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WO2019092229A1 - Compositions de polysulfone comprenant un copolymère polycarbonate-polysiloxane - Google Patents

Compositions de polysulfone comprenant un copolymère polycarbonate-polysiloxane Download PDF

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Publication number
WO2019092229A1
WO2019092229A1 PCT/EP2018/080862 EP2018080862W WO2019092229A1 WO 2019092229 A1 WO2019092229 A1 WO 2019092229A1 EP 2018080862 W EP2018080862 W EP 2018080862W WO 2019092229 A1 WO2019092229 A1 WO 2019092229A1
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Prior art keywords
polymer composition
group
formula
carbon atoms
polycarbonate
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Jiqiang XIA
Raleigh L. DAVIS
Keshav S. Gautam
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Solvay Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions 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
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to polymer compositions including greater than 30 wt.% of at least one polysulfone (PSU), based on the total weight of the polymer composition, at least one polycarbonate-polysiloxane copolymer (SiPC), optionally, at least one poly(ether imide) (PEI), and optionally, at least one reinforcing filler, methods of making the polymer composition, and shaped articles including the polymer composition.
  • PSU polysulfone
  • SiPC polycarbonate-polysiloxane copolymer
  • PEI poly(ether imide)
  • reinforcing filler optionally, at least one reinforcing filler
  • the present invention is generally directed to a polymer composition
  • a polymer composition comprising greater than 30 wt.% of at least one polysulfone (PSU), based on the total weight of the polymer composition, at least one polycarbonate-polysiloxane copolymer (SiPC), optionally, at least one poly(ether imide) (PEI), and optionally, at least one reinforcing filler.
  • PSU polysulfone
  • SiPC polycarbonate-polysiloxane copolymer
  • PEI poly(ether imide)
  • the polymer compositions described herein exhibit significantly improved flame resistance.
  • the present polymer compositions unexpectedly achieve "V-0" UL94 flame resistance ratings.
  • the polymer compositions also exhibited markedly improved toughness as compared with, for example, the toughness observed for compositions of PSU or SiPC copolymer alone.
  • the polymer composition exhibits a UL94 flame resistance rating of "V-0" using a 1.6 mm-thick sample.
  • the polymer composition exhibits a notched Izod impact resistance of 750 to 1000 J/M, preferably 800 to 1000 J/M, as measured according to ASTM D256.
  • the polymer composition exhibits a UL94 flame resistance rating of "V-0" using a 1.6 mm-thick sample and a notched Izod impact resistance of 750 to 1000 J/M, preferably 800 to 1000 J/M, as measured according to ASTM D256.
  • the polymer composition does not comprise a polymer other than the at least one PSU, the at least one SiPC copolymer, and the optional PEI or comprise such a polymer in an amount not exceeding 1 wt.%, for example not exceeding 0.5 wt.% or 0.3 wt.%.
  • the polymer composition comprises less than 0.5 wt.% of a poly(carbonate-arylate ester), a poly(carbonate-arylate ester-siloxane), or a combination thereof.
  • the polymer composition does not comprise any of a poly(carbonate-arylate ester), a poly(carbonate-arylate ester-siloxane), or a combination thereof.
  • the polymer composition includes less than 10 wt.%, preferably less than 5 wt.%, preferably less than 1 wt.% of polyphenylsulfone (PPSU) polymer. Most preferably, the polymer composition does not comprise any PPSU polymer.
  • PPSU polyphenylsulfone
  • the amount of the polysulfone (PSU) ranges from 35 wt. % to 95 wt. %, preferably 40 wt.% to 90 wt.%, and the amount of the at least one polycarbonate-polysiloxane copolymer (SiPC) ranges from 5 wt.% to 65 wt.%), preferably 10 wt.% to 60 wt.%, each based on the total weight of the polymer composition.
  • PSU polysulfone
  • each R 8 is independently selected from the group consisting of a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; and
  • each h is independently selected from the group consisting of integers ranging from 0 to 4.
  • At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, of recurring units in the PSU are recurring units of formula (A).
  • the PSU includes more than 50 mol % of recurring units of formula (A-1) :
  • PSU can be prepared by known methods and is available as UDEL ® PSU from Solvay Specialty Polymers USA, L.L.C.
  • the polymer composition includes greater than 30 wt. % and less than
  • the polymer composition includes at least 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.% of the PSU, based on the total weight of the polymer composition.
