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WO2025233276A1 - Compositions de revêtement en poudre polymère - Google Patents

Compositions de revêtement en poudre polymère

Info

Publication number
WO2025233276A1
WO2025233276A1 PCT/EP2025/062213 EP2025062213W WO2025233276A1 WO 2025233276 A1 WO2025233276 A1 WO 2025233276A1 EP 2025062213 W EP2025062213 W EP 2025062213W WO 2025233276 A1 WO2025233276 A1 WO 2025233276A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
pas
polymer composition
paek
particle size
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.)
Pending
Application number
PCT/EP2025/062213
Other languages
English (en)
Inventor
Debora SALA
Manuele DELVINO
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.)
Syensqo Specialty Polymers Usa LLC
Original Assignee
Syensqo Specialty Polymers Usa LLC
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 Syensqo Specialty Polymers Usa LLC filed Critical Syensqo Specialty Polymers Usa LLC
Publication of WO2025233276A1 publication Critical patent/WO2025233276A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones

Definitions

  • the present disclosure relates to the field of high temperature resistant coatings. More particularly, the coatings comprise compositions comprising a poly(arylether ketone) polymer and a poly(arylene sulfide) polymer and they are endowed with high temperature performance, good chemical resistance and, at the same time, high adhesion to metal surfaces and toughness.
  • the present disclosure is directed to the use of a powder composition comprising a poly(arylether ketone) polymer and a poly(arylene sulfide) polymer for use in the preparation of coatings, in particular metal surface coatings to protect metal parts from corrosion even at high temperature and under harsh chemical environments.
  • Metal protection is a target across all industries: anti-corrosion in industrial and O&G, electrical insulation in transportation.
  • compositions that meet the above-mentioned requirements and can be hence used for coating applications.
  • the term “consisting essentially of” or “essentially consisting” indicates that the referred to composition contains less than 5 wt%, typically less than 2 wt% or less than 1 wt%, of any other ingredient.
  • the present invention relates to a polymer composition as defined in the appended claims.
  • the composition comprises a poly(arylene sulfide) polymer, hereinafter referred to as “PAS polymer”, and a poly(arylether ketone) polymer, hereinafter referred to as “PAEK polymer”.
  • PAS polymer poly(arylene sulfide) polymer
  • PAEK polymer poly(arylether ketone) polymer
  • Also disclosed herein is a method of coating metal surfaces comprising applying the disclosed polymer compositions to a metal surface.
  • the Applicant found that the disclosed polymer composition coated on a metal surface achieved good adhesion under the cross-cut test (ASTM D3359-23) and good hardness under the pencil hardness test (ASTM D 3363- 05).
  • the polymer composition of the invention comprises a PAS polymer and a PAEK polymer in a PAS/PAEK weight ratio from 10/90 to 75/25, wherein the polymer composition is in the form of a powder having an average particle size (dso) higher than 1.0 micrometer and/or below 100.0 micrometers, the average particle size measured by laser diffraction particle size analysis as volume particle size distribution.
  • dso average particle size
  • the polymer composition comprises the PAS polymer and the PAEK polymer in a PAES/PAEK weight ratio from 20/80 to 75/25, preferably in a PAS/PAEK weight ratio from 20/80 to 70/30, and still more preferably in a PAS/PAEK weight ratio from 30/70 to 70/30.
  • the polymer composition is in the form of a powder, and the powder has an average particle size (dso) higher than 1.0 micrometer, typically higher than 2.0 micrometers, preferably higher than 3.0 micrometers.
  • the average particle size (dso) is generally below 50.0 micrometers, preferably below 30.0 micrometers. Satisfactory results in terms of performance were obtained with powders having an average particle size (dso), in the range 10.0 to 30.0 micrometers.
  • the particle size distribution is measured by laser diffraction particle size analysis. Unless explicitly indicated the particle size distribution is a volume-based particle size distribution.
  • the average particle size (dso) of the polymer composition in the form of the powder is described with respect to the polymer composition.
  • Each of the PAS polymer and the PAEK polymer can have an individual average particle size (dso).
  • This individual average particle size (dso) is not so limited as described herein so long as the average particle size (dso) of the polymer composition in the form of a powder is within the ranges as described herein.
  • both the PAS polymer powder and the PAEK polymer powder will have average particle size (dso) higher than 1.0 micrometer and/or below 100.0 micrometers.
  • the average particle size (dso) of the PAS polymer and the PAEK polymer is preferably higher than 2.0 micrometers, more preferably higher than 3.0 micrometers and/or below 50.0 micrometers, preferably below 30.0 micrometers.
  • poly(arylene sulfide) polymer refers to any polymer including at least 50 mol% of a recurring unit (RPAS) having the following formula: -[-Ar-S-]-, where Ar is an arylene.
