WO2006037756A1 - High performance shaped articles, methods of making, and uses thereof - Google Patents

High performance shaped articles, methods of making, and uses thereof Download PDF

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Publication number
WO2006037756A1
WO2006037756A1 PCT/EP2005/054937 EP2005054937W WO2006037756A1 WO 2006037756 A1 WO2006037756 A1 WO 2006037756A1 EP 2005054937 W EP2005054937 W EP 2005054937W WO 2006037756 A1 WO2006037756 A1 WO 2006037756A1
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WO
WIPO (PCT)
Prior art keywords
shaped article
polymer
article according
essentially
dimensional
Prior art date
Application number
PCT/EP2005/054937
Other languages
French (fr)
Inventor
Geoffrey Underwood
Brian A. Stern
Anthony Lippl
Shari Weinberg
Selvaraj Savariar
Mohammad Jamal El-Hibri
Original Assignee
Solvay Advanced Polymers, L.L.C.
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.)
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=35445694&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2006037756(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP20040106879 external-priority patent/EP1518883A2/en
Priority claimed from EP04106875A external-priority patent/EP1524297A1/en
Priority claimed from EP04106878A external-priority patent/EP1524298A1/en
Application filed by Solvay Advanced Polymers, L.L.C. filed Critical Solvay Advanced Polymers, L.L.C.
Priority to JP2007535144A priority Critical patent/JP2008516029A/en
Priority to US11/576,509 priority patent/US20090026128A1/en
Priority to CN2005800337048A priority patent/CN101035862B/en
Priority to EP10182512.3A priority patent/EP2272915B1/en
Priority to EP05791842.7A priority patent/EP1802704B1/en
Publication of WO2006037756A1 publication Critical patent/WO2006037756A1/en
Priority to ZA2007/02789A priority patent/ZA200702789B/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20Manufacture of shaped structures of ion-exchange resins
    • C08J5/22Films, membranes or diaphragms
    • C08J5/2206Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218Synthetic macromolecular compounds
    • C08J5/2256Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06Polysulfones; Polyethersulfones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06Polysulfones; Polyethersulfones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2938Coating on discrete and individual rods, strands or filaments