  • the amount of PSU in the polymer composition ranges from 35 wt.% to 95 wt.%, preferably 35 wt.% to 90 wt.%, 40 wt.% to 90 wt.%, 45 wt.% to 90 wt.%, 50 wt.% to 90 wt.%, 55 wt.% to 90 wt.% of the polymer composition based on the total weight of the polymer composition.
  • the amount of PSU in the polymer composition ranges from greater than 30 wt.% to 55 wt.%, preferably 35 wt.% to 55 wt.%, 40 wt.%) to 55 wt.%), of the polymer composition based on the total weight of the polymer composition.
  • the PSU is the only poly(aryl ether sulfone) (PAES) polymer in the polymer composition.
  • PAES poly(aryl ether sulfone)
  • the polycarbonate-polysiloxane copolymer (“SiPC copolymer”) is a copolymer comprising polycarbonate repeat units and polysiloxane repeat units, where the mol% of polycarbonate repeat units and polysiloxane repeat units together represents more than 50 mol % of the repeat units of the copolymer.
  • the polycarbonate repeat units are repeat units of formula (B) : i) polycarbonate repeat units of formula (B) :
  • Z is selected from the group consisting of a bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -S0 2 -, -O- and -CO-.
  • Z is a group -C(R 2 )(R 3 )-, where R 2 and R 3 are independently selected from a hydrogen and an alkyl group having 1-4 carbon atoms. Most preferably, R 2 and R 3 are methyl groups;
  • each R 1 is independently selected from the group consisting of a halogen, an alkyl group having 1-20 carbon atoms, and an aryl group;
  • each p is independently selected from the group consisting of integers ranging from 0 to 4; and ii) polysiloxane repeat units of formula (C) :
  • each R 4 and R 5 are independently selected from the group consisting of a hydrogen, a halogen, a hydrocarbyl, and a halogen-substituted hydrocarbyl.
  • R 4 is a methyl group and R 5 is a methyl or phenyl group;
  • R 6 and R 7 are independently selected from the group consisting of organic residues having an aromatic nucleus
  • n is selected from integers ranging from 5 to more than 100.
  • m is selected from the group consisting of integers ranging from 5 to 1000, preferably from 5 to 200.
  • R 6 and R 7 are independently selected from the group consisting of a 3-(o-hydroxyphenyl)propylene group, a 2-(p- hydroxyphenyl)ethylene group, and groups represented by the formulas :
  • the moiety -O-R - in Formula (C) is a group of formula :
  • G is selected from the group consisting of a hydrogen, a hydrocarbyl, and a halogen-substituted hydrocarbyl (preferably methoxy), and
  • At least 75 mol %, 85 mol %, 95 mol %, 99 mol %, of repeat units in the SiPC copolymer are the polycarbonate and polysiloxane repeat units.
  • the polysiloxane repeat unit is preferably a polydimethylsiloxane repeat unit.
  • the ratio of the weight of the polycarbonate repeat units to the weight of the polysiloxane repeat units ranges from 0.05 to 3.
  • the SiPC copolymer preferably includes 0.5 % to 30 %, preferably 1 % to 30 %, preferably 4 % to 8 % by weight, of the polysiloxane repeat units.
  • SiPC copolymers their precursors, and methods for their preparation are described, for example, in U.S. Patent Nos. 3,189,662, 5,502,134, 6,072,011, and 8,981,017, each of which is incorporated by reference herein in its entirety.
  • the SiPC copolymer may be a random or a block copolymer, preferably a block copolymer.
  • SiPC copolymers are available, for example, as TARFLON ® NEO from Idemitsu Kosan Co., Ltd, and as LEXAN ® EXL from Saudi Basic Industries Corporation (SABIC).
  • the polymer composition includes less than 70 wt.% of the SiPC copolymer, based on the total weight of the polymer composition.
  • the polymer composition includes 65 wt.% or less, 60 wt.%) or less, 55 wt.%> or less, 50 wt.%> or less, 45 wt.%> or less, 40 wt.%> or less, 35 wt.%) or less of the SiPC copolymer, based on the total weight of the polymer composition. In some embodiments, the polymer composition includes less than 35 wt.%> of the SiPC copolymer, based on the total weight of the polymer composition.
  • the amount of the SiPC copolymer in the polymer composition ranges from 10 wt.% to 65 wt.%, preferably 10 wt.% to 60 wt.%, 10 wt.% to 55 wt.%, 10 wt.% to 50 wt.%, 10 wt.% to 45 wt.% of the polymer composition based on the total weight of the polymer composition.
