EP0000733A1 - Blends of polyarylsulfones and polycarbonates and their application during the manufacture of extruded films - Google Patents

Blends of polyarylsulfones and polycarbonates and their application during the manufacture of extruded films Download PDF

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Publication number
EP0000733A1
EP0000733A1 EP7878100510A EP78100510A EP0000733A1 EP 0000733 A1 EP0000733 A1 EP 0000733A1 EP 7878100510 A EP7878100510 A EP 7878100510A EP 78100510 A EP78100510 A EP 78100510A EP 0000733 A1 EP0000733 A1 EP 0000733A1
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Prior art keywords
bis
hydroxyphenyl
polycarbonate
polycarbonates
weight
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EP7878100510A
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German (de)
French (fr)
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EP0000733B1 (en
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Rudolf Dr. Binsack
Eckart Dr. Reese
Joachim Ing.Grad. Wank
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Bayer AG
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Bayer AG
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Priority claimed from DE19772755025 external-priority patent/DE2755025A1/en
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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

Definitions

  • the present invention relates to polyarylsulfone-polycarbonate mixtures of 90% by weight to 60% by weight of linear polyarylsulfone and 10% by weight to 40% by weight of polycorbonate with an Mw (weight average molecular weight) greater than 60,000.
  • the mixing ratio is preferably between 85% by weight to 70% by weight of polyarylsulfone and between 15% by weight and 3J% by weight of polycarbonate.
  • Such mixtures can be used for the production of cast films (Examples 8 and 9 of the DT-OS and 14 and 16 of US-PS).
  • the polycarbonates which are usually suitable for injection molding and extrusion and whose Mw is, for example, about 35,000 are specified as polycarbonates (example 2 of the DT-OS).
  • films made from such mixtures show a strong tendency to stress corrosion cracking.
  • polyarylsulfone-polycarbonate mixtures according to the invention provide extrusion films with an excellent property profile, even though they contain as the polycarbonate component a polycarbonate that cannot be extruded without reducing the molecular weight and although the mixtures are not suitable for the production of cast films.
  • Polyarylsulfones which are suitable according to the invention are in principle all known linear aromatic polysulfones and polyether sulfones with Mw (weight average molecular weight measured for example by means of light scattering) between about 15,000 and about 55,000, preferably between about 20,000 and 4,000.
  • Preferred polyarylsulfones are those of the following structural units of the formula (I) obtainable from bisphenols and dihalogenarylsulfones wherein Ar 1 is a biphenylene or oxibiphenylene radical, n 0 or 1, Z is a p-phenylene radical, m-phenylene radical or divalent radical of the following formula.
  • R is a divalent C 1 -C 12 alkyl or alkylidene radical, C 5 -C 12 cycloalkylene or cycloalkylidene radical, C 7 -C 12 aralkylene or aralkylidene radical or C 8 -C 12 -Arlene-bise.lkyliden rest or the grouping -O-, -S-, -SO-, -SO 2 -, -CO- or a simple bond.
  • the aromatic polycarbonates can be prepared by known methods, e.g. after the melt transesterification process from bisphenol and diphenyl carbonate and the two-phase interface process from bisphenols and phosgene, as described in the above-mentioned literature.
  • the aromatic polycarbonates can be branched through the incorporation of small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used), of three- or more than three-functional compounds, in particular those having three or more than three phenolic hydroxyl groups
  • Polycarbonates of this type are, for example le in the German disclosure g ungsschriften 1,570,533, 1,595,762, 2,116,974, 2,113,347 and 2,500,092, British Patent 1,079,821 and U.S. Patent No. 3,544,514 described.
  • the weight average molecular weights of the polycarbonates suitable according to the invention should be above 60,000, preferably between 65,000 and 120,000 and in particular between 75,000 and 95,000. (Determined from the intrinsic viscosity, measured in CH 2 Cl 2 solution).
  • Aromatic polycarbonates for the purposes of the invention are in particular homopolycarbonates made from bis-2- (4-hydroxyphenyl) propane (bisphenol-A) and copolycarbonates made from at least 30 mol%, preferably at least 60 mol% and in particular at least 80 mol% of bisphenol A and up to 70 mol%, preferably up to 40 mol% and in particular up to 20 mol% from other diphenols.
  • bisphenol-A bis-2- (4-hydroxyphenyl) propane
  • copolycarbonates made from at least 30 mol%, preferably at least 60 mol% and in particular at least 80 mol% of bisphenol A and up to 70 mol%, preferably up to 40 mol% and in particular up to 20 mol% from other diphenols.
  • the molar percentages each refer to the total molar amount of condensed diphenols).
