WO2017216379A1 - Polymère pour un revêtement antisalissure - Google Patents

Polymère pour un revêtement antisalissure Download PDF

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Publication number
WO2017216379A1
WO2017216379A1 PCT/EP2017/064839 EP2017064839W WO2017216379A1 WO 2017216379 A1 WO2017216379 A1 WO 2017216379A1 EP 2017064839 W EP2017064839 W EP 2017064839W WO 2017216379 A1 WO2017216379 A1 WO 2017216379A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
thiol
residues
hydrophilic
hydrophobic
Prior art date
Application number
PCT/EP2017/064839
Other languages
German (de)
English (en)
Inventor
Andreas Brinkmann
Jill Nieradzik
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority to EP17736578.0A priority Critical patent/EP3472226A1/fr
Publication of WO2017216379A1 publication Critical patent/WO2017216379A1/fr

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the invention relates to a polymer for an antifouling layer, producible by the reaction of a thiol with one or more coupling partners of the thiol, wherein the thiol and the coupling partner are chosen so that the polymer over a certain proportion of hydrophobic blocks and over a certain proportion of hydrophilic blocks.
  • the invention further relates to a mixture for producing such a polymer and to the use of such a polymer for an antifouling coating.
  • the invention relates to a process for the preparation of a corresponding polymer.
  • Gaining weight eg in vehicles, ships and boats
  • Change in surface increase in roughness change in hydrodynamic behavior, which in turn leads to increased fuel consumption, eg in ships,
  • biocides are added to the (optionally) contaminated by microorganisms medium to kill them or as a prophylaxis against the accumulation of such microorganisms.
  • a disadvantage of this method is that thereby biocides are released at least in the medium, so that the corresponding media can not be readily disposed of in the environment.
  • biocide-containing coating as so-called antifouling coatings.
  • the surfaces to be protected are coated with a biocide-containing coating material which releases biocide on the surface by different mechanisms of action and kills organisms located there.
  • a disadvantage of this method is that significant amounts of biocide are released into the respective medium and the corresponding coatings "bleed" in the long term if all the biocide has been released c)
  • biocide-free coatings based on silicones or other hydrophobic coating materials The purpose of the surface design is to cause reduced attachment of organisms without killing them, often causing a reduction in the force required to remove microorganisms from the surface.
  • the coating material according to the invention should be curable by various mechanisms in order to be able to take account of different application requirements.
  • This object is achieved by a polymer for an antifouling layer, producible by the reaction of a thiol with one or more coupling partners of the thiol, wherein the thiol and the coupling partner or partners are selected so that the polymer> 30 wt .-% hydrophobic blocks and > 5% by weight of hydrophilic blocks, based in each case on the total weight of the polymer, the hydrophobic blocks each having> 10 hydrophobic functions and the hydrophilic blocks each having> 3 hydrophilic functions and the thiol comprising at least two thiol groups.
  • Hydrophobic blocks within the meaning of the present invention are those portions of the polymer which (by themselves) have water-repellent properties.
  • Hydrophilic blocks in the context of the present invention are those subregions of the polymer which (considered alone) have hydrophilic properties.
  • Water-attracting or water-repellent means that the respective pure substance as a coating material of a surface has a static water edge angle of> 90 ° (water-repellent) or ⁇ 90 ° (water-attracting).
  • hydrophobic blocks within the meaning of the present invention, which are counted on the respective weight fraction comprise in each case> 10, preferably> 50, more preferably> 100 hydrophobic functions and the hydrophilic blocks which are counted for the respective weight fraction comprise> 3 in each case, preferably> 10 and more preferably> 20 hydrophilic functions.
  • the length of a hydrophobic block is determined in each case by a limiting hydrophilic function (terminal block) or two such functions, always viewed along the main chain of the polymer.
  • the length of a hydrophilic block is determined by the limitation of a hydrophobic function (terminal block) or two such functions, each along the main chain of the polymer.
