EP1325052A1 - Polyisocyanates fluores sequences - Google Patents

Polyisocyanates fluores sequences

Info

Publication number
EP1325052A1
EP1325052A1 EP01980346A EP01980346A EP1325052A1 EP 1325052 A1 EP1325052 A1 EP 1325052A1 EP 01980346 A EP01980346 A EP 01980346A EP 01980346 A EP01980346 A EP 01980346A EP 1325052 A1 EP1325052 A1 EP 1325052A1
Authority
EP
European Patent Office
Prior art keywords
fluorine
blocked
polyisocyanates
equivalent
containing polyisocyanates
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.)
Withdrawn
Application number
EP01980346A
Other languages
German (de)
English (en)
Inventor
Eberhard Koenig
Beate Baumbach
Christian Füssel
Juan Gonzalez-Blanco
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.)
Covestro Deutschland AG
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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1325052A1 publication Critical patent/EP1325052A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8074—Lactams
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • the invention relates to new fluorine-containing blocked polyisocyanates, their production and use for the production of polyurethane plastics, preferably as a crosslinking component for stoving enamels, in particular for the coil coating process.
  • Modification component is mentioned either in the OH or in the NCO component of coating materials.
  • Blocked polyisocyanates containing built-in fluorine are described, for example, in US Pat. Nos. 5,541,281 and 5,576,411. These are polyisocyanates with allophanate, isocyanurate and urethane groups, which are produced by reacting fluorine-substituted alcohols and monomeric diisocyanates. It is clear to the person skilled in the art that the production of fluorine-containing polyisocyanates from the basic isocyanates u. a. because of the to be carried out to remove the toxic starting isocyanates (cleaning)
  • Thin film distillation is a relatively complex process.
  • fluorine-containing isocyanates have a limited area of application and thus represent so-called niche products.
  • the object of the invention is now to show an alternative solution for providing fluorine-containing polyisocyanates.
  • An alternative to the known way is seen in the modification of commercially available paint polyisocyanates with fluoroalcohols.
  • the object of the invention is therefore to develop fluorine-containing blocked polyisocyanates by a simple method from conventional lacquer polyisocyanates, which can be used to produce polyurethane plastics, preferably stoving lacquers with a water- and dirt-repellent surface.
  • the invention relates to blocked fluorine-containing polyisocyanates containing
  • the new blocked polyisocyanates are essential to the invention from three components aliphatic polyisocyanate,
  • Another object of the invention is a process for the preparation of blocked, fluorine-containing polyisocyanates, characterized in that polyisocyanates are optionally introduced in a solvent with stirring at a temperature of 50 - 70 ° C, then the monofunctional, fluorine-substituted alcohol is added and at 80 - 110 ° C until the calculated NCO content is reacted and then the remaining NCO groups are reacted with the appropriate amount of blocking agent at 70 - 110 ° C. NCO groups are then no longer detectable, e.g. B. by means of the IR spectrum.
  • the polyurates according to the invention are produced using the known biuret, isocyanurate, allophanate, iminooxadiazinedione (asymmetric
  • aliphatic or cycloaliphatic diisocyanates are 1,6-diisocyanatohexane (HDI), l-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI), bis- (4-isocyanatocyclohexyl ) - methane (H i2 MDI or Desmodur W ® / Bayer AG), 2,6 or 2,5-bis-isocyanato-norbornan or 1,4-bis-isocyanatomethyl-cyclohexane and 1,3- or 1,4-tetramethyl-xylylene diisocyanate.
  • Isocyanurate groups are predominantly preferred
  • Polyisocyanates based on 1,6-diisocyanatohexane, IPDI and Desmodur W ® As a blocking agent for the polyisocyanates according to the invention, oximes such. B. butanone oxime, secondary aliphatic amines, such as. B. diisopropylamine, CH-acidic compounds such. B. Malon or acetoacetic ester, NH-acidic heterocycles, such as. B. 1,2,4-triazole, imidazole or 3,5-dimethylpyrazole, lactams, such as. B. ⁇ -caprolactam, alcohols, such as. B. methanol, ethanol or n-propanol or any mixtures of these blocking agents. ⁇ -Caprolactam, diisopropylamine or ethanol are particularly preferred.
  • aliphatic or cycloaliphatic alcohols with a molecular weight of 150 to 500 and a fluorine content of 30-80% by weight are suitable as fluorine units for the production of the polyisocyanates according to the invention.
  • the addition products of perfiuoroethyl iodide, perfluorobutyl iodide or perfluorhexyl iodide with allyl alcohol to the corresponding fluorinated alcohols such as pentafluoropentan-1-ol (M 178, fluorine content: 53%), nonafluorheptan-1-ol (C 7 H 7 F 9 O, M 278, F - 61.5%) and Undecanfluornonan-1-ol (M 378, F -55%).
  • 4,4,5,5,6,6JJJ-Nonafluorheptan-l-ol is particularly preferred, which is available, for example, from the following reference: NO Brace, J. Fluorine Chern. 1982,
  • Another object of the invention is the use of the fluorine-containing, blocked polyisocyanate according to the invention as a crosslinking agent in the production of