  • diphenols bis (4-hydroxyphenyl) methane (bisphenol F), 2,4-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2 Bis (3-methyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane 2,4-bis (3,5-dimethyl-4-hydrexyphenyl) -2-methylbutane and 1,1-bis (3,5-dimethyl-4-hydroxyphenyl -) - cyclohexane are suitable.
  • Copolycarbonates preferred according to the invention contain bisphenol A and 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z).
  • Preferred mixing processes are processes 2 to 4, and mixing process 4 is particularly preferred.
  • Suitable apparatuses for the production of the polycarbonate mixtures according to the invention are rollers, kneading and screw machines.
  • Preferred apparatus are screw machines, in particular twin-screw machines.
  • the extrusion films can be produced from the blends according to the invention in a known manner, for example on normal, catchy three-zone counters according to the state of the art, with the deformation into films and wide slit nozzles into specialist films, and also via film blowing heads into blown films.
  • extrusion films according to the invention have a particularly advantageous property profile, which makes them suitable, for example, for use on the electric sect.
  • the extrusion films according to the invention have high mechanical strength, high resistance to stress corrosion cracking in the heat and to organic liquids, high heat resistance and long-term heat resistance.
  • they are characterized by their resistance to unsaturated polyester resin solutions.
  • additives or fillers known in polycarbonate and polysulfone chemistry can also be added to the mixtures according to the invention.
  • dyes such as dyes, pigments, mold release agents, stabilizers against the effects of moisture, heat and UV, lubricants, fillers, such as glass powder, quartz products, graphite, molybdenum sulfide, metal powder, powders of high-melting plastics, e.g. Polytetrafluoroethylene powder, natural fibers such as cotton, sisal and asbestos, furthermore glass fibers of various types, metal threads and fibers which are stable and do not noticeably damage the polycarbonates while they are in the melt of the polycarbonates.
  • fillers such as glass powder, quartz products, graphite, molybdenum sulfide, metal powder, powders of high-melting plastics, e.g. Polytetrafluoroethylene powder, natural fibers such as cotton, sisal and asbestos, furthermore glass fibers of various types, metal threads and fibers which are stable and do not noticeably damage the polycarbonates while they are in the melt of the polycarbonates.
  • a linear polyarylsulfone produced by condensation of 4,4'-dichlorodiphenyl sulfone and bis-2- (4-hydroxy-plenyl) propane with a M w of 20,000 and 20 wt .-% of a polycarbonate based on bisphenol A with a M w of 95,000 are melted together in a 2-shaft screw, the cylinder temperatures being 340 ° C.
  • the enamel is pressed out as a strand.
  • the strand is cooled and granulated.
  • the granules obtained are melted on a single screw with a degassing zone, and expressed the melt through a slit die and drawn off via a chill roll Arilage to about 40 / um thick Folion.
  • the property values obtained are listed in the table below.
  • the polymers acc. Example 1 were dissolved together in methylene chloride, the concentration of the polymer mixture in methylonyl chloride being 17% by weight. After filtering and degassing, the solution was poured in a known manner on Tromel casting machines to give approximately 40 ⁇ m thick films. In order to remove the residual solvent content, the film obtained was after-dried at 120 ° C. The properties of the film are listed in the table below.
  • Example 1 From 80 wt .-% of a polysulfone acc.
  • Example 1 produced and processed on a single-screw screw with a blow head to about 60 microns thick films.
  • the cylinder temperatures were 280 ° C in the feed zone and 310 ° C in the following zones.
  • the nozzle temperature was also set to 310 ° C.
  • the nozzle gap was 0.8 mm.
  • the tube was expanded in a ratio of 1: 4.
  • the withdrawal speed of the film winder was set so that at the chosen screw speeds the required film thickness of 60 / m was obtained.
  • the property values of the film obtained are listed in the attached table.

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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)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

1. Polyaryl-sulphone/polycarbonate mixtures comprising 90% by weight to 60% by weight of a linear polyaryl-sulphone and 10% by weight to 40% by weight of a homopolycarbonate of bis-2-(4-hydroxyphenyl)-propane (bisphenol A) or a copolycarbonate of at least 30 mol % of bisphenol A and up to 70 mol % of other diphenols, the polycarbonate component having a ~Mw (weight-average molecular weight) greater than 60,000.

Description

Gegenstand der vorliegenden Erfindung sind Polyarylsulfon-Polycarbonat-Abmischungen aus 90 Gew.-% bis 60 Gew.-% linearem Polyarylsulfon und 10 Gew.-% bis 40 Gew.-% Polycorbonat mit einem Mw (Gewichtsy.ittelmolekulargewieht) größer 60 000.The present invention relates to polyarylsulfone-polycarbonate mixtures of 90% by weight to 60% by weight of linear polyarylsulfone and 10% by weight to 40% by weight of polycorbonate with an Mw (weight average molecular weight) greater than 60,000.