Definitions

  • the present invention relates to high-performance polymeric shaped articles which are essentially at most two-dimensional. These include essentially one-dimensional shaped articles like filaments or to high performance polymeric essentially two-dimensional shaped articles like films, sheets and slabs. It relates also to performing methods of making said shaped articles, and to end-uses of said shaped articles.
  • the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer a poor to medium heat resistance.
  • service requirements for numerous essentially one- or two-dimensional polymeric shaped articles include long term thermal exposure beyond 220°C, with excursions up to 300°C.
  • Non limitative examples of essentially two-dimensional shaped articles with such service requirements include cookware-, bakeware-, CPI-, semiconductor-, automotive-, industrial, and aerospace- coatings, as well as essentially two- dimensional shaped articles for aerospace applications other than coatings.
  • the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer a poor transparency.
  • these ones are notably essentially one- or two-dimensional polymeric shaped articles made out of high-temperature crystalline polymers like aromatic polyamides.
  • the essentially one- or two-dimensional polymeric shaped articles of the prior art may be difficult to shape.
  • shaped articles made of KAPTON ® resins cannot be fabricated by melt extrusion.
  • the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer poor to medium mechanical performances.
  • essentially one- or two-dimensional polymeric shaped articles with improved mechanical performances including notably good retention of modulus at high temperature and reduced loss of mechanical properties over extended time and temperature cycles.
  • the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer poor to medium chemical resistance to chemical agents, notably to strong acids, strong bases, aliphatic hydrocarbons and aromatic hydrocarbons, and have medium to poor hydro lytic stability.
  • chemical agents notably to strong acids, strong bases, aliphatic hydrocarbons and aromatic hydrocarbons, and have medium to poor hydro lytic stability.
  • the essentially one- or two-dimensional polymeric shaped articles of the prior art may be very expensive.
  • these ones are notably shaped articles made of Kapton ® resins.
  • Kapton ® resins there is another need for high performance essentially one- or two-dimensional polymeric shaped articles at a moderate cost.
  • an essentially at most two-dimensional shaped article comprising at least one polymer composition (C) comprising at least one high glass transition temperature sulfone polymer (P).
  • any shaped article is three-dimensional, and can thus be characterized notably by three characteristic dimensions ("length”, “width” and “height”).
  • characteristic dimensions length, width and “height”
  • some shaped articles are such that one or two of their characteristic dimensions is (are) considerably lower than respectively the other two ones or the third one.
  • the terms "considerably lower” should generally be understood as “more than 5 times lower” and preferably as “more than 10 times lower”, unless they characterize a "two-dimensional thickness” as defined hereafter in the description.
  • an essentially two-dimensional shaped article is intended to denote a shaped article of which one of its characteristic dimensions ("thickness-height") is considerably lower than its other two ones ("width” and "length"), while an essentially one-dimensional shaped article is intended to denote a shaped article of which two out of its characteristic dimensions (“thickness-width” and “thickness-height") are considerably lower than its third one ("length”).
  • essentially two-dimensional articles have essentially the appearance of a geometric surface, while essentially one-dimensional articles have essentially the appearance of a geometric line.
  • an essentially two-dimensional article can be viewed as a suria.ce (with a certain length and a certain width) differing from a geometric surface in that it has a certain non-zero thickness (typically in a direction perpendicular to the surface), said non-zero thickness being however considerably lower than the square root of the surface area developed by the surface itself and, more precisely, said non-zero thickness being considerably lower than both the length and the width of the surface itself ;
  • an essentially one-dimensional article can be viewed as a line (of a certain length) differing from a geometric line, essentially in that it has a non-zero "two- dimensional thickness" (typically in a plane perpendicular to the line, with a certain non-zero thickness-width and a certain non-zero thickness-height as characteristic dimensions), said non-zero two-dimensional thickness being however considerably lower (here specifically, the terms "considerably lower", which characterize a two-dimensional thickness, should generally be understood as "more than 25 times
  • the geometric surface can be curved or plane, twisted or untwisted ; the geometric line can be a straight line or a curved line.
  • Essentially zero-dimensional articles i.e. articles having essentially the appearance of a geometric point (sometimes also referred to as "material point"), with essentially no length, no width and no height, like powdery spherical particles of polymer or powdery spherical inorganic particles coated with a polymer (with a typical diameter of a few microns), are not shaped articles within the meaning of the present invention.
  • an essentially at most two-dimensional shaped article can be either an essentially two-dimensional shaped article or an essentially one- dimensional shaped article.
  • the local thickness ⁇ associated to a material point of coordinates (x,y,z), is defined as the length of the shortest straight line D including the material point of concern, which goes right through the shaped article (i.e. which goes from the material point where D enters the shaped article to the material point where D exits the shaped article).
  • high glass transition temperature sulfone polymer [polymer (P)] is intended to denote any polymer, of which more than 50 wt. % of the recurring units are recurring units (Rl) :
  • Preferred recurring units (Rl) are those wherein Q is a group chosen among the following structures :
  • n integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms;
  • n integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms;
  • recurring units (Rl) are chosen from :
  • recurring units (Rl) are recurring units :
  • polymer (P) further comprises recurring units (R2) :
  • R being an aliphatic divalent group of up to 6 carbon atoms, such as methylene, ethylene, isopropylene and the like [polymer (P*)].
  • Recurring units (R2) are preferably chosen from :
  • Polymer (P*) may notably be a random, alternating or block copolymer. Preferably, it is a block copolymer.
  • polymer (P) is chosen from polymers other than block copolymers comprising at least one block of a polymer comprising at least 50 mole % of recurring units formed by the polymerization of at least one alkylene oxide.
  • Polymer (P) comprises preferably more than 70 wt. %, and more preferably more than 90 wt. % of recurring units (Rl). Still more preferably, all the recurring units of polymer (P) are recurring units (Rl).
  • a polymer the recurring units of which are recurring units (ii) can be advantageously manufactured by the polycondensation reaction between 4,4'-bis[(4-chlorophenylsulfonyl)- 1 , 1 '-biphenyl and biphenol.
  • Polymer (P) has a glass transition temperature advantageously of at least about 240°C, and preferably of at least about 250°C. In addition, polymer (P) has a glass transition temperature of advantageously at most about 275 °C.
  • Polymer (P) is advantageously amorphous. Polymer (P) exhibits advantageously a high compatibility with other high temperature polymers other than polymer (P).
  • Polymer (P) has advantageously matched thermal (e.g. CLTE, decomposition) characteristics, benefiting notably coating application.
  • Polymer composition (C) can consist of a sole ingredient [the case being, polymer (P)] or of several ones.
  • polymer composition (C) may further comprise notably other polymers than polymer (P), fillers and conventional ingredients of sulfone polymer compositions such as stabilizers, i.e., metal oxides such as zinc oxide, antioxidants and flame retardants.
  • a preferred method comprises mixing polymer (P) and the optional ingredients in powder or granular form in an extruder and extruding the mixture into strands and chopping the strands into pellets.
  • Polymer composition (C) has at least one glass transition temperature advantageously of at least about 240°C, and preferably of at least about 250°C.
  • polymer composition (C) has at least one glass transition temperature of advantageously at most about 275 °C.
  • Polymer composition (C) comprises advantageously more than 10 wt. % of polymer (P).
  • a preferred polymer composition (C) is one comprising more than 50 wt. % of polymer (P) [polymer composition (Cl)].
  • Polymer composition (Cl) comprises preferably more than 80 wt. %, more preferably more than 95 wt. % of polymer (P). Still more preferably, polymer composition (Cl) consists essentially of, or even consists of, polymer (P).
  • a preferred polymer composition (C) is one further comprising at least one polymer (P2) chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof [polymer composition (C2)].
  • P2 polymer chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof [polymer composition (C2)].
  • polyetherimide is intended to denote any polymer, of which more than 50 % wt of the recurring units are recurring units (R3), comprising two imide groups as such (R3-A) and/or in their corresponding amic acid forms [(R3-B) and (R3-C)] :
  • R' being a hydrogen atom or an alkyl radical comprising
  • n integer from 1 to 6 ;
  • n integer from 1 to 6 .
  • Recurring units (R3) are preferably recurring units (k), in imide form (k-A) and/or in amic acid forms [(k-B) and (k-C)] :
  • polyphenylsulfone polysulfone
  • polyethersulfone polyetherethersulfone
  • PEES Polyetherethersulfone
  • Polyphenylsulfone is available as RADEL ® R PPSF from Solvay Advanced Polymers, L.L.C.. Polysulfone is available as UDEL ® PSF from Solvay Advanced Polymers, L.L.C.. Polyethersulfone is available as RADEL ® A PES from Solvay Advanced Polymers, L.L.C.. Polyetherethersulfone Qj) is the polymer formed from the polycondensation of 4,4'-dihalodiphenylsulfone and hydroquinone.
  • Polymer composition (C2) comprises advantageously polymer (P) as main polymer [i.e., in polymer composition (C2), the weight fraction of polymer (P) is greater than or equal to the weight fraction of polymer (P2)].
  • Polymer composition (C2) comprises preferably more than 40 wt. %, and more preferably more than 50 wt. % of polymer (P).
  • polymer composition (C2) comprises advantageously less than 80 wt. %, and preferably less than 70 wt. % of polymer (P).
  • a preferred polymer composition (C) is one further comprising at least one filler [polymer composition (C3)].
  • suitable fillers include flake, spherical and fibrous particulate reinforcement fillers and nucleating agents such as talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, and the like.
  • suitable fillers include notably glass fiber, carbon fiber, graphite fiber, fibers formed of silicon carbide, alumina, titania, boron and the like, and may include mixtures comprising two or more such fibers.
  • Polymer composition (C3) comprises preferably at least one fibrous filler. Very preferably, it comprises glass fiber.
  • the weight amount of filler comprised in polymer composition (C3) is advantageously at least 5 wt. %, and preferably at least 20 wt. % based on the total weight of the polymer composition. Besides, it is advantageously at most 40 wt. %, and preferably at most 30 wt. % based on the total weight of the polymer composition.
  • Polymer composition (C3) comprises preferably more than 50 wt. % of polymer (P). Still more preferably, polymer composition (C3) comprises preferably more than 75 wt. % of polymer (P).
  • polymer composition (C3) may further comprise at least one polymer (P2) chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof, as above defined.
  • P2 polymer chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof, as above defined.
  • polymer composition (C) is comprised in shaped article (A) in an amount of advantageously more than 25 wt. %, preferably more than 50 wt. %, and still more preferably more than 90 wt. %, based on the total weight of shaped article (A).
  • shaped article (A) consists essentially of, or even consists of, polymer composition (C).
  • Shaped article (A) is capable of working at a use temperature of advantageously at least 200°C, preferably at least 220°C. In addition, shaped article (A) is capable of working at a use temperature of advantageously at most 270°C, preferably at most 250°C.
  • Shaped article (A) has a thickness t advantageously lower than 100 mm.
  • a first preferred shaped article (A) is essentially two-dimensional [shaped article (Al)].