  • the amount of the SiPC copolymer ranges from
  • the amount of the SiPC copolymer ranges from 45 wt.%> to less than 70 wt.%>, preferably from 45 wt.%> to 65 wt.%>, 45 wt.% to 60 wt.%, based on the combined weight of PSU and the SiPC copolymer.
  • the polymer composition includes at least one poly(ether imide) (PEI), preferably in an amount ranging from 1 wt.% to
  • a poly(ether imide) denotes any polymer comprising at least 50 mol %, based on the total number of moles in the polymer, of recurring units (R PEI ) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one ether
  • Recurring units may optionally further comprise at least one amide group which is not included in the amic acid form of an imide group.
  • the recurring units (R PEI ) are selected from the group consisting of following formulas (I), (II), (III), (IV), (V) and mixtures thereof :
  • - Ar is a tetravalent aromatic moiety and is selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms;
  • - Ar' is a trivalent aromatic moiety and is selected from the group consisting of a substituted, unsubstituted, saturated, unsaturated, aromatic monocyclic and aromatic polycyclic group having from 5 to 50 C atoms;
  • - R is selected from the group consisting of substituted and unsubstituted divalent organic radicals, for example selected from the group consisting of
  • - Y is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH 3 ) 2 and -C n H 2n - (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 ) 2 and -C n F 2n -
  • n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-, and
  • R" is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali earth metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, alkali earth metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium and
  • - i, for each R" is independently zero or an integer ranging from 1 to 4, with the provisio that at least one of Ar, Ar' and R comprise at least one ether group and that the ether group is present in the polymer chain backbone.
  • Ar is selected from the group consisting of formulas :
  • X is a divalent moiety, having divalent bonds in the 3,3', 3,4', 4,3" or the 4,4' positions and is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH 3 ) 2 and -C n H 2n - (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 ) 2 and -C n F 2n - (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-; or X is a group of the formula -0-Ar"-0- wherein Ar" is a aromatic moiety selected from the
  • Ar' is selected from the group consisting of formulas :
  • X is a divalent moiety, having divalent bonds in the 3,3', 3,4', 4,3" or the 4,4' positions and is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH 3 ) 2 and -C n H 2n - (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 ) 2 and -C n F 2n - (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-; or X is a group of the formula -0-Ar"-0- wherein Ar' ' is a aromatic moiety selected
  • At least 50 mol. %, 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 all of the recurring units in the PEI are recurring units (R PEI ) of formulas (I), (II), (III), (IV), (V) and/or mixtures thereof, as defined above.
  • a poly(ether imide) denotes any polymer comprising at least 50 mol.%, based on the total number of moles in the polymer, of recurring units (R PEI ) of formula (VII) :
  • R is selected from the group consisting of substituted and unsubstituted divalent organic radicals, for example selected from the group consisting of (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and halogenated derivatives thereof ;
  • - Y is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH 3 ) 2 and -C n H 2n - (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 ) 2 and -C n F 2n - (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ;
  • alkylidenes of 1 to 6 carbon atoms cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-, and
  • R" is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali earth metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, alkali earth metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium and
  • - i, for each R" is independently zero or an integer ranging from 1 to 4, with the provisio that at least one of Ar, Ar' and R comprise at least one ether group and that the ether group is present in the polymer chain backbone.
  • - T can either be wherein the divalent bonds of the - O - or the - O - Ar' ' - O - group are in the 3,3', 3,4', 4,3', or the 4,4' positions,
  • Ar' ' is a aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and poly eye lie group having 5 to 50 carbon atoms, for example a substituted or unsubtitutated phenylene, a substitued or unsubstituted biphenyl group, a susbtituted ou unsubstituted naphtalene group or a moiety comprising two substituted or unsubtitutated phenylene.
  • Ar' ' is of the general formula (VI), as detailed above ; for example, Ar" is of formula (XIX) :
  • polyetherimides (PEI) of the present invention may be prepared by any of the methods well-known to those skilled in the art including the reaction of a diamino compound of the formula H 2 N-R-NH 2 (XX), where R is as defined before, with any aromatic bis(ether anhydride)s of the formula (XXI) :
  • the preparation can be carried out in solvents, e.g., o-dichlorobenzene, m-cresol/toluene, ⁇ , ⁇ -dimethylacetamide, at temperatures ranging from 20°C to 250°C.