Vorzugsweise liegt das Mischungsverhältnis zwischen 85 Gew.-% bis 70 Gew.-% an Polyarylsulfon und zwischen 15 Gew.-% und 3J Gew.-% an Polycarbonat.The mixing ratio is preferably between 85% by weight to 70% by weight of polyarylsulfone and between 15% by weight and 3J% by weight of polycarbonate.

Mischungen aus Pelyaryläthersulfonen und Polycarbonaten sind bereits beschrieben (siehe DT-OS 1 719 244 und US-PS 3 365 517): ebenfalls ihre Verwendung zur Herstellung von Folien (Seite 21 der DT-OS 1 719 244).Mixtures of pelyaryl ether sulfones and polycarbonates have already been described (see DT-OS 1 719 244 and US Pat. No. 3,365,517): likewise their use for the production of films (page 21 of DT-OS 1 719 244).

Durch diese Mischungen sollen einerseits die unerwün.^ch=e Belastungsversprödung der Polyaryläthersulfone und anderer- seits die Spannungsrisanfälligkeit der Polycarbonate gegenüber Lösungsmitteln behoben werden (Seite 2 der DT-OS).These mixtures are intended, on the one hand, to remedy the undesirable embrittlement of the polyaryl ether sulfones and, on the other hand, the susceptibility to stress of the polycarbonates to solvents (page 2 of the DT-OS).

Derartige Mischungen können für die Herstellung von Gießfolien verwendet werden (Beispiele 8 und 9 der DT-OS sowie 14 und 16 von US-PS). In den genannten Literaturstellen sind als Polycarbonate die üblicherweise für Spritzguß und Extrusion geeigneten Polycarbonate angegeben deren Mw beispielsweise etwa 35000 beträgt (Beispiel 2 der DT-OS). Folien aus derartigen Mischungen zeigen jedoch eine starke Neigung zu Spannungsrißkorrosion.Such mixtures can be used for the production of cast films (Examples 8 and 9 of the DT-OS and 14 and 16 of US-PS). In the references mentioned, the polycarbonates which are usually suitable for injection molding and extrusion and whose Mw is, for example, about 35,000 are specified as polycarbonates (example 2 of the DT-OS). However, films made from such mixtures show a strong tendency to stress corrosion cracking.

Wird die in der DT-OS 17 19 244 bzw. US-PS 3.365.517 beschriebene Polyoarbonatkomponente mit einem Mw von 35.000 durch ein hochmolekulares, ohne Kolekulargewichtsabbau nicht extrudierbares Polycarbonat ersetzt und aus derartigen Mischungen Gießfolien hergestellt, zeigen diese Produkte ebenfalls eine starke Neigung zu Spannungsrißkorrosion sowie mangelhafte mechanische Eigenschaftsvsarte .If the polyoarbonate component described in DT-OS 17 19 244 or US Pat. No. 3,365,517 with an Mw of 35,000 is replaced by a high molecular weight polycarbonate that cannot be extruded without molecular weight reduction and cast films made from such mixtures, these products also show a strong tendency Stress corrosion cracking and poor mechanical properties.

Demgegenüber war es überraschend, daß die erfindungsgemäßen Polyarylsulfon-Polycarbonat-Abmdschungen Extrusiohsfolien mit einem'ausgezeiehneten Eigenschaftsbild liefern, obwohl sie als Polycarbonatkomponente ein ohne Kolekulargewichtsabbau nicht extrudierbares Polycarbonat enthalten und obwohl die Abmischungen nicht zur Herstellung von Gießfolien geeignet sind.In contrast, it was surprising that the polyarylsulfone-polycarbonate mixtures according to the invention provide extrusion films with an excellent property profile, even though they contain as the polycarbonate component a polycarbonate that cannot be extruded without reducing the molecular weight and although the mixtures are not suitable for the production of cast films.

ErfindungsgemäB geeignete Polyarylsulfone sind grundsätzlich alle bekannten linearen aromatischen Polysulfone und PolyäthersuFfone mit Mw (Gewichtsmittelmo'skular- gewicht gemessen beispielsweise mittels Lichtstreuc.ng) zwischen etwa 15000 und etwa 55000, vorzugsweise zwischen etwa 20000 und 4000Q.Polyarylsulfones which are suitable according to the invention are in principle all known linear aromatic polysulfones and polyether sulfones with Mw (weight average molecular weight measured for example by means of light scattering) between about 15,000 and about 55,000, preferably between about 20,000 and 4,000.