  • the thickness t of shaped article (Al) complies preferably with the relationship : t ⁇ (V/k 2 ) 173 [ which is equivalent to V > (k.t) . (k.t) . t ] (rel- 1 ) wherein V is the overall plain volume of the shaped article and k is equal to 10, t is expressed in mm and V is expressed in mm 3 .
  • the thickness t of shaped article (Al) complies very preferably with above relationship (rel-1), except k is now equal to 100.
  • the thickness t of shaped article (Al) complies preferably with the relationship : t ⁇ (S/2) 1/2 / k [ which is equivalent to S > 2 . (k.t) . (k.t) ] (rel-2) wherein S is the overall surface area developed by the shaped article, k is equal to 10, t is expressed in mm and S is expressed in mm 2 .
  • the thickness t of shaped article (Al) complies very preferably with above relationship (rel-2), except k is now equal to 100.
  • shaped article (Al) is chosen from articles having a thickness lower than 500 ⁇ m [shaped article (Al-I)]. Shaped article (Al-I) is commonly referred to as a film. Shaped article (Al-I) has a thickness of preferably less than 250 ⁇ m.
  • Shaped article (Al-I) has a thickness of preferably more than 5 ⁇ m.
  • Shaped article (Al-I) complies preferably with relationship (rel-1) in which k has been changed to 1000. Very preferably, it complies with relationship (rel-1) in which k has been changed to 10000.
  • Shaped article (Al-I) is preferably flexible. It is sometimes very preferred that article (Al-I) can be flexed in such a way that it can get the appearance of a parallelepiped rectangle-like volume the thickness of which is considerably lower than its length and its width ; roughly speaking, it looks then like a "plane with an extremely low thickness".
  • Shaped article (Al-I) can be an uncoated film.
  • shaped article can be a film coated on an essentially two- or on a three-dimensional substrate.
  • the essentially two- or the three- dimensional substrate can be notably a fabrics, a polymeric film free of polymer (P), a sheet of paper, a wood or a metal component.
  • shaped article (Al-I) is advantageously few sensitive to interiacial segregation and delamination iailure. In addition, it has advantageously a long-term thermal stability. These good properties are usually achieved notably because of the high glass transition temperature of polymer (P). Further, as coated film, shaped article (Al-I) has advantageously excellent retention of beneficial coating morphology versus coated films on the prior art, especially those made from a semi-crystalline polymer.
  • An embodiment of article (Al-I) is one wherein the substrate is a metal component.
  • Another embodiment of article (Al-I) is one wherein the substrate differs from a metal component.
  • preferred substrates are fabrics, end polymeric films free of polymer (P).
  • shaped article (Al) is chosen from shaped articles having a thickness from 500 ⁇ m to 5000 ⁇ m [shaped article (Al -2)] .
  • Shaped article (Al -2) has preferably the appearance of a parallelepiped rectangle-like volume the thickness of which is considerably lower than its length and its width ; roughly speaking, it looks then like a "plane with a very low thickness". Then, shaped article (Al -2) is commonly referred to as a sheet. In a third preferred variation of shaped article (Al), shaped article (Al) is chosen from shaped articles having a thickness above 5000 ⁇ m [shaped article (Al-3)].
  • Shaped article (Al-3) has preferably the appearance of a parallelepiped rectangle-like volume the thickness of which is considerably lower than its length and its width ; roughly speaking, it looks then like a "plane with a low thickness”. Then, shaped article (Al-3) is commonly referred to as a slab.
  • Shaped article (Al-3) is advantageously rigid.
  • shaped article (Al) is a hollow body [shaped article (Al -4)] .
  • the thickness of the walls of shaped article (Al -4) is advantageously equal to the thickness t of shaped article (Al -4).
  • Shaped article (Al -4) has a thickness t of preferably at least 250 ⁇ m, more preferably at least 500 ⁇ m. Shaped article (Al -4) has a thickness t of preferably at most 5000 ⁇ m, more preferably at most 2500 ⁇ m.
  • a second preferred shaped article (A) is essentially one-dimensional [shaped article (A2)].
  • Shaped article (A2) has a thickness t which is preferably lower than 10 mm, more preferably less than 250 ⁇ m, still more preferably less than 50 ⁇ m, and the most preferably less than 10 ⁇ m.
  • the thickness t of shaped article (A2) complies preferably with the relationship : t ⁇ (V/k') 1/3 [which is equivalent to V > (k'.t) . t . t ] (rel-3) wherein k' is equal to 10, V as above defined, t is expressed in mm and V is expressed in mm 3 .
  • the thickness t of shaped article (A2) complies very preferably with above relationship (rel-3), except k' is now equal to 100.
  • the thickness t of shaped article (A2) complies still more preferably with above relationship (rel-3), except k' is now equal to 1000.
  • the thickness t of shaped article (A2) complies the most preferably with above relationship (rel-3), except k' is now equal to 10000.
  • the thickness of shaped article (A2) complies preferably with the relationship : t ⁇ (S/k') 1/2 / 2 [which is equivalent to S > 4 . (k'.t) . t ] (rel-4) S as above defined, k'is equal to 10, t is expressed in mm and S is expressed in mm 2 .
  • the thickness t of shaped article (A2) complies very preferably with above relationship (rel-4), except k' is now equal to 100.
  • the thickness t of shaped article (A2) complies still more preferably with above relationship (rel-4), except k' is now equal to 1000.
  • the thickness t of shaped article (A2) complies the most preferably with above relationship (rel-4), except k' is now equal to 10000.
  • shaped article (A2) has the appearance of a cylinder- like plain volume the diameter of which is considerably lower than its length ; roughly speaking, it looks then like a "straight line with an extremely low diameter" [shaped article (A2-1)].
  • Shaped article (A2-1) is commonly referred to as a filament.
  • shaped article (A2) in particular when shaped article (A2) is a filament, good results can be obtained notably when shaped article (A2) consists essentially of, or even consists of, polymer composition (C).
  • shaped article (A2) is a coating coated on an essentially one-dimensional substrate, like an inorganic fiber, a polymeric fiber free of polymer (P) or a metal [shaped article (A2-2)].
  • Shaped article (A2-2) has then preferably the appearance of a circular crown surrounding a cylinder- like plain volume composed by the essentially one- dimensional substrate, the thickness of the crown being considerably lower than the length and the diameter of the cylinder- like plain volume.
  • the thickness t of shaped article (A2-2) is still more preferably less than 50 ⁇ m, and the most preferably less than 10 ⁇ m. Besides, it is advantageously lower than the diameter of the essentially one-dimensional substrate.
  • Shaped article (A2-2) is advantageously few sensitive to interiacial segregation and delamination iailure. In addition, it has advantageously a long- term thermal stability. These good properties are usually achieved notably because of the high glass transition temperature of polymer (P).
  • An embodiment of article (A2-2) is one wherein the substrate is a metal, in particular a metal electrical wire.
  • Another embodiment of article (A2-2) is one wherein the substrate differs from a metal. According to this embodiment, preferred substrates are inorganic fibers, and polymeric fibers free of polymer (P).
  • electrical insulation applications can require continuous use temperatures in the 200-250°C range.
  • insulations include dry power distribution transformers, aerospace wire insulation, and motor windings.
  • accelerated testing must be done at temperatures ranging from 220-270°C which is much higher than the slated use temperatures.
  • Other aspects of the present invention concern performing methods of making shaped article (A) as above described.
  • the invention concerns a method of making shaped article (A) as above described, which comprises liquefying polymer (P) [method (Ml)].
  • "Liquefying polymer (P)” means causing polymer (P) to become liquid or fluid. Liquefying can be achieved by any technique known by the skilled person.
  • polymer (P) is advantageously in the form of powder or of granules.
  • liquefying polymer (P) is achieved through melting polymer (P) under the action of heat.
  • Method (Ml-I) comprises advantageously extruding polymer (P), or more generally, polymer composition (C).
  • liquefying polymer (P) is achieved through solvent casting.
  • n-methyl pyrrolidone can be cited.
  • composition (X) comprising a solvent of polymer (P) and polymer (P) in dissolved state is usually prepared.
  • Composition (X) may optionally comprise notably inorganic additives.
  • Said inorganic additives are usually not soluble in the solvent, and thus not in dissolved state in composition (X).
  • Composition (X) may also optionally comprise notably organic additives. Said organic additives may be or not soluble in the solvent, and thus respectively in dissolved state or not in composition (X).
  • the application of composition (X) on the substrate can be achieved by any known technique. It is preferably achieved through immersion, liquid spray and/or coating, in particular roller-, dip-, spin- and/or curtain-coating.
  • the invention concerns also a method of making shaped article (A) as above described, which comprises applying on a substrate, a composition (Y) comprising polymer (P) in dispersed state and a dispersion liquid of polymer (P) [method (M2)].
  • the dispersion liquid includes advantageously water. Preferably, it consists of water.
  • composition (Y) on the substrate can be achieved by any known technique. It is preferably achieved through immersion, liquid spray and/or coating, in particular roller-, dip-, spin- and/or curtain-coating.
  • Composition (Y) can be notably a slurry or a latex.
  • a slurry is intended to denote a composition comprising polymer (P) in the form of particles having an average diameter in weight ranging from about 3 to about 300 ⁇ m, and at least one dispersing agent such as a polyvinyl alcohol.
  • the slurry may further comprise at least one emulsifying agent such as a cationic, an anionic or a non ionic surfactant.
  • a latex is intended to denote a composition comprising polymer (P) in the form of particles having an average diameter in weight ranging from about 0.03 ⁇ m to about 3 ⁇ m, and at least one emulsifying agent.
  • the latex may further comprise at least one dispersing agent.
  • the dispersion of the particles of polymer (P) in the dispersion liquid is usually stable as a function of time ; the wording "emulsion" is commonly used to refer to such stable dispersion.
  • composition (Y) is a slurry.
  • composition (Y) is a latex.
  • the invention concerns also a method of making shaped article (A) as above described, which comprises applying on a substrate, polymer (P) in powder form or, more generally, polymer composition (C) in powder form [method (M3)].
  • method (M3) the application of polymer (P) or of polymer composition (C) on the substrate can be achieved by any known technique. It is preferably achieved through powder spray.
  • Still another aspect of the present invention concerns a high-performance semi- finished or finished multi-component article.
  • the present invention concerns also a semi- finished or finished multi-component article (B) comprising at least one component consisting of shaped article (A) as above described or prepared by method (M) as above described.
  • Article (B) can be any semi- finished or finished multi-component article which includes advantageously a component consisting of a high-performance shaped article.
  • a first preferred article (B) is one comprising a substrate coated with a shaped article (A) which is a film coated on an essentially two- or a three- dimensional substrate.
  • a second preferred article (B) is one comprising an essentially one- dimensional substrate coated with a coating [essentially one-dimensional shaped article (A)].
  • a third preferred article (B) is a membrane.
  • the membrane can be used for any suitable purpose.
  • the membrane is used for purifying a liquid, preferably impure water or blood, more preferably water.
  • the membrane is used for separating gases.
  • the invention will be further understood with reference to the following non-limiting examples.
  • a 10 wt. % polymer solid solution was prepared by charging 1Og of a polymer the recurring units of which consist of
  • a dispersion is prepared. To this end, 10-40 % of ground polymer the recurring units of which consist of
  • Example 3 with an average particle size in weight in the range of 3-30 ⁇ m, 1-10 wt. % portion of a non white pigment, 50-80 wt., 1-5 wt. % of an emulsifying agent and 1-5 wt. % of a dispersing agent are ball milled for 24 hours.
  • the dispersion coating is sprayed using conventional techniques onto metal substrates. The coating is cured at 150°C for 15 minutes, then 250°C for 15 minutes and finally 300°C for 15 minutes to produce a tough, transparent film.
  • Score cross-hatch adhesion test
  • Films were made from 10 lots of a resin of a polymer the recurring units of which consist of