  • solvents e.g., o-dichlorobenzene, m-cresol/toluene, ⁇ , ⁇ -dimethylacetamide
  • these polyetherimides can be prepared by melt
  • aromatic bis(ether anhydride)s of formula (XXI) include, for example
  • the organic diamines of formula (XX) are chosen from the group consisting of m-phenylenediamine, p-phenylenediamine, 2,2-bis(p- aminophenyl)propane, 4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino diphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, and mixtures thereof; preferably, the organic diamines of formula (XX) are chosen from the group consisting of m-phenylenediamine and p-phenylenediamine and mixture thereof.
  • a poly(ether imide) denotes any polymer comprising at least 50 mol.%, based on the total number of moles in the polymer, of recurring units (R PEI ) of formulas (XXIII) or (XXIV), in imide forms, or their corresponding amic acid forms and mixtures thereof :
  • At least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, at least 99 mol. % of the recurring units in the PEI are recurring units (R PEI ) of formulas (XXIII) or (XXIV), in imide forms, or their corresponding amic acid forms and mixtures thereof.
  • aromatic polyimides are notably commercially available from Sabic Innovative Plastics as ULTEM ® polyetherimides.
  • the polymer composition optionally includes at least one reinforcing filler such as a fibrous or particulate filler.
  • a fibrous reinforcing filler is a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness.
  • such a material has an aspect ratio, defined as the average ratio between the length and the smallest of the width and thickness of at least 5.
  • the aspect ratio of the reinforcing fibers is at least 10, more preferably at least 20, still more preferably at least 50.
  • the particulate fillers have an aspect ratio of at most 5, preferably at most 2.
  • the reinforcing filler is selected from mineral fillers, such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, boron nitride; glass fibers; carbon fibers, boron carbide fibers; wollastonite; silicon carbide fibers; boron fibers, graphene, carbon nanotubes (CNT), and the like.
  • the reinforcing filler is glass fiber, preferably chopped glass fiber, or carbon fiber, preferably chopped carbon fibers.
  • Glass fibers are silica-based glass compounds that contain several metal oxides which can be tailored to create different types of glass.
  • the main oxide is silica in the form of silica sand; the other oxides such as calcium, sodium and aluminum are incorporated to reduce the melting temperature and impede crystallization.
  • Glass fibers have a round cross-section or a non-circular cross- section (so called "flat glass fibers"), including oval, elliptical or rectangular.
  • the glass fibers may be added as endless fibers or as chopped glass fibers.
  • the glass fibers have generally an equivalent diameter of 5 to 20 preferably of 5 to 15 ⁇ and more preferably of 5 to 10 ⁇ .
  • R, S and T glass fibers are high modulus glass fibers that have typically an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343.
  • E, R, S and T glass fibers are well known in the art. They are notably described in Fiberglass and Glass Technology, Wallenberger, Frederick T.;
  • R, S and T glass fibers are composed essentially of oxides of silicon, aluminum and magnesium.
  • those glass fibers comprise typically from 62-75 wt. % of Si0 2 , from 16-28 wt. % of A1 2 0 3 and from 5-14 wt. % of MgO.
  • R, S and T glass fibers comprise less than 10 wt. % of CaO.
  • the fibrous filler in particular the glass fibers, may have a cross-sectional longest diameter of at least 15 ⁇ , preferably at least 20 ⁇ , more preferably at least 22 ⁇ , still more preferably at least 25 ⁇ . It is advantageously of at most 40 ⁇ , preferably at most 35 ⁇ , more preferably at most 32 ⁇ , still more preferably at most 30 ⁇ . Excellent results were obtained when the cross- sectional longest diameter was in the range of 15 to 35 preferably of 20 to 30 ⁇ and more preferably of 25 to 29 ⁇ .
  • the fibrous filler in particular the glass fibers may have a cross-sectional shortest diameter of at least 4 ⁇ , preferably at least 5 ⁇ , more preferably at least 6 ⁇ , still more preferably at least 7 ⁇ . It is advantageously of at most 25 ⁇ , preferably at most 20 ⁇ , more preferably at most 17 ⁇ , still more preferably at most 15 ⁇ . Excellent results were obtained when the cross- sectional shortest diameter was in the range of 5 to 20 preferably of 5 to 15 ⁇ and more preferably of 7 to 11 ⁇ .
