WO2019121829A1 - Procédés et compositions pour le traitement de surface de substrats et articles obtenus avec ceux-ci - Google Patents

Procédés et compositions pour le traitement de surface de substrats et articles obtenus avec ceux-ci Download PDF

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Publication number
WO2019121829A1
WO2019121829A1 PCT/EP2018/085711 EP2018085711W WO2019121829A1 WO 2019121829 A1 WO2019121829 A1 WO 2019121829A1 EP 2018085711 W EP2018085711 W EP 2018085711W WO 2019121829 A1 WO2019121829 A1 WO 2019121829A1
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WO
WIPO (PCT)
Prior art keywords
particulates
functionalized
precipitated silica
substrate
compound
Prior art date
Application number
PCT/EP2018/085711
Other languages
English (en)
Inventor
Ling Qi
Julien Jolly
Kévin BOUGIS
Bertrand Pavageau
Original Assignee
Rhodia Operations
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 Rhodia Operations filed Critical Rhodia Operations
Publication of WO2019121829A1 publication Critical patent/WO2019121829A1/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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention pertains to a coating technology for improving surface properties, in particular hydrophobic and/or icephobic surface properties, of substrates such as steel, stainless steel, aluminum, glass or ceramic substrates which are found for example in the automotive, aircraft, naval, building or energy industries.
  • Another example is represented by ice accretion and ice adhesion deleterious phenomena appearing on different surfaces and which, under cold weather conditions, can result in severe problems on power lines, telecommunications, transportation in general, aircraft or power production by wind turbines. Icing of wind turbines is a problem which not only affects their energy production performance, but also causes mechanical and electrical failures.
  • a first object of the present invention relates to an article comprising a substrate and a coating composition deposited onto the surface of said substrate, said coating composition comprising (i) one or more crosslinked polyurethane polymers and (ii) particulates of precipitated silica functionalized with a linear polyfluorinated compound presenting at least one a,w alcoxysilane end group(s).
  • the coating composition is composed of a single layer containing said functionalized silica particulates embedded inside the crosslinked polyurethane polymers.
  • the polyfluorinated compound grafted on the surface of the precipitated silica particulates is preferably a perfluoro compound, and even more preferably a perfluoro polyether compound.
  • the precipitated silica, before and/or after functionalization as explained herein after present preferably in its dry state one or more, and even more preferably all, of the following features:
  • the precipitated silica used in the invention may be prepared for example according to methods of preparation as described in EP 0520862, WO 99/07237 or WO 99/49850.
  • the precipitated silica used according to the invention can be advantageously a precipitated silica sold under the trademark Tixosil ® 365 by the SOLVAY Company.
  • Precipitated silica implemented in the context of the invention preferably has a BET surface area of at least 50 m 2 /g, in particular at least 75 m 2 /g, especially at least 90 m 2 /g, for example between 100 and 400 m 2 /g. It may be between 100 and 250 m 2 /g, especially between 110 and 250 m 2 /g.
  • the moiety corresponds to the linear polyfluorinated compound bearing at least one a,w alcoxysilane end group, said at least one end groups having chemically reacted by direct condensation with the silanol groups present at the surface of the Si0 2 particulates to generate a permanent siloxane bond between the same.
  • the functionalizing compound maybe schematically represented by the following formula:
  • R 1 -R 3 independently from each other designate an alkyl radical, preferably a C 1 -C 3 alkyl radical and even more preferably is methyl or ethyl
  • R designates a linear fluorinated, preferably perfluorinated, bivalent radical
  • T is a perfluorinated group, more preferably -CF 3 or a group of formula - Si-fOF ⁇ XORsXOR f ,) in which R4-R6 independently from each other designate an alkyl radical, preferably a C 1 -C 3 alkyl radical ans even more preferably is methyl or ethyl.
  • the functionalizing compound to be used is a linear compound terminated at least on one side, and more preferably on each side, by a trialcoxysilane group (reacting group), and the main chain of which being highly fluorinated, and preferably is perfluorinated (i.e. all the hydrogen atoms borne by carbon atoms have been substituted by fluorine atoms).
  • - R’ designates a linear perfluorinated bivalent radical comprising more than 50 wt. %, preferably more than 90 wt. %, more preferably composed essentially of, and still more preferably composed of statistically distributed repeating units of formula [-CF 2 -CF 2 -0-] m and [-CF2-0-] n , in which m and n are both integers higher than 0 and the m/n ratio is comprised from 2 A to 3 / 2 , preferably between 0.80 and 1.20, said m/n ratio being further preferably higher than 1.0,
  • perfluoro polyether polymers when said group T is a perfluorinated group, the perfluoro polyether is also referred to as a“monoftmctional perfluoro polyether”, while when said group T is a group of formula -Si-(OR4)(OR5)(OR6) as defined above, the perfluoro polyether is also referred as a“bifunctional perfluoro polyether”.
  • the next steps involved in the present invention will be the preparation of an organic suspension of the functionalized precipitated silica particulates described before, and of an organic solution of crosslinkable polyurethane polymer precursors.