  • the fluorine-containing blocked polyisocyanates according to the invention are preferably used as crosslinking agents (components) for the preparation of binders for polyurethane coatings.
  • a storage-stable paint binder from the polyisocyanate according to the invention as a crosslinking agent and e.g. of an OH component
  • the OH component is that in polyurethane chemistry and preferably in
  • Paint technology usual OH and / or NH-containing components into consideration, for example Poly (meth) acrylate resins containing OH groups, polyols, polyester polyols, polyester urethanes, (poly) amino alcohols, polyamines, etc.
  • the invention therefore furthermore relates to paint binders containing the fluorinated, blocked polyisocyanates according to the invention and crosslinker components containing OH and / or NH and, if appropriate, customary additives and / or auxiliaries.
  • lacquers produced as crosslinkers with the fluorine-containing, blocked polyisocyanates according to the invention impart water-repellent and subsequently self-cleaning properties to the resulting lacquer surface. They are used to coat any substrates such as stone, masonry, concrete, wood, glass, ceramics, plastics, and metals. They are preferably used for coating metal sheets such as body parts of vehicles.
  • Another subject is therefore also substrates which are coated with the lacquers containing the blocked fluorine-containing polyisocyanates according to the invention.
  • the water edge angle and the critical angle of inclination serve as physical parameters for evaluating these properties.
  • Devices for measuring water edge angles are commercially available.
  • the water edge angle of a drop of water on a paint surface says something about the degree of wetting of the drop on the paint.
  • the water edge angle itself is created by projecting a tangent onto the drops lying on a flat surface. If the curvature of the drop is a hemisphere, then this tangent forms an angle of 90 ° with the paint surface (FIG. 1). In the case of water-repellent surfaces, the drop is pushed away from the surface with the same volume, the wetting area becomes smaller and the measured area
  • Water edge angle greater than 90 °. In extreme cases, such as drops of mercury, there is only one point of contact with the surface. The contact angle is then 180 °.
  • the fluorinated, blocked polyisocyanates according to the invention can be prepared in a simple manner with the lacquer polyisocyanates present on an industrial scale.
  • the new crosslinkers result in good water or dirt-repellent coil coating lacquers, as will be explained in more detail in the following examples.
  • This perfluorinated alcohol can by a process known from the literature by radical addition of commercially available perfluorobutyl iodide to AUyl alcohol and subsequent hydrodeiodination with z.
  • This alcohol is a colorless liquid (bp. 5 mbar 83-85 ° C) with a molecular weight of 278 and a fluorine content of 171 g or 61.5%.
  • the two polyisocyanates, MPA and the perfluoroalcohol are heated to 100 ° C. with stirring.
  • the mixture is stirred at 100 ° C for about 1 hour until the calculated NCO content of 9.2% is reached or just below.
  • the total amount of solid caprolactam is introduced and stirred at 110 ° C until after about 2 hours no more NCO content is detectable, for.
  • An analogous crosslinker is produced with the polyisocyanate component according to Example 2 and ⁇ -caprolactam but without the perfluoroalcohol.
  • This crosslinker has a solids content of 65% and a blocked NCO equivalent of 528 g.
  • Binder I contains 1.69% by weight, based on solids, of fluorine in built-in form.
  • the clear lacquer batches are mixed homogeneously using a Skandex mixer.
  • the varnishes are adjusted to the processing viscosity (approx. 70 sec. DIN 4/23 ° C) by adding Solventnaphta 200 S.
  • the clear coats are applied by knife coating on chromated aluminum sheets (1 mm thick). Immediately after applying the paint, the sheets / paints are baked in the Aalborg oven on the turntable at an oven temperature of 350 ° C. With a residence time of 38 seconds at 350 ° C, an object temperature (PMT) of 232 ° C is set. Before applying the above clear coats in a dry layer thickness of 8-10 ⁇ m, a brown pigmented basecoat layer (19-22 ⁇ m) was already applied. c) clearcoat properties
  • the fluorine-containing lacquer I has a significantly larger water edge angle, ie the wetting area of the water drop is smaller, and a smaller angle of inclination than the comparison lacquer, ie the tendency to unroll and thus self-cleaning of the surface is promoted. This could be demonstrated by the soot uptake of a drop of water with the above-described "manual test to test the self-cleaning properties".
  • the soot uptake of a drop of water with the above-described "manual test to test the self-cleaning properties”.
  • On the fluorine-containing varnish I the complete is until the water drop is saturated after 5 cm Soot amount taken (100% take-away). Soot remains on Comparative Paint II, especially at the edges of the walkway, and the carry-over is only approx. 30%.
  • the fluorine-containing coating shows clearly self-cleaning properties.