  • the fibrous filler in particular the glass fibers, may have an aspect ratio of at least 2, preferably at least 2.2, more preferably at least 2.4, still more preferably at least 3.
  • the aspect ratio is defined as a ratio of the longest diameter in the cross-section of the glass fiber to the shortest diameter thereof.
  • the aspect ratio of the glass fibers is of at most 8, preferably at most 6, more preferably of at most 4. Excellent results were obtained when said ratio was of from about 2 to about 6, and preferably, from about 2.2 to about 4.
  • the shape of the cross-section of the glass fiber, its length, its cross- sectional diameter and its aspect ratio can be easily determined using optical microscopy.
  • the amount of the reinforcing filler may range in the case of particulate fillers, from 1 wt. % to 40 wt. %, preferably from 5 wt. % to 35 wt. % and most preferably from 10 wt. % to 30 wt. %, and in the case of fibrous fillers from 5 wt. % to 50 wt. %, preferably from 10 wt. % to 40 wt. %, and most preferably from 15 wt. % to 30 wt. % based on the total weight of the polymer composition.
  • the polymer composition includes about 25 to about 35 wt. %, most preferably about 30 wt.
  • the polymer composition includes less than 10 wt.%, less than 5 wt.%, less than 1 wt.% of a fibrous filler, a particulate filler, or both. In some aspects, the polymer composition is free of a fibrous filler, a particulate filler, or both.
  • the polymer composition may further include optional additives such as titanium dioxide, zinc sulfide, zinc oxide, ultraviolet light stabilizers, heat stabilizers, antioxidants such as organic phosphites and phosphonites, acid scavengers, processing aids, nucleating agents, lubricants, flame retardants, smoke-suppressing agents, anti-static agents, anti-blocking agents, and conductivity additives such as carbon black.
  • optional additives such as titanium dioxide, zinc sulfide, zinc oxide, ultraviolet light stabilizers, heat stabilizers, antioxidants such as organic phosphites and phosphonites, acid scavengers, processing aids, nucleating agents, lubricants, flame retardants, smoke-suppressing agents, anti-static agents, anti-blocking agents, and conductivity additives such as carbon black.
  • their total concentration is preferably less than 10 wt. %, more preferably less than 5 wt. %, and most preferably less than 2 wt. %, based on the total weight of polymer composition.
  • the polymer composition includes less than
  • the polymer composition is free of a flame retardant.
  • the polymer composition can be prepared by melt-mixing a the PSU, the SiPC, the optional PEI, the optional reinforcing filler, and any optional additives, to provide a molten mixture, followed by extrusion and cooling of the molten mixture.
  • Exemplary embodiments also include a method of increasing the flame resistance of a composition comprising greater than 30 wt.% of a PSU, based on the total weight of the polymer composition, by adding a SiPC as described herein to the polymer composition.
  • compositions described herein are advantageously provided in the form of pellets, which may be used in injection molding or extrusion processes known in the art.
  • the preparation of the polymer composition can be carried out by any known melt-mixing process that is suitable for preparing thermoplastic molding compositions. Such a process is typically carried out by heating the
  • thermoplastic polymer above the melting temperature of the thermoplastic polymer thereby forming a melt of the thermoplastic polymer.
  • the process for the preparation of the composition can be carried out in a melt-mixing apparatus, for which any melt-mixing apparatus known to the one skilled in the art of preparing polymer compositions by melt mixing can be used.
  • Suitable melt- mixing apparatus are, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders.
  • the constituting components for forming the composition are fed to the melt-mixing apparatus and melt-mixed in that apparatus.
  • the components may be fed simultaneously as a powder mixture or granule mixture, also known as dry-blend, or may be fed separately.
  • Shaped Articles Comprising the Polymer Composition and Methods of Making Exemplary embodiments also include shaped articles comprising the polymer-metal junction and methods of making the shaped articles.
  • the polymer composition may be well suited for the manufacture of articles useful in a wide variety of applications.
  • the excellent flame resistance of the polymer compositions makes them ideal for use in applications such as medical, health care, electrical, electronic, and smart device applications
  • the polymer compositions described herein can be used for the
  • manufacture of shaped articles in particular, parts of electronic devices, more particularly parts of portable or mobile electronic devices.
  • mobile electronic device is intended to denote any electronic device that is designed to be conveniently transported and used in various locations while exchanging/providing access to data, e.g. through wireless connections or mobile network connection.