  • the PAS polymer can have at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or at least 99.9 mol% of recurring units (RPAS).
  • the recurring unit (RPAS) is advantageously represented by a formula selected from the following group of formulae: wherein R, at each instance, is independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6-C24 arylene group, and a Ce-C aryloxy group; T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl and -CH2-; k, at each instance, is 0 or an independently selected integer from 1 to 4; and I, at each instance, is 0 or an independently selected integer from 1 to 3.
  • the PAS polymer can include any isomeric relationship of the sulfide linkages in polymer backbone; e.g., when the arylene group is a phenylene group, the sulfide linkages can be ortho, meta, para, or combinations thereof.
  • Suitable examples of a PAS polymer as described above include, but are not limited to, poly(2,4-toluene sulfide), poly(4,4'-biphenylene sulfide), poly(para- phenylene sulfide) (PPS), poly(ortho-phenylene sulfide), poly(meta-phenylene sulfide), poly(xylene sulfide), poly(ethylisopropylphenylene sulfide), poly(tetramethylphenylene sulfide), poly(butylcyclohexylphenylene sulfide), poly(hexyldodecylphenylene sulfide), poly(octadecylphenylene sulfide), poly(phenylphenylene sulfide), poly-(tolylphenylene sulfide), poly(benzylphenylene sulfide) and
  • the PAS polymer can be obtained by a process known in the art. Reference can notably be made to WO 2015/095362 (Chevron Philipps), WO 2015/177857 (Solvay) and WO 2016/079243 (Solvay). [0028] Preferably, -Ar- is represented by either Formula (1 ) or (2), more preferably
  • the PAS polymer consists essentially of recurring units (RPAS) of Formula (4).
  • the PAS polymer can have a weight average molecular weight (“Mw”) of at least 10,000 g/mol, at least 20,000 g/mol, at least 25,000 g/mol, at least 30,000 g/mol, or at least 35,000 g/mol. In some embodiments, the PAS polymer has an Mw of no more than 150,000 g/mol, no more than 100,000 g/mol, no more than 90,000 g/mol, no more than 85,000 g/mol, or no more than 80,000 g/mol.
  • Mw weight average molecular weight
  • the PAS polymer has an Mw of from 10,000 g/mol to 150,000 g/mol, from 20,000 g/mol to 100,000 g/mol, from 25,000 g/mol to 90,000 g/mol, from 30,000 g/mol to 85,000 g/mol, or from 35,000 g/mol to 80,000 g/mol.
  • Mw can be measured with gel permeation chromatography (“GPC”) using a 4- chloronapthalene standard.
  • the PAS polymer can be semi-crystalline.
  • the person of ordinary skill in the art will recognize that when a polymer is amorphous, it lacks a detectable Tm. Accordingly, when a PAS polymer has a Tm, the person of ordinary skill in the art will recognize that it refers to semi-crystalline polymer.
  • the PAS polymer can also have a AHf of at least 10 J/g, at least 20 J/g, at least, or at least 25 J/g. Alternatively, or in addition, the PAS polymer can have a AHf of no more than 90 J/g, no more than 70 J/g or no more than 60 J/g.
  • the PAS polymer can have a AHf of from 10 J/g to 90 J/g or from 20 J/g to 70 J/g.
  • the PAS polymer can have a melting temperature (“Tm”) of at least 200°C, at least 220°C, at least 240°C, or at least 250°C.
  • Tm melting temperature
  • the PAS polymer can have a Tm of no more 350°C, no more than 320°C, no more than 300 °C, or no more than 285°C.
  • the PAS polymer can have a Tm of from 200°C to 350°C, from 220°C to 320°C, from 240°C to 300°C, or from 250°C to 285°C.
  • the polymer composition of the invention comprises a poly(arylether ketone) (PAEK) polymer.
  • PAEK poly(arylether ketone)
  • the PAEK polymer is a polymer comprising more than 50 mol% of recurring units (RPAEK), wherein recurring units (RPAEK) comprise a Ar — C(O) — Ar' group, wherein Ar and Ar', equal to or different from each other, are aromatic groups.
  • the PAEK polymer comprises at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.%, at least 99.5 mol%, or at least 99.9 mol% of recurring units (RPAEK) .
  • mol.% is relative to the total number of moles of recurring units in the PAEK polymer.
  • recurring units are selected from the group consisting of formulae (J 1 - A) to (J'-O) below:
  • the PAEK polymer is conveniently poly(etherether ketone) (PEEK).
  • PEEK poly(etherether ketone)
  • the PEEK polymer has recurring units (RPAEK) represented by formula (J'-A).
  • PEEK polymers suitable for the compositions of the invention have a melt flow rate, measured according to ASTM standard D1238 at 400°C and 2.16 kg in the range of 2 to 40 g/10 min, preferably 2 to 20 g/10 min.
  • the presently disclosed polymer compositions can contain at least one additive, such as those commonly used in coating applications.
  • Non-limiting examples of suitable additives are anti-rust agents, antioxidants, thermal stabilizers, anti-wear agents, including those for high pressure, tracers, rheological modifiers, flowability controlling agents, corrosion inhibitors, pigments, dyestuffs, and fillers.
  • Each of the disclosed at least one additive can be present in the polymer composition in an amount from 0 to 15 wt% based on the total weight of the polymer composition.