Abstract

Essentially at most two-dimensional shaped article (A) comprising at least one polymer composition (C) comprising at least one high glass transition temperature sulfone polymer (P). Methods of making it and uses thereof.

Description

High performance shaped articles, methods of making, and uses thereof
The present invention relates to high-performance polymeric shaped articles which are essentially at most two-dimensional. These include essentially one-dimensional shaped articles like filaments or to high performance polymeric essentially two-dimensional shaped articles like films, sheets and slabs. It relates also to performing methods of making said shaped articles, and to end-uses of said shaped articles.
REFERENCE TO RELATED APPLICATIONS This application claims priority to EP application 04106875.0, filed on December 22, 2004, to U.S. provisional application 60/615,023, filed October 4, 2004, to EP application 04106878.4, filed on December 22, 2004, to U.S. provisional application 60/619,695, filed October 19, 2004, to EP application 04106879.2, filed on December 22, 2004, to U.S. provisional application 60/619,694, filed October 19, 2004, and to U.S. provisional application 60/670,266, filed April 12, 2005, whose disclosures are incorporated herein by reference.
The essentially one- or two-dimensional polymeric shaped articles of the prior art may offer a poor to medium heat resistance. Yet, service requirements for numerous essentially one- or two-dimensional polymeric shaped articles include long term thermal exposure beyond 220°C, with excursions up to 300°C. Non limitative examples of essentially two-dimensional shaped articles with such service requirements include cookware-, bakeware-, CPI-, semiconductor-, automotive-, industrial, and aerospace- coatings, as well as essentially two- dimensional shaped articles for aerospace applications other than coatings. Thus, there is a need for essentially one- or two-dimensional polymeric shaped articles with an improved heat resistance.
In addition, the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer a poor transparency. Among these ones are notably essentially one- or two-dimensional polymeric shaped articles made out of high-temperature crystalline polymers like aromatic polyamides. Thus, there is another need for essentially one- or two-dimensional polymeric shaped articles with an improved transparency. In addition, the essentially one- or two-dimensional polymeric shaped articles of the prior art may be difficult to shape. For example, shaped articles made of KAPTON® resins cannot be fabricated by melt extrusion. Thus, there is another need for essentially one- or two-dimensional polymeric shaped articles with an improved processability.
In addition, the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer poor to medium mechanical performances. Thus, there is another need for essentially one- or two-dimensional polymeric shaped articles with improved mechanical performances, including notably good retention of modulus at high temperature and reduced loss of mechanical properties over extended time and temperature cycles.
In addition, the essentially one- or two-dimensional polymeric shaped articles of the prior art may offer poor to medium chemical resistance to chemical agents, notably to strong acids, strong bases, aliphatic hydrocarbons and aromatic hydrocarbons, and have medium to poor hydro lytic stability. Thus, there is another need for essentially one- or two-dimensional polymeric shaped articles with improved chemical resistance.
In addition, the essentially one- or two-dimensional polymeric shaped articles of the prior art may be very expensive. Among these ones are notably shaped articles made of Kapton® resins. Thus, there is another need for high performance essentially one- or two-dimensional polymeric shaped articles at a moderate cost.
At least part, and preferably all of these needs, and possibly still other additional needs, are met by an essentially at most two-dimensional shaped article (A) comprising at least one polymer composition (C) comprising at least one high glass transition temperature sulfone polymer (P).
From a practical point of view, any shaped article is three-dimensional, and can thus be characterized notably by three characteristic dimensions ("length", "width" and "height"). However, some shaped articles are such that one or two of their characteristic dimensions is (are) considerably lower than respectively the other two ones or the third one. Here and wherever else used in the present description, the terms "considerably lower" should generally be understood as "more than 5 times lower" and preferably as "more than 10 times lower", unless they characterize a "two-dimensional thickness" as defined hereafter in the description. Precisely, for the purpose of the present invention an essentially two- dimensional shaped article is intended to denote a shaped article of which one of its characteristic dimensions ("thickness-height") is considerably lower than its other two ones ("width" and "length"), while an essentially one-dimensional shaped article is intended to denote a shaped article of which two out of its characteristic dimensions ("thickness-width" and "thickness-height") are considerably lower than its third one ("length"). Otherwise said, from a mathematic point of view, essentially two-dimensional articles have essentially the appearance of a geometric surface, while essentially one-dimensional articles have essentially the appearance of a geometric line. Thus, an essentially two- dimensional article can be viewed as a suria.ce (with a certain length and a certain width) differing from a geometric surface in that it has a certain non-zero thickness (typically in a direction perpendicular to the surface), said non-zero thickness being however considerably lower than the square root of the surface area developed by the surface itself and, more precisely, said non-zero thickness being considerably lower than both the length and the width of the surface itself ; an essentially one-dimensional article can be viewed as a line (of a certain length) differing from a geometric line, essentially in that it has a non-zero "two- dimensional thickness" (typically in a plane perpendicular to the line, with a certain non-zero thickness-width and a certain non-zero thickness-height as characteristic dimensions), said non-zero two-dimensional thickness being however considerably lower (here specifically, the terms "considerably lower", which characterize a two-dimensional thickness, should generally be understood as "more than 25 times lower" and preferably as "more than 100 times lower") than the square of the length of the line itself, more precisely, said non-zero thickness-width and said non-zero thickness-height being both considerably lower than the length of the line itself. The geometric surface can be curved or plane, twisted or untwisted ; the geometric line can be a straight line or a curved line. Essentially zero-dimensional articles i.e. articles having essentially the appearance of a geometric point (sometimes also referred to as "material point"), with essentially no length, no width and no height, like powdery spherical particles of polymer or powdery spherical inorganic particles coated with a polymer (with a typical diameter of a few microns), are not shaped articles within the meaning of the present invention. Thus, within the meaning of the present invention, an essentially at most two-dimensional shaped article can be either an essentially two-dimensional shaped article or an essentially one- dimensional shaped article.
The thickness of a shaped article of a regular or irregular volume is preferably defined as : t = IV τ(x,y,z) dx dy dz / V, wherein x, y and z are the coordinates of an elementary volume dV (dV being equal to dx times dy times dz) of the shaped article of overall plain volume V, and τ is the local thickness.
The local thickness τ, associated to a material point of coordinates (x,y,z), is defined as the length of the shortest straight line D including the material point of concern, which goes right through the shaped article (i.e. which goes from the material point where D enters the shaped article to the material point where D exits the shaped article).
For the purpose of the invention, the term "high glass transition temperature sulfone polymer" [polymer (P)] is intended to denote any polymer, of which more than 50 wt. % of the recurring units are recurring units (Rl) :
Figure imgf000005_0001
(Rl) wherein Ar and Q, equal or different, are divalent radicals comprising at least aromatic ring.
Preferred recurring units (Rl) are those wherein Q is a group chosen among the following structures :
Figure imgf000005_0002
Figure imgf000006_0001
Figure imgf000006_0002
with R being :
Figure imgf000006_0003
with n = integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms;
and mixtures thereof; and
- Ar is a group chosen among the following structures
Figure imgf000006_0004
Figure imgf000007_0001
Figure imgf000007_0002
with R being :
Figure imgf000007_0003
with n = integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms;
and mixtures thereof.
More preferably, recurring units (Rl) are chosen from :
Figure imgf000007_0004
(0
Figure imgf000007_0005
u)
Figure imgf000007_0006
111)
Figure imgf000008_0001
(iv) and mixtures thereof.
More preferably, recurring units (Rl) are recurring units :
Figure imgf000008_0002
(ϋ)
In a particular embodiment of the invention, polymer (P) further comprises recurring units (R2) :
Figure imgf000008_0003
(R2) wherein Ar' is chosen among :
Figure imgf000008_0004
Figure imgf000009_0001
, with R being an aliphatic divalent group of up to 6 carbon atoms, such as methylene, ethylene, isopropylene and the like [polymer (P*)].
Recurring units (R2) are preferably chosen from :
Figure imgf000009_0002
(j)
Figure imgf000009_0003
(Jj)
Figure imgf000009_0004
ϋjj)
Figure imgf000009_0005
Ov) and mixtures thereof.
Polymer (P*) may notably be a random, alternating or block copolymer. Preferably, it is a block copolymer.
Advantageously, polymer (P) is chosen from polymers other than block copolymers comprising at least one block of a polymer comprising at least 50 mole % of recurring units formed by the polymerization of at least one alkylene oxide.
Polymer (P) comprises preferably more than 70 wt. %, and more preferably more than 90 wt. % of recurring units (Rl). Still more preferably, all the recurring units of polymer (P) are recurring units (Rl).
Excellent results are obtained with polymers (P) which are homopolymers the recurring units of which are recurring units (ii).
A polymer the recurring units of which are recurring units (ii) can be advantageously manufactured by the polycondensation reaction between 4,4'-bis[(4-chlorophenylsulfonyl)- 1 , 1 '-biphenyl and biphenol.
Polymer (P) has a glass transition temperature advantageously of at least about 240°C, and preferably of at least about 250°C. In addition, polymer (P) has a glass transition temperature of advantageously at most about 275 °C.
Polymer (P) is advantageously amorphous. Polymer (P) exhibits advantageously a high compatibility with other high temperature polymers other than polymer (P).