  • mobile electronic devices include mobile phones, personal digital assistants, laptop computers, tablet computers, radios, cameras and camera accessories, watches, calculators, music players, global positioning system receivers, portable games, hard drives and other electronic storage devices, and the like.
  • the at least one part of the mobile electronic device according to the present invention may be selected from a large list of articles such as fitting parts, snap fit parts, mutually moveable parts, functional elements, operating elements, tracking elements, adjustment elements, carrier elements, frame elements, switches, connectors and (internal and external) components of housing, which can be notably produced by injection molding, extrusion or other shaping technologies.
  • An aspect of the present invention is directed to mobile electronic devices comprising at least one structural part made of a polymer composition described herein, and in particular to a laptop, a mobile phone, a GPS, a tablet, personal digital assistants, portable recording devices, portable reproducing devices and portable radio receives.
  • polymer compositions described herein are very well suited for the production of housing components of mobile electronic devices.
  • the at least one part of the mobile electronic device according to the present invention is advantageously a component of a mobile electronic device housing.
  • mobile electronic device housing is meant one or more of the back cover, front cover, antenna housing, frame and/or backbone of a mobile electronic device.
  • the housing may be a single component-article or, more often, may comprise two or more components.
  • backbone is meant a structural component onto which other components of the device, such as electronics, microprocessors, screens, keyboards and keypads, antennas, battery sockets, and the like are mounted.
  • the backbone may be an interior component that is not visible or only partially visible from the exterior of the mobile electronic device.
  • the housing may provide protection for internal components of the device from impact and contamination and/or damage from environmental agents (such as liquids, dust, and the like). Housing components such as covers may also provide substantial or primary structural support for and protection against impact of certain components having exposure to the exterior of the device such as screens and/or antennas. Housing components may also be designed for their aesthetic appearance and touch.
  • the mobile electronic device housing is selected from the group consisting of a mobile phone housing, a tablet housing, a laptop computer housing and a tablet computer housing. Excellent results were obtained when the part of the mobile electronic device according to the present invention was a mobile phone housing.
  • the shaped articles may be made from the polymer composition using any suitable melt-processing method such as injection molding, extrusion molding, roto-molding, or blow-molding.
  • Exemplary embodiments are also directed to methods of making shaped articles by additive manufacturing, where the shaped article is printed from the polymer composition.
  • the methods include printing layers of the shaped article from the polymer composition as described below.
  • Additive manufacturing systems are used to print or otherwise build a shaped object from a digital representation of the shaped object by one or more additive manufacturing techniques.
  • additive manufacturing techniques include extrusion-based techniques, selective laser sintering, powder/binder jetting, electron-beam melting, and
  • stereolithography processes For each of these techniques, the digital representation of the shaped object is initially sliced into multiple horizontal layers. For each layer, a tool path is then generated, which provides instructions for the particular additive manufacturing system to print the given layer.
  • some embodiments include a method of making a shaped article comprising printing layers of the polymer composition to form the shaped article by an extrusion-based additive manufacturing system (for example FFF), a powder-based additive manufacturing system (for example SLS), or a continuous Fiber-Reinforced Thermosplastic (FRTP) printing method.
  • FFF extrusion-based additive manufacturing system
  • SLS powder-based additive manufacturing system
  • FRTP continuous Fiber-Reinforced Thermosplastic
  • Makrolon ® 3108 PC available from Bayer Materials Science, Inc.
  • the polymer compositions of the Examples and Comparative Examples shown in Table 1 were prepared by first drying the polymer ingredients for at least 16 hours in desiccated ovens. The PSU was dried at a temperature of 300°C, while the PC and SiPC were dried at a temperature of 175 °F. Following drying, the ingredients of each example were tumble-blended for about
  • the example and comparative polymer compositions were injection molded to produce the ASTM tensile and flexural specimens and UL94 flame resistance specimens described below.
  • the flame resistance properties of the polymer compositions were evaluated according to UL94 using specimens measuring 12.7 mm x 127 mm with thicknesses of 1.6 mm.
  • V-2 burning stops within 30 seconds on a vertical specimen; drips of flaming particles are allowed.
  • V-l burning stops within 30 seconds on a vertical specimen; drips of particles allowed as long as they are not inflamed.
  • V-0 burning stops within 10 seconds on a vertical specimen; drips of particles allowed as long as they are not inflamed.