Derartige Polyarylsulfone sind in den folgenden Literaturstellen beispielsweise beschrieben:

  • in den bereits genannten DT-OS 1 719 244 und US-PS 3 365 517.
Such polyarylsulfones are described, for example, in the following references:
  • in the aforementioned DT-OS 1 719 244 and US-PS 3 365 517.

Vorzugsweise geeignete Polyarylsulfone sind die aus Bisphenolen und Dihalogenarylsulfonen erhältlichen der nachfolgenden Struktureinheiten der Formel (I)

Figure imgb0001
worin Ar1einen Biphenylen- oder Oxibiphenylen-Rest, n 0 oder 1, Z einen p-Phenylenrest, m-Phenylenrest oder zweibindigen Rest der folgenden Formel. (II)
Figure imgb0002
entspricht, worin R einen zweiwertigen C1-C12-Alkylcn- bzw. Alkyliden-Rest, C5-C12-Cycloalkylen- bzw. Cycloalkylidenrest, C7-C12-Aralkylen- bzw. Aralkyliden-Rest oder C8-C12-Arylen-bise.lkyliden-Rest oder die Gruppierung -O-, -S-, -SO-, -SO2-, -CO- oder eine einfache Bindung bedeutet.Preferred polyarylsulfones are those of the following structural units of the formula (I) obtainable from bisphenols and dihalogenarylsulfones
Figure imgb0001
 wherein Ar 1 is a biphenylene or oxibiphenylene radical, n 0 or 1, Z is a p-phenylene radical, m-phenylene radical or divalent radical of the following formula. (II)
Figure imgb0002
 corresponds in which R is a divalent C 1 -C 12 alkyl or alkylidene radical, C 5 -C 12 cycloalkylene or cycloalkylidene radical, C 7 -C 12 aralkylene or aralkylidene radical or C 8 -C 12 -Arlene-bise.lkyliden rest or the grouping -O-, -S-, -SO-, -SO 2 -, -CO- or a simple bond.

Erfirnungsgemäß geeignete Polycarbonate sind aromatische Homopolycarbonate und aromatische Ccpolycarbonate, denen z.B. ein oder mehrere der folgenden Diphenole zugrunde liegen:

  • Hydrochinon
  • Resorcin
  • Dihydroxydiphenyle
  • Bis-(hydroxyphenyl)-alkane
  • Bis-(hydroxyphenyl)-cycloalkene
  • Bis-(hydroxyphenyl)-sulfide
  • Bis-(hydroxyphenyl)-äther
  • Bis-(hydroxyphenyl)-ketone
  • Bis-Xhydroxyphenyl)-sulfoxide
  • Bis-(hydroxyphenyl)-sulfone
  • x,x'-Bis-(hydroxyphenyl)-diisopropylbenzole

sowie deren kernalkylierte und kernhalogenierte Verbindungen. Diese und weitere geeignete Diphenol sind z.B. in den US-Patentschriften 3 028 365, 2 999 835, 3 148 172, 3 271 368, 2 991 273, 3 271 367, 3 280 078, 3 014 891 und 2 999 846, in den deutschen Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, 2 211 956, 2 211 957, der franz. Patentschrift, 1 561 518 und in der Monographie "H. Schnell, Chemistry and Physics of Polycarbonates, Intersciene Publishers, New York, 1964" beschrieben.Polycarbonates suitable according to the invention are aromatic homopolycarbonates and aromatic copolycarbonates which are based, for example, on one or more of the following diphenols:
  • Hydroquinone
  • Resorcinol
  • Dihydroxydiphenyls
  • Bis (hydroxyphenyl) alkanes
  • Bis (hydroxyphenyl) cycloalkenes
  • Bis (hydroxyphenyl) sulfides
  • Bis (hydroxyphenyl) ether
  • Bis (hydroxyphenyl) ketones
  • Bis-xhydroxyphenyl) sulfoxides
  • Bis (hydroxyphenyl) sulfones
  • x, x'-bis (hydroxyphenyl) diisopropylbenzenes

and their nuclear alkylated and nuclear halogenated compounds. These and other suitable diphenol are described, for example, in US Pat. Nos. 3,028,365, 2,999,835, 3,148,172, 3,271,368, 2,991,273, 3,271,367, 3,280,078, 3,014,891, and 2,999,846 German Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, 2 211 956, 2 211 957, the French. Patent, 1,561,518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Intersciene Publishers, New York, 1964".