  • the presently disclosed polymer compositions can be manufactured by powder blending. Such a process is typically carried out by mixing fine powders of the PAS polymer and the PAEK polymer in the desired amounts.
  • fine powders refers to powder at least 90% of which pass thru a 150 micrometres screen or finer. This process can be carried out in a solid or fine powder mixer.
  • the mixer types that can be used for this purpose include tumble type mixers, ribbon type mixers, impeller type mixers, also known as high intensity mixers, shaker type mixers, as well as other types of solids and powders mixers known in the art.
  • the polymer composition of the invention can be manufactured by preparing a blend comprising the PAS polymer and the PAEK polymer in the desired weight ratio and then making a powder.
  • the blend comprising the PAS polymer and the PAEK polymer can be made for instance by melt mixing of the polymers.
  • inventive compositions are applied over the substrate to be coated.
  • the polymer composition can be applied to the substrate by powder coating or slurry coating.
  • the inventive composition is applied in dry, free flowing, solid powder form over the substrate to be coated.
  • the substrate is not particularly limited, and may, for example, be an inorganic material, an organic material, an organic-inorganic composite material.
  • the inorganic material may, for example, be concrete, natural stone, glass, metal, such as iron, stainless steel, aluminum, copper, brass, titanium.
  • the organic material may, for example, be plastic, rubber, wood.
  • the organic-inorganic composite material may, for example, be fiber-reinforced plastic, resin-reinforced concrete, fiber-reinforced concrete.
  • metal is preferred.
  • the metal can be aluminum, steel, stainless steel, iron, copper, brass, titanium, alloys thereof, or any combination thereof.
  • inventive compositions may be applied as a one-coating system or as coating layer in a multi-layer arrangement.
  • the shape and/or size of the substrate are not particularly limited.
  • Any known coating method may be used. Mention can be made of an electrostatic coating method, an electrostatic spraying method, an electrostatic dipping method, a misting method, a flow immersion method, a blowing method, a spraying method, a melt spraying method, or a plasma spraying method.
  • the composition of the invention is applied to the substrate, preferably a metal substrate, by means of electrostatic powder coating technique.
  • the powder is applied electrostatically onto a substrate, which is heated at a suitable temperature to cause the powder to become fluid.
  • the temperature of the metal surface may conveniently be between 300°C and 400°C.
  • the layer formed by the powder composition of the invention on the metal surface is typically between 30 micrometers and 100 micrometers , preferably between 40 micrometers and 70 micrometers , more preferably between 50 micrometers and 70 micrometers .
  • Examples of objects to be coated include a tank, a vessel, a valve, a pump, a joint, a piping material, a part, and a sealing material, a cookware article, a smart device article, an automotive article, and the like.
  • the PAS polymer was a Ryton® PPS polymer having a melting temperature of 280°C and a melt flow rate of 100 g/10 min (measured according to ASTM method D1238 at 316°C, 5 kg). It is a commercially available poly(phenylene sulfide) polymer obtained from Solvay Specialty Polymers USA, LLC. The average particle size distribution by volume of the PAS polymer is given below in Table I.
  • the PAEK polymer was KetaSpire® PEEK having a melting temperature of 340°C and a melt flow rate of 3 g/10 min (measured according to ASTM method D1238 at 400°C, 2.16 kg). It is a commercially available poly(etherether ketone) polymer obtained from Solvay Specialty Polymers USA, LLC. The average particle size distribution of the PAEK polymer is given below in Table II.
  • the cross-cut test is a method of determining the resistance of coatings to separation from substrates by utilizing a tool to cut a right-angle lattice pattern into the coating, penetrating all the way to the substrate. All loose particles in the area of the cross-cut are removed with a soft brush. The surface is then evaluated visually with the eye by comparing the sectional raster image with the reference images from DIN EN ISO 2409. A cross-cut characteristic is assigned according to the number of squares that have flaked off and the appearance. Depending on the condition of the damage, a distinction is made between cross-cut parameters from 0 (very good adhesive strength) to 5 (very poor adhesive strength).
  • Table VII provides the results of the cross-cut adhesion test and pencil test for the PEAK and PAS polymers used in the preparation of the compositions.
  • the PAEK polymer coating was treated at 360°C for 10 minutes, while the PAS polymer coating was treated at 350°C for 30 minutes to account for the lower melting temperature of poly(phenylene sulfide).
  • compositions of the invention provide a balance between hardness of the coating and adhesion to various metallic substrates.
  • Compositions containing as little as 10 parts of PAS (Mix 6) showed improved adhesion to all substrates and increased hardness.
  • a good balance of properties is shown for compositions containing 30 parts of PEAK and 70 parts of PAS.