Polymer (P) has advantageously matched thermal (e.g. CLTE, decomposition) characteristics, benefiting notably coating application.
Polymer composition (C) can consist of a sole ingredient [the case being, polymer (P)] or of several ones. In addition to polymer (P), polymer composition (C) may further comprise notably other polymers than polymer (P), fillers and conventional ingredients of sulfone polymer compositions such as stabilizers, i.e., metal oxides such as zinc oxide, antioxidants and flame retardants. Should the polymer composition comprise at least two ingredients, it is advantageously prepared by any conventional mixing method. A preferred method comprises mixing polymer (P) and the optional ingredients in powder or granular form in an extruder and extruding the mixture into strands and chopping the strands into pellets. Polymer composition (C) has at least one glass transition temperature advantageously of at least about 240°C, and preferably of at least about 250°C. In addition, polymer composition (C) has at least one glass transition temperature of advantageously at most about 275 °C.
Polymer composition (C) comprises advantageously more than 10 wt. % of polymer (P). In a certain embodiment of the present invention, a preferred polymer composition (C) is one comprising more than 50 wt. % of polymer (P) [polymer composition (Cl)]. Polymer composition (Cl) comprises preferably more than 80 wt. %, more preferably more than 95 wt. % of polymer (P). Still more preferably, polymer composition (Cl) consists essentially of, or even consists of, polymer (P).
In another embodiment of the present invention, a preferred polymer composition (C) is one further comprising at least one polymer (P2) chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof [polymer composition (C2)].
For the purpose of the invention, the term "polyetherimide" is intended to denote any polymer, of which more than 50 % wt of the recurring units are recurring units (R3), comprising two imide groups as such (R3-A) and/or in their corresponding amic acid forms [(R3-B) and (R3-C)] :
Figure imgf000011_0001
(R3-A)
Figure imgf000011_0002
(R3-B)
Figure imgf000012_0001
(R3-C) wherein :
- the — > denotes isomerism so that in any recurring unit the groups to which the arrows point may exist as shown or in an interchanged position;
- E is typically :
Figure imgf000012_0002
with R' being a hydrogen atom or an alkyl radical comprising
L H? Jn from 1 to 6 carbon atoms ; with n = integer from 1 to 6 ;
Figure imgf000012_0003
being :
Figure imgf000012_0004
Figure imgf000012_0005
with n = integer from 1 to 6 ;
- Ar" is typically :
Figure imgf000013_0001
with Y being :
Figure imgf000013_0002
with n = integer from 1 to 6 .
Recurring units (R3) are preferably recurring units (k), in imide form (k-A) and/or in amic acid forms [(k-B) and (k-C)] :
Figure imgf000013_0003
(k-A)
Figure imgf000013_0004
(k-B)
Figure imgf000014_0001
(k-C) wherein in formulae (k-B) and (k-C) the — > denotes isomerism so that in any recurring unit the groups to which the arrows point may exist as shown or in an interchanged position.
For clarity, the structural repeat units of polyphenylsulfone, polysulfone, polyethersulfone, and polyetherethersulfone are listed below : Polyphenylsulfone (PPSF)
Figure imgf000014_0002
(j)
Polyetherethersulfone (PEES)
Figure imgf000014_0003
(Jj)
Polyethersulfone (PES)
Figure imgf000014_0004
(jjj) and/or mixtures of (jj) and (jjj)
Figure imgf000015_0001
Polyphenylsulfone is available as RADEL® R PPSF from Solvay Advanced Polymers, L.L.C.. Polysulfone is available as UDEL® PSF from Solvay Advanced Polymers, L.L.C.. Polyethersulfone is available as RADEL® A PES from Solvay Advanced Polymers, L.L.C.. Polyetherethersulfone Qj) is the polymer formed from the polycondensation of 4,4'-dihalodiphenylsulfone and hydroquinone. Polymer composition (C2) comprises advantageously polymer (P) as main polymer [i.e., in polymer composition (C2), the weight fraction of polymer (P) is greater than or equal to the weight fraction of polymer (P2)]. Polymer composition (C2) comprises preferably more than 40 wt. %, and more preferably more than 50 wt. % of polymer (P). Besides, polymer composition (C2) comprises advantageously less than 80 wt. %, and preferably less than 70 wt. % of polymer (P).
Still in another embodiment of the present invention, a preferred polymer composition (C) is one further comprising at least one filler [polymer composition (C3)]. Non limitative examples of suitable fillers include flake, spherical and fibrous particulate reinforcement fillers and nucleating agents such as talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, and the like. Other suitable fillers include notably glass fiber, carbon fiber, graphite fiber, fibers formed of silicon carbide, alumina, titania, boron and the like, and may include mixtures comprising two or more such fibers.
Polymer composition (C3) comprises preferably at least one fibrous filler. Very preferably, it comprises glass fiber.
The weight amount of filler comprised in polymer composition (C3) is advantageously at least 5 wt. %, and preferably at least 20 wt. % based on the total weight of the polymer composition. Besides, it is advantageously at most 40 wt. %, and preferably at most 30 wt. % based on the total weight of the polymer composition. Polymer composition (C3) comprises preferably more than 50 wt. % of polymer (P). Still more preferably, polymer composition (C3) comprises preferably more than 75 wt. % of polymer (P).
Optionally, polymer composition (C3) may further comprise at least one polymer (P2) chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof, as above defined.
Besides, polymer composition (C) is comprised in shaped article (A) in an amount of advantageously more than 25 wt. %, preferably more than 50 wt. %, and still more preferably more than 90 wt. %, based on the total weight of shaped article (A). The most preferably, shaped article (A) consists essentially of, or even consists of, polymer composition (C).
Shaped article (A) is capable of working at a use temperature of advantageously at least 200°C, preferably at least 220°C. In addition, shaped article (A) is capable of working at a use temperature of advantageously at most 270°C, preferably at most 250°C.
Shaped article (A) has a thickness t advantageously lower than 100 mm.
A first preferred shaped article (A) is essentially two-dimensional [shaped article (Al)]. The thickness t of shaped article (Al) complies preferably with the relationship : t < (V/k2)173 [ which is equivalent to V > (k.t) . (k.t) . t ] (rel- 1 ) wherein V is the overall plain volume of the shaped article and k is equal to 10, t is expressed in mm and V is expressed in mm3. The thickness t of shaped article (Al) complies very preferably with above relationship (rel-1), except k is now equal to 100.
In addition, the thickness t of shaped article (Al) complies preferably with the relationship : t < (S/2)1/2 / k [ which is equivalent to S > 2 . (k.t) . (k.t) ] (rel-2) wherein S is the overall surface area developed by the shaped article, k is equal to 10, t is expressed in mm and S is expressed in mm2.
The thickness t of shaped article (Al) complies very preferably with above relationship (rel-2), except k is now equal to 100.
In a first preferred variation of shaped article (Al), shaped article (Al) is chosen from articles having a thickness lower than 500 μm [shaped article (Al-I)]. Shaped article (Al-I) is commonly referred to as a film. Shaped article (Al-I) has a thickness of preferably less than 250 μm.
Shaped article (Al-I) has a thickness of preferably more than 5 μm.
Shaped article (Al-I) complies preferably with relationship (rel-1) in which k has been changed to 1000. Very preferably, it complies with relationship (rel-1) in which k has been changed to 10000.
Shaped article (Al-I) is preferably flexible. It is sometimes very preferred that article (Al-I) can be flexed in such a way that it can get the appearance of a parallelepiped rectangle-like volume the thickness of which is considerably lower than its length and its width ; roughly speaking, it looks then like a "plane with an extremely low thickness".
Shaped article (Al-I) can be an uncoated film.
Alternatively, shaped article (Al-I) can be a film coated on an essentially two- or on a three-dimensional substrate. The essentially two- or the three- dimensional substrate can be notably a fabrics, a polymeric film free of polymer (P), a sheet of paper, a wood or a metal component.
As coated film, shaped article (Al-I) is advantageously few sensitive to interiacial segregation and delamination iailure. In addition, it has advantageously a long-term thermal stability. These good properties are usually achieved notably because of the high glass transition temperature of polymer (P). Further, as coated film, shaped article (Al-I) has advantageously excellent retention of beneficial coating morphology versus coated films on the prior art, especially those made from a semi-crystalline polymer.
An embodiment of article (Al-I) is one wherein the substrate is a metal component. Another embodiment of article (Al-I) is one wherein the substrate differs from a metal component. According to this embodiment, preferred substrates are fabrics, end polymeric films free of polymer (P).
In a second preferred variation of shaped article (Al), shaped article (Al) is chosen from shaped articles having a thickness from 500 μm to 5000 μm [shaped article (Al -2)] .
Shaped article (Al -2) has preferably the appearance of a parallelepiped rectangle-like volume the thickness of which is considerably lower than its length and its width ; roughly speaking, it looks then like a "plane with a very low thickness". Then, shaped article (Al -2) is commonly referred to as a sheet. In a third preferred variation of shaped article (Al), shaped article (Al) is chosen from shaped articles having a thickness above 5000 μm [shaped article (Al-3)].
Shaped article (Al-3) has preferably the appearance of a parallelepiped rectangle-like volume the thickness of which is considerably lower than its length and its width ; roughly speaking, it looks then like a "plane with a low thickness". Then, shaped article (Al-3) is commonly referred to as a slab.
Shaped article (Al-3) is advantageously rigid.
In a fourth preferred variation of shaped article (Al), shaped article (Al) is a hollow body [shaped article (Al -4)] .
The thickness of the walls of shaped article (Al -4) is advantageously equal to the thickness t of shaped article (Al -4).
Shaped article (Al -4) has a thickness t of preferably at least 250 μm, more preferably at least 500 μm. Shaped article (Al -4) has a thickness t of preferably at most 5000 μm, more preferably at most 2500 μm.
A second preferred shaped article (A) is essentially one-dimensional [shaped article (A2)].
Shaped article (A2) has a thickness t which is preferably lower than 10 mm, more preferably less than 250 μm, still more preferably less than 50 μm, and the most preferably less than 10 μm.
The thickness t of shaped article (A2) complies preferably with the relationship : t < (V/k')1/3 [which is equivalent to V > (k'.t) . t . t ] (rel-3) wherein k' is equal to 10, V as above defined, t is expressed in mm and V is expressed in mm3.
