropanol, acetone, tetrahydrofuran ran , Butyl acetate. Is this done?
  • an inorganic or organic acid for example, HCl, HNO 3 , formic acid or acetic acid should be added to stabilize the resulting nanoparticles in the aqueous suspension.
  • the amount of acid may be 0.1 to 5 wt .-%, based on the total amount of nanoparticles.
  • aqueous suspension of the acid-modified nanoparticles is then preferably the grain fraction having a particle diameter of less than 20 nm separated by centrifugation.
  • the coating agent preferably a silane or siloxane
  • the nanoparticles thus treated precipitate are separated and dried to a powder, for example by freeze-drying.
  • Suitable coating agents are preferably silanes or siloxanes or mixtures thereof.
  • suitable coating agents are all substances which can bind physically to the surface of the mixed oxides (adsorption) or which can bond to form a chemical bond on the surface of the mixed oxide particles. Since the surface of the mixed oxide particles is hydrophilic and free hydroxy groups are available, suitable coating agents are alcohols, compounds having amino, hydroxyl, carbonyl, carboxyl or mercapto functions, silanes or siloxanes. Examples of such coating compositions are polyvinyl alcohol, mono-, di- and tricarboxylic acids, amino acids, amines, waxes, surfactants, hydroxycarboxylic acids, organosilanes and organosiloxanes.
  • Suitable silanes or siloxanes are compounds of the formulas
  • R, R ', R ", R 1 " identical or different from each other, an alkyl radical having 1-18 C atoms or a phenyl radical or an alkylphenyl or a phenylalkyl radical having 6 - 18 C-atoms or a radical of the general formula - ( Cmhbm-OJp-Cqhbq + i or a radical of the general formula -C 3 H 2s Y or a radical of the general formula -XZ t- i,
  • n is an integer meaning 1 ⁇ n ⁇ 1000, preferably 1 ⁇ n ⁇ 100
  • m is an integer 0 ⁇ m ⁇ 12
  • p is an integer 0 ⁇ p ⁇ 60
  • q is an integer 0 ⁇ q ⁇ 40
  • r is an integer 2 ⁇ r ⁇ 10 and s is an integer 0 ⁇ s ⁇ 18 and
  • Y is a reactive group, for example ⁇ , ⁇ -ethylenically unsaturated groups, such as (meth) acryloyl, vinyl or allyl groups, amino, amido, ureido, hydroxyl, epoxy, isocyanato, mercapto, sulfonyl, phosphonyl,
  • X is a t-functional oligomer with t an integer 2 ⁇ t ⁇ 8 and
  • the t-functional oligomer X is preferably selected from:
  • radicals of oligoethers are compounds of the type - (C a H 2a O) b - C a H 2a - or O- (C a H 2 aO) b -O -CaH 2a with 2 ⁇ a ⁇ 12 and 1 ⁇ b ⁇ 60, for example a diethylene glycol, triethylene glycol or tetraethylene glycol radical, a dipropylene glycol, tripropylene glycol, tetrapropylene glycol radical, a dibutylene glycol, tributylene glycol or tetrabutylene glycol radical.
  • residues of Oligoestem are compounds of the type -C b H 2b - (C (CO) C a H 2a - (CO) OC b H 2b -) c - or -OC b H 2b - (C (CO) C) a H 2a - (CO) O- C b H 2b -) c -O- with a and b different or equal
  • silanes of the type defined above are, for. Hexamethyldisiloxane, octamethyltrisiloxane, other homologous and isomeric compounds of the series Si n O n-1 (CH 3 ) 2 n + 2, where n is an integer 2 ⁇ n ⁇ 1000, e.g. B. Polydimethylsiloxane 200® fluid (20 cSt).
  • the corresponding difunctional compounds also come with epoxy, isocyanato, vinyl, allyl and di (meth) acryloyl groups used, for example, polydimethylsiloxane with vinyl end groups (850 - 1150 cST) or TEGORAD 2500 from. Tego Chemie Service.
  • Maleic acid copolymers as modifying compound e.g. BYK Silclean 3700 from Byk Chemie or TEGO® Protect 5001 from Tego Chemie Service GmbH.
  • R "" H or alkyl
  • R is an alkyl, such as. Methyl, ethyl, n-propyl, i-propyl, butyl,
  • R 1 is an alkyl, such as. Methyl, ethyl, n-propyl, i-propyl, butyl,
  • R ' is a cycloalkyl n is an integer from 1 - 20 x + y 3 x 1 or 2 y 1 or 2
  • R " 1 " H, alkyl
  • Preferred silanes are the silanes listed below: triethoxysilane, octadecyltimethoxysilane, 3- (trimethoxysilyl) -propylmethacrylate, 3- (trimethoxysilyl) -propylacrylate, 3- (trimethoxysilyl) -methylmethacrylate, 3- (trimethoxysilyl) -methylacrylate, 3- (trimethoxysilyl) ethylmethacrylate, 3- (trimethoxysilyl) -ethylacrylate, 3- (trimethoxysilyl) -pentylmethacrylate, 3- (trimethoxysilyl) -pentylacrylate, 3- (trimethoxysilyl) -hexylmethacrylate, 3- (trimethoxysilyl) -hexylacrylate, 3- (trimethoxysilyl) -butylmethacrylate , 3- (trimeth
  • Tetramethoxysilanes Tetramethoxysilanes, tetraethoxysilanes, oligomeric tetraethoxysilanes (DYNASIL® 40 from Degussa), tetra-n-propoxysilanes, 3-glycidyloxypropyltrimethoxysilanes, 3-glycidyloxypropyltriethoxysilanes,
  • the coating compositions are preferably added in molar ratios of nanoparticles to silane of from 1: 1 to 10: 1.
  • the amount of solvent in the deagglomeration is generally 80 to 90 wt .-%, based on the total amount of nanoparticles and solvent.
  • the deagglomeration by grinding and simultaneous modification with the coating agent is preferably carried out at temperatures of 20 to 150 ° C, more preferably at 20 to 90 0 C.
  • the suspension is subsequently separated from the grinding beads.
  • the suspension can be heated to complete the reaction for up to 30 hours.
  • the nanoparticles according to the invention preferably those which have been modified on the surface with silanes or siloxanes as described above, improve the tribological sliding properties of lubricants for winter sports equipment, in particular as an additive in ski waxes.
  • Such ski waxes generally consist of paraffins, which have different viscosities depending on the type of snow and contain various additives. example
  • corundum powder or hydrophobized corundum powder was additionally rubbed with a cork and the sanding structure was again worked out with a textured brush.
  • corundum powder or hydrophobic corundum the products described above were used.
  • the nano corundum skis glided faster and reached a higher level
  • the sample with the surface-modified nanocorner mixed into the wax at 10% by weight put back about 10% more distance in the opposite slope than the reference sample.