  • Comparative Examples CI and C14 show that compositions of 100 wt.% SiPC copolymer and 100 wt.% PSU, respectively, either failed the flame resistance test (NR) or achieved a low score of "V-2".
  • the compositions comprising 30 wt.% or less of PSU Comparative Examples CI and C14 show that compositions of 100 wt.% SiPC copolymer and 100 wt.% PSU, respectively, either failed the flame resistance test (NR) or achieved a low score of "V-2".
  • the compositions comprising 30 wt.% or less of PSU Comparative
  • Examples C2 to C4) lead to a V-2 or lower flame resistance score and therefore were not considered satisfactory.
  • Comparative Example C15 including 50 wt.% of poly(ether sulfone) (PES) and 50 wt.% of SiPC copolymer achieved a V-2 flame resistance rating in each of the flame resistance tests. This low rating was exhibited despite the fact that the 100 wt.% PES composition of Comparative Example C16 showed a V-0 rating.
  • PES poly(ether sulfone)
  • Comparative Example C17 shows that a composition including PSU and a polycarbonate achieved a V-2 flame resistance rating, thereby not leading to a satisfactory flame resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition polymère qui comprend plus de 30 % en poids d'une polysulfone (PSU), sur la base du poids total de la composition polymère, au moins un copolymère polycarbonate-polysiloxane (SiPC), éventuellement au moins un poly(éther-imide) (PEI), et éventuellement au moins une charge renforçante. Les procédés de fabrication de la composition polymère et des articles profilés comprenant la composition polymère sont également décrits.
PCT/EP2018/080862 2017-11-13 2018-11-12 Compositions de polysulfone comprenant un copolymère polycarbonate-polysiloxane Ceased WO2019092229A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189662A (en) 1961-01-23 1965-06-15 Gen Electric Organopolysiloxane-polycarbonate block copolymers
US5502134A (en) 1989-07-07 1996-03-26 Idemitsu Petrochemical Co., Ltd. Resin composition containing a polycarbonate-polydimethylsiloxane
US6072011A (en) 1991-07-01 2000-06-06 General Electric Company Polycarbonate-polysiloxane block copolymers
US8017699B1 (en) * 2010-10-20 2011-09-13 Sabic Innovative Plastics Ip B.V. Polyimide polyphenylsulfone blends with improved flame resistance
US20140371360A1 (en) * 2013-05-24 2014-12-18 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
WO2014202673A1 (fr) * 2013-06-21 2014-12-24 Solvay Specialty Polymers Usa, Llc Compositions renforcées
US8981017B2 (en) 2009-12-10 2015-03-17 Idemitsu Kosan Co., Ltd. Polycarbonate-polyorganosiloxane copolymer, process for production of the copolymer, and polycarbonate resin containing the copolymer
WO2017003843A1 (fr) * 2015-06-30 2017-01-05 Sabic Global Technologies B.V. Composition thermoplastique avec propriétés de résistance chimique et de résistance aux chocs équilibrées

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189662A (en) 1961-01-23 1965-06-15 Gen Electric Organopolysiloxane-polycarbonate block copolymers
US5502134A (en) 1989-07-07 1996-03-26 Idemitsu Petrochemical Co., Ltd. Resin composition containing a polycarbonate-polydimethylsiloxane
US6072011A (en) 1991-07-01 2000-06-06 General Electric Company Polycarbonate-polysiloxane block copolymers
US8981017B2 (en) 2009-12-10 2015-03-17 Idemitsu Kosan Co., Ltd. Polycarbonate-polyorganosiloxane copolymer, process for production of the copolymer, and polycarbonate resin containing the copolymer
US8017699B1 (en) * 2010-10-20 2011-09-13 Sabic Innovative Plastics Ip B.V. Polyimide polyphenylsulfone blends with improved flame resistance
US20140371360A1 (en) * 2013-05-24 2014-12-18 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same
WO2014202673A1 (fr) * 2013-06-21 2014-12-24 Solvay Specialty Polymers Usa, Llc Compositions renforcées
WO2017003843A1 (fr) * 2015-06-30 2017-01-05 Sabic Global Technologies B.V. Composition thermoplastique avec propriétés de résistance chimique et de résistance aux chocs équilibrées

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Title
"Fiberglass and Glass Technology", vol. XIV, 2010, pages: 197 - 225
JOHN MURPHY: "Additives for Plastics Handbook", pages: 43 - 48

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