The thickness t of shaped article (A2) complies very preferably with above relationship (rel-3), except k' is now equal to 100.
The thickness t of shaped article (A2) complies still more preferably with above relationship (rel-3), except k' is now equal to 1000.
The thickness t of shaped article (A2) complies the most preferably with above relationship (rel-3), except k' is now equal to 10000.
In addition, the thickness of shaped article (A2) complies preferably with the relationship : t < (S/k')1/2 / 2 [which is equivalent to S > 4 . (k'.t) . t ] (rel-4) S as above defined, k'is equal to 10, t is expressed in mm and S is expressed in mm2.
The thickness t of shaped article (A2) complies very preferably with above relationship (rel-4), except k' is now equal to 100. The thickness t of shaped article (A2) complies still more preferably with above relationship (rel-4), except k' is now equal to 1000.
The thickness t of shaped article (A2) complies the most preferably with above relationship (rel-4), except k' is now equal to 10000.
In a first preferred variation of shaped article (A2), shaped article (A2) has the appearance of a cylinder- like plain volume the diameter of which is considerably lower than its length ; roughly speaking, it looks then like a "straight line with an extremely low diameter" [shaped article (A2-1)]. Shaped article (A2-1) is commonly referred to as a filament.
For certain variations of shaped article (A2), in particular when shaped article (A2) is a filament, good results can be obtained notably when shaped article (A2) consists essentially of, or even consists of, polymer composition (C). In a second preferred variation of shaped article (A2), shaped article (A2) is a coating coated on an essentially one-dimensional substrate, like an inorganic fiber, a polymeric fiber free of polymer (P) or a metal [shaped article (A2-2)]. Shaped article (A2-2) has then preferably the appearance of a circular crown surrounding a cylinder- like plain volume composed by the essentially one- dimensional substrate, the thickness of the crown being considerably lower than the length and the diameter of the cylinder- like plain volume.
The thickness t of shaped article (A2-2) is still more preferably less than 50 μm, and the most preferably less than 10 μm. Besides, it is advantageously lower than the diameter of the essentially one-dimensional substrate.
Shaped article (A2-2) is advantageously few sensitive to interiacial segregation and delamination iailure. In addition, it has advantageously a long- term thermal stability. These good properties are usually achieved notably because of the high glass transition temperature of polymer (P).
An embodiment of article (A2-2) is one wherein the substrate is a metal, in particular a metal electrical wire. Composition (C), and more particularly polymer (P), act then usually as insulating agent. Electrical insulation could be achieved notably through an article (A2-2) coating a conductive metal device. Another embodiment of article (A2-2) is one wherein the substrate differs from a metal. According to this embodiment, preferred substrates are inorganic fibers, and polymeric fibers free of polymer (P).
In addition, electrical insulation applications can require continuous use temperatures in the 200-250°C range. Examples of such insulations include dry power distribution transformers, aerospace wire insulation, and motor windings. In order to qualify materials for such applications, accelerated testing must be done at temperatures ranging from 220-270°C which is much higher than the slated use temperatures. Other aspects of the present invention concern performing methods of making shaped article (A) as above described.
In this regard, the invention concerns a method of making shaped article (A) as above described, which comprises liquefying polymer (P) [method (Ml)]. "Liquefying polymer (P)" means causing polymer (P) to become liquid or fluid. Liquefying can be achieved by any technique known by the skilled person.
According to method (Ml), polymer (P) is advantageously in the form of powder or of granules.
According to a first preferred embodiment of method (Ml) [method (Ml-I)], liquefying polymer (P) is achieved through melting polymer (P) under the action of heat.
Method (Ml-I) comprises advantageously extruding polymer (P), or more generally, polymer composition (C).
According to a second preferred embodiment of method (Ml) [method (Ml -2)], liquefying polymer (P) is achieved through solvent casting.
As a non limitative example of suitable solvent, n-methyl pyrrolidone can be cited.
According to method (Ml -2), a composition (X) comprising a solvent of polymer (P) and polymer (P) in dissolved state is usually prepared. Composition (X) may optionally comprise notably inorganic additives.
Said inorganic additives are usually not soluble in the solvent, and thus not in dissolved state in composition (X).
Composition (X) may also optionally comprise notably organic additives. Said organic additives may be or not soluble in the solvent, and thus respectively in dissolved state or not in composition (X). The application of composition (X) on the substrate can be achieved by any known technique. It is preferably achieved through immersion, liquid spray and/or coating, in particular roller-, dip-, spin- and/or curtain-coating.
The invention concerns also a method of making shaped article (A) as above described, which comprises applying on a substrate, a composition (Y) comprising polymer (P) in dispersed state and a dispersion liquid of polymer (P) [method (M2)].
The dispersion liquid includes advantageously water. Preferably, it consists of water. The application of composition (Y) on the substrate can be achieved by any known technique. It is preferably achieved through immersion, liquid spray and/or coating, in particular roller-, dip-, spin- and/or curtain-coating.
Composition (Y) can be notably a slurry or a latex.
For the purpose of the present invention, a slurry is intended to denote a composition comprising polymer (P) in the form of particles having an average diameter in weight ranging from about 3 to about 300 μm, and at least one dispersing agent such as a polyvinyl alcohol. The slurry may further comprise at least one emulsifying agent such as a cationic, an anionic or a non ionic surfactant. For the purpose of the present invention, a latex is intended to denote a composition comprising polymer (P) in the form of particles having an average diameter in weight ranging from about 0.03 μm to about 3 μm, and at least one emulsifying agent. The latex may further comprise at least one dispersing agent. In case of a latex, the dispersion of the particles of polymer (P) in the dispersion liquid is usually stable as a function of time ; the wording "emulsion" is commonly used to refer to such stable dispersion.
According to a first preferred embodiment of method (M2) [method (M2-1)], composition (Y) is a slurry.
According to a second preferred embodiment of method (M2) [method (M2-2)], composition (Y) is a latex.
The invention concerns also a method of making shaped article (A) as above described, which comprises applying on a substrate, polymer (P) in powder form or, more generally, polymer composition (C) in powder form [method (M3)]. According to method (M3), the application of polymer (P) or of polymer composition (C) on the substrate can be achieved by any known technique. It is preferably achieved through powder spray.
Still another aspect of the present invention concerns a high-performance semi- finished or finished multi-component article.
In this regard, the present invention concerns also a semi- finished or finished multi-component article (B) comprising at least one component consisting of shaped article (A) as above described or prepared by method (M) as above described. Article (B) can be any semi- finished or finished multi-component article which includes advantageously a component consisting of a high-performance shaped article.
A first preferred article (B) is one comprising a substrate coated with a shaped article (A) which is a film coated on an essentially two- or a three- dimensional substrate.
A second preferred article (B) is one comprising an essentially one- dimensional substrate coated with a coating [essentially one-dimensional shaped article (A)].
A third preferred article (B) is a membrane. The membrane can be used for any suitable purpose.
According to a first preferred use, the membrane is used for purifying a liquid, preferably impure water or blood, more preferably water.
According to a second preferred use, the membrane is used for separating gases. The invention will be further understood with reference to the following non-limiting examples. Example 1
A 10 wt. % polymer solid solution was prepared by charging 1Og of a polymer the recurring units of which consist of
Figure imgf000022_0001
into a 250 ml round bottom flask containing 90 g of n-methyl pyrrolidone. The flask was fitted with stirring paddle and heating mantel and the mixture was heated to 80°C under moderate stirring (300 rpm). After 2 hours the polymer had completely dissolved, yielding a straw golden solution with a viscosity of about 1000 centipoises at 40°C. This solution was used to produce 1 mil (25.4 μm) coatings on a substrate using a 10 mil (254 μm) clearance drawn down bar (doctor blade). The coating was cured at 150°C for 15 minutes, then 200°C for 15 minutes and finally 250°C for 15 minutes to produce a tough, transparent film. The film had a pencil hardness of 4H and passed a cross-hatch adhesion test (Score = 5). Example 2
A dispersion is prepared. To this end, 10-40 % of ground polymer the recurring units of which consist of
Figure imgf000023_0001
, with an average particle size in weight in the range of 3-30 μm, 1-10 wt. % portion of a non white pigment, 50-80 wt., 1-5 wt. % of an emulsifying agent and 1-5 wt. % of a dispersing agent are ball milled for 24 hours. The dispersion coating is sprayed using conventional techniques onto metal substrates. The coating is cured at 150°C for 15 minutes, then 250°C for 15 minutes and finally 300°C for 15 minutes to produce a tough, transparent film. The film has a pencil hardness of 4H and passed a cross-hatch adhesion test (Score = 1). Example 3
Films were made from 10 lots of a resin of a polymer the recurring units of which consist of
Figure imgf000023_0002
, with glass transition temperatures ranging from 259.4 to 262.1°C. The reduced viscosity of the various lots ranged from 0.33 to 0.43. The melt flow of the various lots ranged from 15.5 to 26.4.
Said resins were dried in a dehumidifying oven at 150°C overnight for approximately 16 hours. Then, the resins were extruded into films using a 25 mm Optical Control Systems Model 20/26 Extruder with a 10.16 cm wide die. The heat zones were all set at 385°C to achieve a melt of approximately 380°C, and the extruder screw was rotated at 15 rpm. A film was cast onto two sequential chill rolls the first maintained at 215°C and the other at 210°C. The film was taken up at approximately 2 m/min and was about 8.25 cm wide and 50 microns thick. The throughput was approximately 2.25 kg/hr.