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions polymères comprenant un polymère de poly(sulfure d'arylène) (PAS) et un polymère de poly(aryl éther cétone) (PAEK). La composition polymère se présente sous la forme d'une poudre, et la poudre présente, en tant que distribution granulométrique en volume, une taille moyenne de particule (d50) supérieure à 1,0 micromètre et/ou inférieure à 100,0 micromètres telle que mesurée par analyse de taille de particule par diffraction laser. L'invention concerne également un procédé de revêtement de substrats, en particulier de surfaces métalliques, comprenant l'application des compositions polymères décrites sur un substrat.
PCT/EP2025/062213 2024-05-07 2025-05-05 Compositions de revêtement en poudre polymère Pending WO2025233276A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24174512 2024-05-07
EP24174512.4 2024-05-07

Publications (1)

Publication Number Publication Date
WO2025233276A1 true WO2025233276A1 (fr) 2025-11-13

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ID=91030353

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/062213 Pending WO2025233276A1 (fr) 2024-05-07 2025-05-05 Compositions de revêtement en poudre polymère

Country Status (1)

Country Link
WO (1) WO2025233276A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015095362A1 (fr) 2013-12-19 2015-06-25 Chevron Phillips Chemical Company Lp Procédé de production de poly(sulfure d'arylène)
WO2015177857A1 (fr) 2014-05-20 2015-11-26 株式会社島津製作所 Système d'introduction d'échantillons
WO2016079243A1 (fr) 2014-11-21 2016-05-26 Solvay Sa Procédé de production de poly(sulfure d'arylène)
US20190338119A1 (en) * 2016-12-28 2019-11-07 Toray Industries, Inc. Resin composition for bonding metal, production formed by bonding metal with resin composition, and manufacturing method thereof
WO2022223261A1 (fr) * 2021-04-19 2022-10-27 Solvay Specialty Polymers Usa, Llc Compositions et procédés pour la production de particules polymères submicroniques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015095362A1 (fr) 2013-12-19 2015-06-25 Chevron Phillips Chemical Company Lp Procédé de production de poly(sulfure d'arylène)
WO2015177857A1 (fr) 2014-05-20 2015-11-26 株式会社島津製作所 Système d'introduction d'échantillons
WO2016079243A1 (fr) 2014-11-21 2016-05-26 Solvay Sa Procédé de production de poly(sulfure d'arylène)
US20190338119A1 (en) * 2016-12-28 2019-11-07 Toray Industries, Inc. Resin composition for bonding metal, production formed by bonding metal with resin composition, and manufacturing method thereof
WO2022223261A1 (fr) * 2021-04-19 2022-10-27 Solvay Specialty Polymers Usa, Llc Compositions et procédés pour la production de particules polymères submicroniques

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