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  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne des agents de glisse pour du matériel de sport d'hiver, de préférence des farts de ski. Afin d'améliorer les propriétés tribologiques, ces agents de glisse contiennent du nanocorindon qui est de préférence modifié en surface par un silane ou un siloxane.
PCT/EP2007/008633 2006-10-06 2007-10-01 Agent de glisse pour matériel de sport d'hiver WO2008043481A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610047302 DE102006047302A1 (de) 2006-10-06 2006-10-06 Gleitmittel für Wintersportgeräte
DE102006047302.7 2006-10-06

Publications (1)

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WO2008043481A1 true WO2008043481A1 (fr) 2008-04-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITVE20110016A1 (it) * 2011-03-15 2012-09-16 Marco Maggiolo Sistema di velocizzazione per attrezzi degli sport invernali
EP3604469A4 (fr) * 2017-03-29 2021-01-20 Seoul National University R&DB Foundation Composition de fart haute performance et son procédé de préparation
WO2022117637A1 (fr) * 2020-12-01 2022-06-09 Isantin Gmbh Composition pour réduire le frottement par glissement d'un article sur la neige, la glace et/ou l'eau

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009040105A1 (de) 2009-09-04 2011-03-31 Zipps Skiwachse Gmbh Gleitmittel für Wintersportgeräte mit verbesserten tribologischen Gleiteigenschaften und längerer Gebrauchsdauer, Verfahren zur Herstellung und Anwendung
DE102010001861A1 (de) * 2010-02-11 2011-08-11 Holmenkol Ag, 71254 Pulverförmige Gleitmittel für Sportgeräte
DE102010018279A1 (de) * 2010-04-24 2011-10-27 Technische Universität Carolo-Wilhelmina Zu Braunschweig Verfahren und Vorrichtung zur Herstellung von Nanopartikeln
DE102014119567B4 (de) 2014-12-23 2019-04-11 Zipps Skiwachse Gmbh Gleitmittel für den Gebrauch auf Gleitflächen von Wintersportgeräten und dessen Verwendung

Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2005095533A1 (fr) * 2004-03-30 2005-10-13 Holmenkol Sport-Technologies Gmbh & Co. Kg Modificateur de lubrifiants pour ameliorer les proprietes tribologiques de glisse d'articles de sport d'hiver sur la neige
WO2007020061A1 (fr) * 2005-08-18 2007-02-22 Clariant International Ltd Procede pour realiser un corindon nanometrique a surface modifiee par des silanes

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CH666193A5 (en) * 1986-02-14 1988-07-15 Ims Kunststoff Ag Coating for ski running surface of sintered ldpe and finer additive - giving high ratio of static to kinetic friction, useful for nordic ski
DE102004027683A1 (de) * 2004-06-07 2006-01-05 Florian Felix Additiv zur Verbesserung der tribologischen Gleitreibungseigenschaften von Skibelägen für Wintersportgeräten

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005095533A1 (fr) * 2004-03-30 2005-10-13 Holmenkol Sport-Technologies Gmbh & Co. Kg Modificateur de lubrifiants pour ameliorer les proprietes tribologiques de glisse d'articles de sport d'hiver sur la neige
WO2007020061A1 (fr) * 2005-08-18 2007-02-22 Clariant International Ltd Procede pour realiser un corindon nanometrique a surface modifiee par des silanes

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* Cited by examiner, † Cited by third party
Title
MA H ET AL: "NANO-KORUND - SYNTHESE UND ANWENDUNG FUER FILTRATIONSMEMBRANEN, KATALYSATORTRAEGER, VERSCHLEISSSCHUTZ UND SENSOREN", CHEMIE INGENIEUR TECHNIK, WILEY VCH. VERLAG, WEINHEIM, DE, vol. 73, no. 1/2, 1 January 2001 (2001-01-01), pages 93 - 97, XP001003294, ISSN: 0009-286X *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITVE20110016A1 (it) * 2011-03-15 2012-09-16 Marco Maggiolo Sistema di velocizzazione per attrezzi degli sport invernali
EP3604469A4 (fr) * 2017-03-29 2021-01-20 Seoul National University R&DB Foundation Composition de fart haute performance et son procédé de préparation
WO2022117637A1 (fr) * 2020-12-01 2022-06-09 Isantin Gmbh Composition pour réduire le frottement par glissement d'un article sur la neige, la glace et/ou l'eau

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