Claims

C L A I M S
1 - Essentially at most two-dimensional shaped article (A) comprising at least one polymer composition (C) comprising at least one high glass transition temperature sulfone polymer (P), where polymer (P) is a polymer of which more than 50 wt. % of the recurring units are recurring units (Rl) :
Figure imgf000025_0001
(Rl)
wherein :
- Q is a group chosen among the following structures
Figure imgf000025_0002
Figure imgf000025_0003
with R being :
Figure imgf000026_0001
L H . n c with n = integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms;
and mixtures thereof; and
- Ar is a group chosen among the following structures
Figure imgf000026_0002
Figure imgf000026_0003
with R being :
Figure imgf000027_0001
with n = integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms;
and mixtures thereof.
2 - Shaped article according to claim 1, characterized in that recurring units
(Rl) are recurring units :
Figure imgf000027_0002
(ϋ)
3 - Shaped article according to claim 1 or 2, characterized in that polymer composition (C) consists essentially of polymer (P).
4 - Shaped article according to claim 1 or 2, characterized in that polymer composition (C) further comprises at least one polymer (P2) chosen from polyetherimides, polysulfones, polyethersulfones, polyphenylsulfones, polyetherethersulfones, and copolymers and mixtures thereof.
5 - Shaped article according to claim 1, 2 or 4, characterized in that polymer composition (C) further comprises at least one fibrous filler.
6 - Shaped article according to anyone of the preceding claims, characterized in that it consists essentially of polymer composition (C).
7 - Shaped article according to anyone of the preceding claims, characterized in that it is essentially two-dimensional.
8 - Shaped article according to claim 7, characterized in that it is a film.
9 - Shaped article according to claim 8, characterized in that the film is coated on an essentially two- or a three-dimensional substrate. 10 - Shaped article according to claim 7, characterized in that it is a sheet or a slab.
11 - Shaped article according to claim 7, characterized in that it is a hollow body.
12 - Shaped article according to anyone of claims 1 to 6, characterized in that it is essentially one-dimensional.
13 - Shaped article according to claim 12, characterized in that it is a filament consisting essentially of polymer composition (C).
14 - Shaped article according to claim 12, characterized in that it is a coating coated on an essentially one-dimensional substrate.
15 - Method of making the shaped article according to anyone of the preceding claims, characterized in that it comprises liquefying polymer (P) through melting polymer (P) under the action of heat [method (Ml-I)].
16 - Method of making the shaped article according to anyone of claims 1 to 14, characterized in that it comprises liquefying polymer (P) through solvent casting [method (M 1-2)].
17 - Method of making the shaped article according to anyone of claims 1 to 9, 12 and 14, characterized in that it comprises applying on a substrate, a composition (Y) comprising polymer (P) in dispersed state and a dispersion liquid of polymer (P) [method (M2)] .
18 - Method of making the shaped article according to anyone of claims 1 to 9, 12 and 14, characterized in that it comprises applying on a substrate, polymer composition (C) in powder form [method (M3)].
19 - Semi- finished or finished multi-component article (B) comprising at least one component consisting of the shaped article (A) according to any one of claims 1 to 14 or prepared by the process according to anyone of claims 15 to 18.
20 - Semi- finished or finished multi-component article according to claim 19, characterized in that it is a membrane.
PCT/EP2005/054937 2004-10-04 2005-09-30 High performance shaped articles, methods of making, and uses thereof WO2006037756A1 (en)

Priority Applications (6)