Die aromatischen Polycarbonate können nach bekannten Verfahren hergestellt werden, so z.B. nach dem Schmelzumesterungsverfahren aus Bisphenol und Diphenylcarbonat und dem Zweiphasengrenzflächenverfahren aus Bisphenolen und Phosgen, wie es in der obengenanhten Literatur beschrieben ist.The aromatic polycarbonates can be prepared by known methods, e.g. after the melt transesterification process from bisphenol and diphenyl carbonate and the two-phase interface process from bisphenols and phosgene, as described in the above-mentioned literature.

Die aromatischen Polycarbonate können durch den Einbau geringer Mengen,vorzugsweise von Mengen zwischen 0.05 und 2.0 Mol-% (betegen auf eingesetzte Diphenole), an drei- oder mehr als dreifunktionellen Verbindungen, insbesondere solchen mit drei oder mehr als drei phenolischen Hydroxygruppen verzweigt seinThe aromatic polycarbonates can be branched through the incorporation of small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used), of three- or more than three-functional compounds, in particular those having three or more than three phenolic hydroxyl groups

Polycarbonate dieser Art sind z.B. in den deutschen Offen- legungsschriften 1 570 533, 1 595 762, 2 116 974, 2 113 347 und 2 500 092,der britischen Patentschrift 1 079 821 und der US-Patentschrift 3 544 514 beschrieben.Polycarbonates of this type are, for example le in the German disclosure g ungsschriften 1,570,533, 1,595,762, 2,116,974, 2,113,347 and 2,500,092, British Patent 1,079,821 and U.S. Patent No. 3,544,514 described.

Die Gewichtsmittelmolekulargewichte der erfindungsgemäß geeigneten Polycarbonate sollen über 60000, vorzugswsise zwischen 65000 und 120000 und insbesondere zwischen 75000 und 95000 liegen. (Ermittelt aus der Intrinsic-Viskosität, gemessen in CH2Cl2-Lösung).The weight average molecular weights of the polycarbonates suitable according to the invention should be above 60,000, preferably between 65,000 and 120,000 and in particular between 75,000 and 95,000. (Determined from the intrinsic viscosity, measured in CH 2 Cl 2 solution).

Aromatische Polycarbonate im Sinne der Erfindung sind insbesordere Homopolycarbonate aus Bis-2-(4-hydroxyphenyl)-propan (Bisphenol-A) sowie Copolycarbonate aus mindestens 30 Mol-%, vorzugsweise mindestens 60 Mol-% und insbesondere mindestens 80 Mol-% an Bisphenol A und bis zu 70 Mol-%, vorzugsweise bis zu 40 Mol-% und insbesondere bis zu 20 Mol-% aus anderen Diphenolen. (Die Molprozente beziehen sich jeweils auf Gesamtmolmenge an einkondensierten Diphenolen).Aromatic polycarbonates for the purposes of the invention are in particular homopolycarbonates made from bis-2- (4-hydroxyphenyl) propane (bisphenol-A) and copolycarbonates made from at least 30 mol%, preferably at least 60 mol% and in particular at least 80 mol% of bisphenol A and up to 70 mol%, preferably up to 40 mol% and in particular up to 20 mol% from other diphenols. (The molar percentages each refer to the total molar amount of condensed diphenols).

Als andere Diphenole sind andere Bis-(hydroxyaryl)-C1-C8- alkane als Bisphenol A sowie Bis-(hydroxyaryl)-C5-C6- cycloalkane geeignet, insbesondere Bis-(4-hydroxyphenyl)-C1-C8-alkane und Bis-(4-hydroxyphenyl)-C5-C6-cycloalkane.Bis- (hydroxyaryl) -C 1 -C 8 alkanes other than bisphenol A and bis (hydroxyaryl) -C 5 -C 6 cycloalkanes, in particular bis (4-hydroxyphenyl) -C 1 -C, are suitable as other diphenols 8 alkanes and bis (4-hydroxyphenyl) -C 5 -C 6 cycloalkanes.

Als andere Diphenole sind beispielsweise Bis-(4-hydroxyphenyl)-methan (Bisphenol F), 2,4-Bis-(4-hydroxyphenyl)-butan, 1,1-Bis-(4-hydroxyphenyl)-cyclohexan, 2,2-Bis-(3-methyl-4-hydroxyphenyl)-propan, Bis-(3,5-dimeyhyl-4-hydroxyphenyl)-methan , 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan 2,4-Bis-(3,5-dimethyl-4-hydrexyphenyl)-2-methylbutan und 1,1-Bis-(3,5-dimethyl-4-hydroxyphenyl-)-cyclohexan geeignet.Examples of other diphenols are bis (4-hydroxyphenyl) methane (bisphenol F), 2,4-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2 Bis (3-methyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane 2,4-bis (3,5-dimethyl-4-hydrexyphenyl) -2-methylbutane and 1,1-bis (3,5-dimethyl-4-hydroxyphenyl -) - cyclohexane are suitable.