  • polyurethane polymer precursor compositions are also widely available commercial products, which can be used as such after dilution in an organic solvent, in an amount which will be generally comprised between 50 and 100 % in weight, more preferably between 70 and 95 % in weight.
  • suitable methods are known to the person skilled in the art.
  • substrates could be dipped in dip tanks containing the coating compositions in the form of a slurry, and thereafter dried.
  • Other methods worth being mentioned are spin coating and blade coating.
  • a preferred process which is particularly efficient in the present invention is a deposition carried out by spraying the liquid coating compositions on the surface of the substrate ⁇ spray coating ), providing thin layers in which a spontaneous drying and curing occurs even at ambient temperature of working.
  • the method to be implemented will depend on the thickness desired for the film, which is also dependent from the intended use for the coated substrate.
  • the thickness of the coatings of the invention may be comprised between 1 pm and 100 pm, particularly between 1 pm and 70 pm, and even more particularly between 1 pm and 50 pm.
  • T365 silica lg of T365 is dispersed in 20 ml of o-xylene and 1.4 g of S10 is added to the suspension.
  • the flask is heated at l20°C during 90 min to make the direct condensation of alcoxysilane from functionalizing agent with silanol groups of silica.
  • the slurry is filtrated under vacuum and washed with o-xylene to eliminate the S10 not chemically bonded on the silica surface. Finally, the powder is dried at l20°C overnight. 50 % in weight of S10 is grafted on T365 silica.
  • the functionalized precipitated silica (S10/T365) is dispersed in ethyl acetate (from 1 % to 10 %w). The solution is placed on ultrasonic bath during 30 minutes to obtain a homogeneous dispersion. Preparation of a polyurethane precursors formulation
  • Tolonate TM HDT-LV (3g) is added to butyl acetate (0.92 g) and methyl amyl ketone (0.85 g). Then, the Setalux 1907 BA-75 (9.5g) is added to this mixture and gently mixed with spatula.
  • the 2024-T3 Alclad aluminum substrate is cleaned with methyl amyl ketone, the polyurethane precursors formulation is sprayed and dried until at least 4 hours. In all cases, this step is needed to enhance interactions of coating with aluminum substrate.
  • the coating is referenced as Sample 1.
  • a polyurethane precursors formulation is sprayed on aluminum substrate (PU primer layer) and dried until at least 4 hours before spraying of the functionalized precipitated silica dispersion at 5 %w in ethyl acetate.
  • the coating is referenced as Sample 2.
  • the functionalized precipitated silica dispersion at 5 %w in ethyl acetate is prepared and added to the PU precursors formulation in order to have different percentage of functionalized precipitated silica particles in PU precursors.
  • a polyurethane precursors formulation is sprayed on aluminum substrate (PU primer layer) and dried until at least 4 hours before spraying of the mixture comprising functionalized precipitated silica dispersion at 5 %w in ethyl acetate and PU precursors.
  • an automated tilting cradle consisting of a frame that supports Biolin Optical Tensiometer on an axle turned by a motor on one end and a pivot on the other is used.
  • the motor is driven by the One Attension software to turn Biolin Optical Tensiometer at precise speeds to defined angles.
  • the stage tilts so tilts the camera and thus the image onscreen is similar to what would be seen with a standard contact angle experiment and allows estimating roll-off angles of the coating.
  • Roll-off angles from 0° to 90° can be measured with an angular resolution at 0.1°.
  • the coating is placed on vacuum stage to avoid any movement of the coating.
  • the results are reported in the Table 1.
  • the super hydrophobic properties (WCA > 150 ° and low roll-off angle) are obtained when functionalized precipitated silica dispersion at 5 %w in ethyl acetate is sprayed on PU primer layer.
  • the super hydrophobic behavior is obtained when at least 30 %w of functionalized precipitated silica in PU precursors formulation is incorporated.
  • a critical amount of functionalized precipitated silica in PU matrix is needed to obtain surface nanoroughness producing superhydrophobic properties.
  • Ice-rain testing of samples 1, 2 & 9 are performed in the IFAM ice-chamber (apparatus available at Fraunhofer Institute for Manufacturing Technology and Advanced Materials IFAM, Bremen, Germany).
  • ice grade level defined from 0 (ice-free) to 5 (extensive and nearly complete ice coverage) with increasing ice formation on the surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un article présentant de meilleures propriétés de surface hydrophobes et/ou glaciophobe comprenant un substrat et une composition de revêtement déposée sur la surface dudit substrat, ladite composition de revêtement comprenant (i) un ou plusieurs polymères de polyuréthane réticulés et (ii) des particules de silice précipitée fonctionnalisées avec un composé polyfluoré linéaire présentant au moins un groupe terminal α,ω alcoxysilane, lesdites particules de silice fonctionnalisées étant soit incorporées à l'intérieur des polymères de polyuréthane réticulés soit déposées sur la surface extérieure d'une couche séparée desdits polymères de polyuréthane réticulés. L'invention concerne également un procédé de préparation d'un tel article, et les particules de silice précipitée fonctionnalisées utilisées dans ce procédé.
PCT/EP2018/085711 2017-12-22 2018-12-18 Procédés et compositions pour le traitement de surface de substrats et articles obtenus avec ceux-ci WO2019121829A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17306903.0 2017-12-22
EP17306903 2017-12-22