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JP2007535144A JP2008516029A (en) 2004-10-04 2005-09-30 High performance molded articles, methods for their production, and uses thereof
US11/576,509 US20090026128A1 (en) 2004-10-04 2005-09-30 High Performance Shaped Articles, Methods Of Making, And Uses Thereof
CN2005800337048A CN101035862B (en) 2004-10-04 2005-09-30 High performance shaped articles, methods of making, and uses thereof
EP10182512.3A EP2272915B1 (en) 2004-10-04 2005-09-30 Membrane, method of making, and use thereof
EP05791842.7A EP1802704B1 (en) 2004-10-04 2005-09-30 High performance membranes, methods of making, and uses thereof
ZA2007/02789A ZA200702789B (en) 2004-10-04 2007-04-03 High performance shaped articles,methods of making,and uses thereof

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US61502304P 2004-10-04 2004-10-04
US60/615,023 2004-10-04
US61969504P 2004-10-19 2004-10-19
US61969404P 2004-10-19 2004-10-19
US60/619,695 2004-10-19
US60/619,694 2004-10-19
EP04106878.4 2004-12-22
EP20040106879 EP1518883A2 (en) 2004-12-22 2004-12-22 Polyethersulphone articles
EP04106875A EP1524297A1 (en) 2004-12-22 2004-12-22 Sulfone polymer composition
EP04106878A EP1524298A1 (en) 2004-12-22 2004-12-22 Sulfone polymer composition
EP04106875.0 2004-12-22
EP04106879.2 2004-12-22
US67026605P 2005-04-12 2005-04-12
US60/670,266 2005-04-12

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524297A1 (en) * 2004-12-22 2005-04-20 Solvay Advanced Polymers, L.L.C. Sulfone polymer composition
JP5964627B2 (en) * 2011-04-18 2016-08-03 日東シンコー株式会社 Three-dimensional object for electric insulation and electric insulating sheet material
EP3057688B1 (en) 2013-10-15 2022-01-05 Basf Se Improving the chemical stability of filtration membranes
CN108602947B (en) * 2015-12-01 2023-11-17 索尔维特殊聚合物美国有限责任公司 Polymer compositions comprising poly (ether sulfone) blends and articles made therefrom

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051109A (en) * 1968-03-21 1977-09-27 Imperial Chemical Industries Limited Aromatic polymers
EP0176989A1 (en) * 1984-09-28 1986-04-09 Amoco Corporation Molded articles manufactured from blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone)
EP0215580A2 (en) * 1985-08-19 1987-03-25 Union Carbide Corporation Miscible blends of poly(aryl ether sulfones)
EP0332012A1 (en) * 1988-03-05 1989-09-13 BASF Aktiengesellschaft High temperature resistant polyarylethersulfone-/polyaryleneetherketone moulding compounds with improved phase cohesion
EP0376349A2 (en) * 1988-12-30 1990-07-04 Amoco Corporation Miscible blends of imide containing polymers with poly(aryl sulfones)
JP2003147091A (en) * 2001-11-09 2003-05-21 Sumitomo Chem Co Ltd Aromatic polysulfone resin film and method for producing the same

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1932067C3 (en) * 1969-06-25 1979-09-06 Bayer Ag, 5090 Leverkusen Polyaryl ether sulfones and processes for their preparation
GB1569603A (en) * 1976-07-28 1980-06-18 Ici Ltd Production of aromatic polyethers
US4293670A (en) * 1979-12-26 1981-10-06 Union Carbide Corporation Blends of poly(aryl ether) resins and polyetherimide resins
US4520067A (en) * 1982-06-23 1985-05-28 Union Carbide Corporation Composition useful for making circuit board substrates and electrical connectors
US4937309A (en) * 1983-12-28 1990-06-26 Amoco Corporation Polymer useful for molding into a circuit board subtrate
US4682470A (en) * 1984-04-17 1987-07-28 Echlin, Inc. Catalytic converter for exhaust gases
US4624997A (en) * 1984-09-28 1986-11-25 Union Carbide Corporation Article molded from a blend of a poly(aryl ether ketone) and a poly(aryl ether sulfone)
US4804724A (en) * 1984-09-28 1989-02-14 Amoco Corporation Blends of a biphenyl containing poly (aryl ether sulfone) and a poly (aryl ether ketone)
US4755556A (en) * 1985-02-13 1988-07-05 Amoco Corporation Thermoplastic composites comprising a polyaryl ether sulphone matrix resin
GB8519060D0 (en) * 1985-07-29 1985-09-04 Ici Plc Polymer compositions
JPS62121762A (en) * 1985-08-19 1987-06-03 アモコ・コ−ポレイション Blend of poly (aryl ether sulfone)
DE3614594A1 (en) * 1986-04-30 1988-01-07 Basf Ag HIGH TEMPERATURE RESISTANT MOLDS
US4718548A (en) * 1986-12-19 1988-01-12 Advanced Micro Devices, Inc. Protective housing for a leadless chip carrier or plastic leaded chip carrier package
JPH01301756A (en) * 1987-03-24 1989-12-05 Sumitomo Chem Co Ltd Aromatic polysulfone resin composition having excellent plating characteristic
EP0297363A3 (en) * 1987-06-27 1989-09-13 BASF Aktiengesellschaft High temperature resistant thermoplastic moulding masses with improved melt stability
US4849503A (en) * 1987-12-21 1989-07-18 Amoco Corporation Novel poly(aryl ethers)
JPH062879B2 (en) 1988-12-19 1994-01-12 住友化学工業株式会社 Method for producing aromatic polysulfone resin molding material with improved releasability
US5189115A (en) * 1989-02-21 1993-02-23 Amoco Corporation Polyetherimide copolymers
US4975470A (en) 1989-06-06 1990-12-04 Amoco Corporation Blends comprising poly(aryl ether ketone co-carbonates)
JP2903558B2 (en) * 1989-09-12 1999-06-07 淑夫 今井 Method for producing polysulfone resin film
US5204400A (en) * 1990-06-22 1993-04-20 Amoco Corporation Poly(biphenyl ether sulfone)compositions
US5055631A (en) * 1990-07-11 1991-10-08 Exxon Research & Engineering Company Sulfonated polysulfone membranes for aromatics/saturates separation
US5279739A (en) 1991-08-19 1994-01-18 Koch Membrane Systems, Inc. Durable filtration membrane having optimized molecular weight
JP3126214B2 (en) * 1992-04-23 2001-01-22 積水化学工業株式会社 Aromatic polysulfone film
US5911880A (en) * 1995-12-15 1999-06-15 Research Corporation Technologies, Inc. Self-wetting membranes from engineering plastics
NL1004210C2 (en) * 1996-10-07 1998-04-10 Prime Water Systems N V Water filtration device.
US6013719A (en) * 1998-06-15 2000-01-11 E. I. Du Pont De Nemours And Company Applications of low melt viscosity polytetrafluorethylene
SE0203855L (en) 2002-12-20 2004-06-21 Gambro Lundia Ab Perm-selective membrane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051109A (en) * 1968-03-21 1977-09-27 Imperial Chemical Industries Limited Aromatic polymers
EP0176989A1 (en) * 1984-09-28 1986-04-09 Amoco Corporation Molded articles manufactured from blends of a biphenyl containing poly(aryl ether sulfone) and a poly(aryl ether ketone)
EP0215580A2 (en) * 1985-08-19 1987-03-25 Union Carbide Corporation Miscible blends of poly(aryl ether sulfones)
EP0332012A1 (en) * 1988-03-05 1989-09-13 BASF Aktiengesellschaft High temperature resistant polyarylethersulfone-/polyaryleneetherketone moulding compounds with improved phase cohesion
EP0376349A2 (en) * 1988-12-30 1990-07-04 Amoco Corporation Miscible blends of imide containing polymers with poly(aryl sulfones)
JP2003147091A (en) * 2001-11-09 2003-05-21 Sumitomo Chem Co Ltd Aromatic polysulfone resin film and method for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 09 3 September 2003 (2003-09-03) *

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EP1802704B1 (en) 2014-11-12
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EP2272915A3 (en) 2014-01-15
IN2007CH01384A (en) 2007-08-31
EP2272915B1 (en) 2018-11-28
JP2008516029A (en) 2008-05-15
US20090026128A1 (en) 2009-01-29

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