Erfindungsgemäß bevorzugte Copolycarbonate enthalten Bisphenol A und 1,1-Bis-(4-hydroxyphenyl)-cyclohexan (Bisphenol Z).Copolycarbonates preferred according to the invention contain bisphenol A and 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z).

Die erfindungsgemäßen Polyarylsulfon-Polycarbonat-Äbmischungen können nach folgenden vier Verfahren hergestellt werden:

  • 1. Durch gemeinsames Aufschmelzen des Polycarbonats und des Polyarylsulfons unter gleichzeitiger oder nachfolgender inniger Vermischung der Schmelze und an-schließender Extrusion der homogenisierten Schmelze in einer geeigneten Apparatur.
  • 2. Durch Aufschmelzen des Polyarylsulfons in einer geeigneten Apparatur und Eindosierung des Polycarbonats in die Schmelze des Polyarylsulfons, Homogenisierung und anschließende Extrusion des Gemisches in einer geeigneten Apparatur.
  • 3. Durch Mischen der Lösungen des Polycarbonats und des Polyarylsulfons, Ausdampfen des Lösungsmittels unter Aufschmelzen der Mischung und gleichzeitige Extrusion.
  • 4. Durch Zumischen einer Lösung des Polycarbonats zur Schmelze des Polyarylsulfons, Ausdampfen des Lösungsmittels unter Aufschmelzen des Polycarbonats, Homogenisierung der Schmelze und anschließende Extrusion in einer geeigneten Apparatur.
The polyarylsulfone-polycarbonate mixtures according to the invention can be prepared by the following four processes:
  • 1. By melting the polycarbonate and the polyarylsulfone together with simultaneous or subsequent intimate mixing of the melt and subsequent extrusion of the homogenized melt in a suitable apparatus.
  • 2. By melting the polyarylsulfone in a suitable apparatus and metering the polycarbonate into the melt of the polyarylsulfone, homogenizing and then extruding the mixture in a suitable apparatus.
  • 3. By mixing the solutions of the polycarbonate and the polyarylsulfone, evaporation of the solvent with melting of the mixture and simultaneous extrusion.
  • 4. By adding a solution of the polycarbonate to the melt of the polyarylsulfone, evaporating the solvent while melting the polycarbonate, homogenizing the melt and then extruding it in a suitable apparatus.

Bevorzugte Mischungsverfahren sind die Verfahren 2 bis 4, besonders bevorzugt ist das Mischungsverfahren 4.Preferred mixing processes are processes 2 to 4, and mixing process 4 is particularly preferred.

Als geeignete Apparaturen für die Herstellung der erfindungsgemäßen Polycarbonatgemische sind Walzen, Knat-und Schneckenmaschinen zu verstehen. Bevorzugte Apparaturen sind Schneckenmaschinen, insbesondere Zweiwellenschneckenmaschinen.Suitable apparatuses for the production of the polycarbonate mixtures according to the invention are rollers, kneading and screw machines. Preferred apparatus are screw machines, in particular twin-screw machines.

Die Herstellung der Extrusionsfolien aus den erfindungsgemäßen Abmischungen kann in bekannter Weise z.B auf normalen, dem Stand der Technik gemäßen eingängigen Dreizonenschnesken erfolgen, wobei die Verformung zu Folien sowchl über Breitschlitzdüsen zu Fachfolien, als auch über Folienblasköpfen zu Blasfolien erfolgen kann.The extrusion films can be produced from the blends according to the invention in a known manner, for example on normal, catchy three-zone counters according to the state of the art, with the deformation into films and wide slit nozzles into specialist films, and also via film blowing heads into blown films.

Die erfindungsgemäßen Extrusionsfolien haben ein besonders vorteilhaftes Eigenschaftsbild, was sie beispielsweise für die Verwendung auf dem Elektrosekter geeignet macht.The extrusion films according to the invention have a particularly advantageous property profile, which makes them suitable, for example, for use on the electric sect.

Cnter anderem besitzen die erfindungsgemäßen Extrusionsfolien eine hohe mechanische Festigkeit, eine hohe Beständigkeit gegen Spannungsrißkorrosion in der Hitze und gegenüber organischen Flüssigkeiten, eine hohe Wärmeformbeständigkeit und Dauerwärmebeständigkeit. Insbesondere sind sie durch ihre Beständigkeit gegen ungesättigte Polyesterharzlösungen ausgezeichnet.Among other things, the extrusion films according to the invention have high mechanical strength, high resistance to stress corrosion cracking in the heat and to organic liquids, high heat resistance and long-term heat resistance. In particular, they are characterized by their resistance to unsaturated polyester resin solutions.