Publications (1)

Publication Number Publication Date
WO2019121829A1 true WO2019121829A1 (fr) 2019-06-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3636702A1 (fr) 2019-12-06 2020-04-15 Solvay Specialty Polymers Italy S.p.A. Revêtement hydrophobe
WO2022023476A1 (fr) * 2020-07-30 2022-02-03 Fundación Cidetec Revêtements répulsifs et leur utilisation

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0520862A1 (fr) 1991-06-26 1992-12-30 Rhone-Poulenc Chimie Procédé de préparation de silice précipitée, silices précipitées obtenues et leur utilisation au renforcement des élastomères
WO1999007237A1 (fr) 1997-08-06 1999-02-18 Rhodia Chimie Composition comprenant un liquide absorbe sur un support a base de silice precipitee
WO1999049850A1 (fr) 1998-03-30 1999-10-07 Rhodia Chimie Composition comprenant un liquide absorbe sur un support a base de silice precipitee
EP1810987A1 (fr) 2004-07-09 2007-07-25 Solvay Solexis S.p.A. Séparation de perfluoropolyether monofonctionnels des groupes methylol
US7329784B2 (en) 2005-03-10 2008-02-12 Solvay Solexis Process for preparing peroxidic perfluoropolyethers
WO2012170832A1 (fr) 2011-06-08 2012-12-13 University Of Virginia Patent Foundation Revêtements nanocomposites superhydrophobes
US20140208978A1 (en) 2013-01-30 2014-07-31 Illinois Tool Works, Inc. Super hydrophobic coating
EP2966112A1 (fr) * 2013-03-06 2016-01-13 Unimatec Co., Ltd. Particules composites de nano-silice contenant du fluor et leur procédé de préparation
US20160289810A1 (en) * 2008-10-07 2016-10-06 Ross Technology Corporation Highly Durable Superhydrophobic, Oleophobic and Anti-Icing Coatings and Methods and Compositions for Their Preparation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0520862A1 (fr) 1991-06-26 1992-12-30 Rhone-Poulenc Chimie Procédé de préparation de silice précipitée, silices précipitées obtenues et leur utilisation au renforcement des élastomères
WO1999007237A1 (fr) 1997-08-06 1999-02-18 Rhodia Chimie Composition comprenant un liquide absorbe sur un support a base de silice precipitee
WO1999049850A1 (fr) 1998-03-30 1999-10-07 Rhodia Chimie Composition comprenant un liquide absorbe sur un support a base de silice precipitee
EP1810987A1 (fr) 2004-07-09 2007-07-25 Solvay Solexis S.p.A. Séparation de perfluoropolyether monofonctionnels des groupes methylol
US7329784B2 (en) 2005-03-10 2008-02-12 Solvay Solexis Process for preparing peroxidic perfluoropolyethers
US20160289810A1 (en) * 2008-10-07 2016-10-06 Ross Technology Corporation Highly Durable Superhydrophobic, Oleophobic and Anti-Icing Coatings and Methods and Compositions for Their Preparation
WO2012170832A1 (fr) 2011-06-08 2012-12-13 University Of Virginia Patent Foundation Revêtements nanocomposites superhydrophobes
US20140208978A1 (en) 2013-01-30 2014-07-31 Illinois Tool Works, Inc. Super hydrophobic coating
EP2966112A1 (fr) * 2013-03-06 2016-01-13 Unimatec Co., Ltd. Particules composites de nano-silice contenant du fluor et leur procédé de préparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
THE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, February 1938 (1938-02-01), pages 309

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3636702A1 (fr) 2019-12-06 2020-04-15 Solvay Specialty Polymers Italy S.p.A. Revêtement hydrophobe
WO2022023476A1 (fr) * 2020-07-30 2022-02-03 Fundación Cidetec Revêtements répulsifs et leur utilisation

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