  • Hydrophobic and hydrophilic functions are group or chain constituents which in each case impart the hydrophobic or hydrophilic property to the respective block. Preferred hydrophilic and hydrophobic functions are listed below.
  • the polymers according to the invention have a surprisingly good effect on inhibition of growth. This is - without being bound by theory - attributed to the respective proportions of hydrophilic and hydrophobic blocks in the polymer.
  • the antifouling property of coatings of the polymer according to the invention is preferably determined according to ASTM D3623-78a (2012) "Standard Test Method for Testing Anodizing Panels in Shallow Submergence".
  • a further advantage of the polymers to be used according to the invention is that they are curable (polymerizable) in two ways and can thus form very different mechanical, physical and chemical structural properties on the surface.
  • Preferred coupling partners of the thiol are selected from the group consisting of acrylic group, vinyl group, isocyanate group and epoxy group.
  • hydrophobic functions of the hydrophobic blocks are selected from the group consisting of hydrocarbon radicals, fluorinated hydrocarbon radicals, siloxane radicals, fluorinated siloxane radicals and silazane radicals.
  • Siloxane radicals are particularly preferred in this context as hydrophobic functions.
  • hydrophilic functions of the hydrophilic blocks are selected from the group consisting of glycol radicals, ether radicals, ester radicals, amine radicals and amide radicals.
  • Glycol radicals are particularly preferred in this context as hydrophilic functions.
  • hydrophilic functions in the hydrophilic blocks are glycol radicals and / or the hydrophobic functions in the hydrophobic blocks are siloxane radicals and / or the coupling partner of the thiol group is an acrylic group.
  • the monomers from which the polymer according to the invention is formed comprise two coupling functions or two thiol groups.
  • the preferred coupling function of a thiol is generally an acrylic group.
  • a polymer according to the invention is formed partly by radiation-induced and partly by ion-induced mechanism.
  • a preferred ion-induced mechanism is an addition reaction.
  • mixed polymerization with different mechanisms it is possible to adjust the desired surface functions and properties in a particularly suitable manner.
  • the coating resulting from the polymer comprise a microstructure. In this case, at least partial radiation curing (radical polymerization) is helpful in structuring.
  • a microstructure is understood to mean a structure introduced on the micrometer scale or sub-micrometer scale by means of printing, pressing or molding processes. This structure is introduced by a suitable tool, e.g. a transparent stamp containing a negative structure of the microstructure.
  • a radiation-curing mechanism be chosen.
  • the polymer according to the invention thus makes it possible to use very similar polymers (namely from the same monomers formed) in various ways. For example, it is possible to use the same monomer mixture for different application conditions.
  • a part of the present invention is a mixture for the preparation of a polymer for an antifouling layer according to the invention comprising a thiol and a coupling partner for the thiol, each as defined above.
  • a mixture according to the invention further comprising a compound for starting an ion-induced polymerization (eg a catalyst) and / or a compound for starting a radiation-induced polymerization.
  • a compound for starting an ion-induced polymerization eg a catalyst
  • a compound for starting a radiation-induced polymerization e.g. a radiation-induced polymerization.
  • Preferred compounds for starting an ion-induced polymerization in this case are amines, phosphines and generally Lewis acids such as gadolinium (III) triflates or tetrafluoroborates.
  • Preferred compounds for initiating radiation-induced polymerization in this context are ⁇ -hydroxy, ⁇ -alkoxy or ⁇ -aminoaryl ketones, e.g. o hydroxyketone and azo compounds or acylphosphine oxide.
  • Part of the invention is also the use of a polymer according to the invention for an antifouling coating. It is preferred in this context that the anti-tarnish coating consists of> 90% by weight, more preferably completely of the polymer according to the invention.
  • Part of the invention is also a process for the preparation of a polymer according to the invention comprising the steps: a) providing a mixture according to the invention or the individual constituents of such a mixture and b) polymerizing the thiol and the coupling partner of the thiol by means of an ionic and / or radiation-induced mechanism.
  • the polymer according to the invention can be produced for a growth-inhibiting coating by the process according to the invention.