Den erfindungsgemäßen Abmischungen können noch die in der Polycarbonat- und Polysulfon-Chemie bekannten Additive bzw. Füllstoffe zugesetzt werden.The additives or fillers known in polycarbonate and polysulfone chemistry can also be added to the mixtures according to the invention.

Erwähnt seien in diesem Zusammenhang beispielsweise Farbstoffe, Pigmente, Entformungsmittel, Stabilisatoren gegen Feuchtigkeits-, Hitze- und UV-Einwirkung, Gleitmittel, Füllstoffe,wie Glaspulver, Quarzerzeugnisse, Graphit, Molybdänsulfid, Metallpulver, Pulver höherschmelzender Kunststoffe, z.B. Polytetrafluoräthylenpulver, natürliche Fasern, wie Baumwolle, Sisal und Asbest, ferner Glasfaserr der verschieiensten Art, Metallfäden sowie während des Verweilens in der Schmelze der Polycarbonate stabile und die Polycarbonate nicht merklich schädigende Fasern.In this context, mention may be made, for example, of dyes, pigments, mold release agents, stabilizers against the effects of moisture, heat and UV, lubricants, fillers, such as glass powder, quartz products, graphite, molybdenum sulfide, metal powder, powders of high-melting plastics, e.g. Polytetrafluoroethylene powder, natural fibers such as cotton, sisal and asbestos, furthermore glass fibers of various types, metal threads and fibers which are stable and do not noticeably damage the polycarbonates while they are in the melt of the polycarbonates.

Beispiel 1:Example 1:

80 Gew.-% eines linearen Polyarylsulfons, hergestallt durch Kondensation von 4,4'-Dichlordiphenylsulfon und Bis-2-(4-hydroxy- plenyl)-Propan mit einem M w von 20.000 und 20 Gew.-% eines Polycarbonats auf Basis Bisphenol A mit einem M w von 95.000 werdan zusammen in einer 2-Wellenschnecke aufgeschmolzen, wobei die Zylindertemperaturen 340°C betragen. Die Schmelz wird als Strang ausgepreßt. Der Strang wird gekühlt und granuliert. Das erhaltene Granulat wird auf einer Einwellenschnecke mit Entgasungszone aufgeschmolzen,und die Schmelze über eine Breitschlitzdüse ausgedrückt und über eine Chill-Roll-Arilage zu ca. 40/um dicken Folion abgezogen. Die erhaltenen Eigenschaftswerte sind in nachfolgender Tabelle aufgeführt.80 wt .-% of a linear polyarylsulfone, produced by condensation of 4,4'-dichlorodiphenyl sulfone and bis-2- (4-hydroxy-plenyl) propane with a M w of 20,000 and 20 wt .-% of a polycarbonate based on bisphenol A with a M w of 95,000 are melted together in a 2-shaft screw, the cylinder temperatures being 340 ° C. The enamel is pressed out as a strand. The strand is cooled and granulated. The granules obtained are melted on a single screw with a degassing zone, and expressed the melt through a slit die and drawn off via a chill roll Arilage to about 40 / um thick Folion. The property values obtained are listed in the table below.

Peispiel 2:Example 2:

Herstellung von Folien gem. Beispiel 1, jedoch unter Verwendung von 70 Gew.-% eines Polyarylsulfons gem. Beispiel 1 und 30 Gew.-% eines Bisphenol-A-Polycarbonates, dessen M w 75.000 bsträgt. Die Eigenschaftswerte der erhaltenen Folie sind in nachfolgender Tabelle aufgeführt.Production of foils acc. Example 1, but using 70 wt .-% of a polyarylsulfone acc. Example 1 and 30 wt .-% of a bisphenol A polycarbonate, the M w is 75,000. The property values of the film obtained are listed in the table below.

Beispiel 3: (Vergleichsbeispiel)Example 3: (comparative example)

Die Polymeren gem. Beispiel 1 wurden gemeinsam in Methylenchlorid gelöst, webei die Konzentration der Polymermischung in Methylonoklo- rid 17 Gew.-% beträgt. Die Lösung wurde nach Filtrieren und Entgasen in bekannter Weise auf Tromelgießmaschinen zu ca. 40 µm dicken Folien vergossen. Zur Entfernung des Restgehaltes an Lösungsmitteln wurde die erhaltene Folie bei 120°C nachgatrocknet. Die Eigenschaftswerte der Folie sind in nachfolgender Tabelle aufgeführt.The polymers acc. Example 1 were dissolved together in methylene chloride, the concentration of the polymer mixture in methylonyl chloride being 17% by weight. After filtering and degassing, the solution was poured in a known manner on Tromel casting machines to give approximately 40 μm thick films. In order to remove the residual solvent content, the film obtained was after-dried at 120 ° C. The properties of the film are listed in the table below.