Landscapes

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

Abstract

L'invention concerne de nouveaux polyisocyanates fluorés séquencés, leur préparation et leur utilisation pour la production de matières plastiques de polyuréthanne, de préférence sous la forme de composant réticulant destiné à des peintures au four appliquées notamment selon le procédé d'enduction de bandes en continu.
EP01980346A 2000-09-20 2001-09-07 Polyisocyanates fluores sequences Withdrawn EP1325052A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10046473A DE10046473A1 (de) 2000-09-20 2000-09-20 Fluorhaltige blockierte Isocyanate
DE10046473 2000-09-20
PCT/EP2001/010306 WO2002024781A1 (fr) 2000-09-20 2001-09-07 Polyisocyanates fluores sequences

Publications (1)

Publication Number Publication Date
EP1325052A1 true EP1325052A1 (fr) 2003-07-09

Family

ID=7656885

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01980346A Withdrawn EP1325052A1 (fr) 2000-09-20 2001-09-07 Polyisocyanates fluores sequences

Country Status (9)

Country Link
US (1) US6509433B2 (fr)
EP (1) EP1325052A1 (fr)
JP (1) JP2004509998A (fr)
KR (1) KR20030045075A (fr)
CN (1) CN1461320A (fr)
AU (1) AU2002212211A1 (fr)
CA (1) CA2422393A1 (fr)
DE (1) DE10046473A1 (fr)
WO (1) WO2002024781A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7482420B2 (en) 2004-03-24 2009-01-27 Construction Research & Technology Gmbh Silane-terminated polyurethanes with high strength and high elongation
US8563115B2 (en) * 2008-08-12 2013-10-22 Xerox Corporation Protective coatings for solid inkjet applications
TWI449777B (zh) * 2012-10-31 2014-08-21 Jinex Corp Ltd 短碳鏈氟素聚氨酯化合物及含其之撥水撥油劑
WO2016091633A1 (fr) * 2014-12-08 2016-06-16 Basf Coatings Gmbh Compositions d'agents de revêtement et revêtements produits à partir de celles-ci et utilisation associée

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0263983B1 (fr) * 1986-09-16 1992-12-23 Takeda Chemical Industries, Ltd. Compositions de résine à un seul composant et leur durcissement
US5496642A (en) * 1994-05-09 1996-03-05 Olin Corporation Low VOC, fluorocompound-containing one-component and two-component coating compositions for slippery coatings
US5576411A (en) 1994-09-14 1996-11-19 Bayer Corporation Low surface energy polyisocyanates and their use in one-or two component coating compositions
US5541281A (en) 1994-12-20 1996-07-30 Bayer Corporation Low surface energy polyisocyanates and their use in one- or two-component coating compositions
US5777061A (en) * 1996-02-14 1998-07-07 Bayer Corporation Blocked polyisocyanate crosslinkers for providing improved flow properties to coating compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0224781A1 *

Also Published As

Publication number Publication date
DE10046473A1 (de) 2002-03-28
CN1461320A (zh) 2003-12-10
AU2002212211A1 (en) 2002-04-02
KR20030045075A (ko) 2003-06-09
US6509433B2 (en) 2003-01-21
US20020123642A1 (en) 2002-09-05
CA2422393A1 (fr) 2003-03-13
WO2002024781A1 (fr) 2002-03-28
JP2004509998A (ja) 2004-04-02

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