  • the curing mechanisms can be selected, it being understood that the type of curing (polymerization) can be influenced by adding starter compounds for the particular polymerization mechanism.
  • antifouling coatings can be prepared with the polymers according to the invention.
  • Preferred substrates for the antifouling coatings of the polymers according to the invention are surfaces which are in permanent contact with water or building surfaces.
  • Preferred within the meaning of the present invention are the surfaces in contact with water of ships, bridges and other permanent water contact structures, the surfaces of water tanks and the surfaces of heat exchangers
  • a substrate coated according to the invention measured according to ASTM D3623-78a (2012), remains free of growth by microorganisms for one year.
  • Position 1 is presented in a suitable vessel. Gradually, positions 2 and 3 are added. Just before the application, positions 4 and 5 are added. Last, position 6 is added. Then the material is stirred (Speedmixer 200 rpm / 6 min) until a homogeneous mixture is obtained. Then the material can be applied (eg spraying, brushes, rollers, printing, etc.).
  • organic surfaces such as plastics or other paint layers, inorganic surfaces such as glass or ceramics, natural materials such as wood or metallic surfaces can be used. Each forms a solid coating.
  • Position 1 is presented in a suitable vessel. Gradually, positions 2 to 6 are added. Then the material is stirred (Speedmixer 200 rpm / 6 min) until a homogeneous mixture is obtained. Then the material can be applied (eg spraying, brushes, rollers, printing, etc.). After the acetone has escaped, the applied film can be cured with a UV source such as a mercury vapor lamp.
  • a UV source such as a mercury vapor lamp.
  • organic surfaces such as plastics or other paint layers, inorganic surfaces such as glass or ceramics, natural materials such as wood or metallic surfaces can be used. Each forms a solid coating.
  • Position 1 is presented in a suitable vessel. Gradually, positions 2 to 4 are added. Just before the application positions 5 and 6 are added. Last, position 7 is added. Then the material is stirred (Speedmixer 200 rpm / 6 min) until a homogeneous mixture is obtained. Then the material can be applied (eg spraying, brushes, rollers, printing, etc.). After the acetone has escaped, the applied film can be cured with a UV source such as a mercury vapor lamp. In parallel, the ion-induced curing mechanism takes place. As a substrate, organic surfaces such as plastics or other paint layers, inorganic surfaces such as glass or ceramics, natural materials such as wood or metallic surfaces can be used. Each forms a solid coating. Example 4
  • Position 1 is presented in a suitable vessel. Gradually, positions 2 to 5 are added. Then the material is stirred (Speedmixer 200 rpm / 6 min) until a homogeneous mixture is obtained. Subsequently, the material can be applied (e.g., syringes, brushes, rollers, printing, etc.).
  • Example 5 it has been found that it is not possible to cure the above composition to a sufficient extent for a coating.
  • 10 ⁇ 10 cm PVC test panels were prepared with a coating from Example 1 and outsourced over a breeding season March / May to September / October 2015 off Norderney in the sea. After each month the plate is evaluated for growth according to ASTM D3623 - 78a (2012).
  • Figure 1 presents the results of the vegetation assessment. Each inspection is one month away from the previous one and the first inspection was taken one month after removal from storage.
  • the fouling rating represents the proportion of the test area unoccupied by microorganisms. It can be seen that considerable fouling is still present even after five months. Similar results were also found for coated with coating according to Example 2 and 3 substrates.
  • a hydrophobic block is a hydrophilic block
  • Position 1 Triethylenediamine is placed in a suitable vessel. Then position 2 butyl acetate is added and the mixture is stirred. Preferably, a laboratory magnetic stirrer at about 500 U / min is used. After position 1 has dissolved in position 2, position 3 diethylenetriamine is added, while the product is stirred further. Thereafter, position 4 glycol di (3-mercaptopropionate) is weighed and the mixture is allowed to stir for 5 minutes at medium speed. Finally, just before application to the substrate of the second coupling partner, the Tegomer® V-Si 2250 (polydimethylsiloxane diacrylate) is added, thereby starting the reaction which is observed by a temperature increase. In particular, the substrates mentioned in Example 1 can be used as the substrate. Each forms a solid coating,

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

Abstract

L'invention concerne un polymère pour un revêtement antisalissure, pouvant être obtenu par réaction d'un thiol avec un ou plusieurs partenaires de couplage du thiol, ledit thiol et le ou les partenaires de couplage étant choisis de manière que le polymère comprenne ≥ 30% en poids de blocs hydrophobes et ≥ 5% en poids de blocs hydrophiles, respectivement par rapport au poids total du polymère, les blocs hydrophobes possédant chacun ≥ 10 fonctions hydrophobes et les blocs hydrophiles possédant chacun ≥ 3 fonctions hydrophiles.
PCT/EP2017/064839 2016-06-17 2017-06-16 Polymère pour un revêtement antisalissure WO2017216379A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP17736578.0A EP3472226A1 (fr) 2016-06-17 2017-06-16 Polymère pour un revêtement antisalissure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016210863.8 2016-06-17
DE102016210863.8A DE102016210863A1 (de) 2016-06-17 2016-06-17 Polymer für eine bewuchshemmende Schicht

Publications (1)

Publication Number Publication Date
WO2017216379A1 true WO2017216379A1 (fr) 2017-12-21

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ID=59295162

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/064839 WO2017216379A1 (fr) 2016-06-17 2017-06-16 Polymère pour un revêtement antisalissure

Country Status (3)

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EP (1) EP3472226A1 (fr)
DE (1) DE102016210863A1 (fr)
WO (1) WO2017216379A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489998A1 (fr) * 1989-06-16 1992-06-17 Hayashikane Paint Co., Ltd. Peinture antisalissure
US20090096136A1 (en) * 2007-10-12 2009-04-16 The Regents Of The University Of California Thiol-ene based poly(alkylsiloxane) materials
WO2009058079A1 (fr) * 2007-11-01 2009-05-07 Bactiguard Ab Revêtement lubrifiant, procédé de revêtement et article revêtu
EP2514776A1 (fr) * 2009-12-18 2012-10-24 Chugoku Marine Paints, Ltd. Copolymère vinylique à bloc organopolysiloxane-thio à réticulation métallique, et composition de revêtement antisalissure contenant le copolymère

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9169359B2 (en) * 2011-06-17 2015-10-27 Ndsu Research Foundation Functionalized silicones with polyalkylene oxide side chains
SG11201408581SA (en) * 2012-06-22 2015-01-29 Texas A & M Univ Sys Ternary antifouling compositions and methods

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489998A1 (fr) * 1989-06-16 1992-06-17 Hayashikane Paint Co., Ltd. Peinture antisalissure
US20090096136A1 (en) * 2007-10-12 2009-04-16 The Regents Of The University Of California Thiol-ene based poly(alkylsiloxane) materials
WO2009058079A1 (fr) * 2007-11-01 2009-05-07 Bactiguard Ab Revêtement lubrifiant, procédé de revêtement et article revêtu
EP2514776A1 (fr) * 2009-12-18 2012-10-24 Chugoku Marine Paints, Ltd. Copolymère vinylique à bloc organopolysiloxane-thio à réticulation métallique, et composition de revêtement antisalissure contenant le copolymère

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DR. M. NENDZA: "Prüfung der Auswirkungen von in Antifouling", FOUL-RELEASE-PRODUKTEN EINGESETZTEN SILICONÖLEN (POLYDIMENTHYLSILOXANEN, pages 23, ISSN: 1862-4804
V.A. KUSUMA ET AL: "Crosslinking poly(ethylene oxide) containing siloxanes fabricated through thiol-ene photochemistry", JORNAL OF POLYMER SCIENCE ,PART A:POLYMER CHEMISTRY, vol. 53, 2015, pages 1548 - 1557, XP002773692 *

Also Published As

Publication number Publication date
EP3472226A1 (fr) 2019-04-24
DE102016210863A1 (de) 2017-12-21

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