Beispiel 4: (Vergleichsbeispiel)Example 4: (comparative example)

Aus 80 Gew.-% eines Polysulfons gem. Beispiel 1 und 20 Gew.-% eines Bisphenol-A-Polycarbonats, dessen M w 30.000 beträgt, wird ein Granulat gem. Beispiel 1 hergestellt und auf einer Einwellenschnecke mit Blaskopf zu ca. 60 µm dicken Folien verarbsitet. Die Zylindertemperaturen betrugen in der Einzugszone 280°C und in den folgenden Zonen 310°C Die Düsentemperatur wurde ebenfalls auf 310°C eingestellt. Der Düsenspalt betrug 0,8 mm. Der Schlauch wurde im Verhältnis 1 : 4 aufgeweitet. Die Abzugsgeschwindigkeit des Folienwicklers wurde so eingestellt, daß bei den gewählten Schneckendrehzahlen die gewünschte Foliendicke von 60 /um erhalten wurde. Die Eigenschaftswerte der erhaltenen Folie sind in beiliegender Tabelle aufgeführt.

Figure imgb0003
From 80 wt .-% of a polysulfone acc. Example 1 and 20 wt .-% of a bisphenol A polycarbonate, the M w is 30,000, a granulate is gem. Example 1 produced and processed on a single-screw screw with a blow head to about 60 microns thick films. The cylinder temperatures were 280 ° C in the feed zone and 310 ° C in the following zones. The nozzle temperature was also set to 310 ° C. The nozzle gap was 0.8 mm. The tube was expanded in a ratio of 1: 4. The withdrawal speed of the film winder was set so that at the chosen screw speeds the required film thickness of 60 / m was obtained. The property values of the film obtained are listed in the attached table.
Figure imgb0003

Claims (6)

1. Polyarylsulfon-Polycarbonat-Abmischungen aus 90 Gew.-% bis 60 Gew.-% linearem Polyarylsulfon, und aus 10 Gew.-% bis 40 Gew.-% Polycarbonat mit einem Mw (Gewichtsmittelmolekulargewicht) größer 60.000.1. Polyarylsulfone-polycarbonate blends of 90 wt .-% to 60 wt .-% linear polyarylsulfone, and from 10 wt .-% to 40 wt .-% polycarbonate with a M w (weight average molecular weight) greater than 60,000. 2. Abmischungen gemäß Anspruch 1, dadurch gekennzeichnet, daß das Mw der Polycarbonatkomponente zwischen 65 000 und 120 000 liegt.2. Mixtures according to claim 1, characterized in that the Mw of the polycarbonate component is between 65,000 and 120,000. 3. Abmischungen gemäß Anspruch 1, dadurch gekennzeichnet, daß das Mw der Polycarbonatkomponente zwischen 75 000 und 95 000 liegt.3. Mixtures according to claim 1, characterized in that the Mw of the polycarbonate component is between 75,000 and 95,000. 4. Abmischungen gemäß Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie 85 Gew.-% bis 70 Gew.-% lineares Polyarylsulfon und 15 Gew.-% bis 30 Gew.-% Polycarbonat enthalten.4. Mixtures according to claims 1 to 3, characterized in that they contain 85 wt .-% to 70 wt .-% linear polyarylsulfone and 15 wt .-% to 30 wt .-% polycarbonate. 5. Verwendung der Abmischungen gemäß Ansprüche 1 bis 4 zur Herstellung von Extrusionsfolien.5. Use of the blends according to claims 1 to 4 for the production of extrusion films. 6. Extrusionsfolien erhältlich aus den Abmischungen der Ansprüche 1 bis 4.6. Extrusion films obtainable from the blends of claims 1 to 4.
EP78100510A 1977-08-04 1978-07-26 Blends of polyarylsulfones and polycarbonates and their application during the manufacture of extruded films Expired EP0000733B1 (en)

Applications Claiming Priority (4)

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DE2735144 1977-08-04
DE19772735144 DE2735144A1 (en) 1977-08-04 1977-08-04 Linear poly:aryl:sulphone and high mol. wt. polycarbonate mixt. - extrudable to high strength films resistant to unsaturated polyester solns. and stress corrosion
DE19772755025 DE2755025A1 (en) 1977-12-09 1977-12-09 Linear poly:aryl:sulphone and high mol. wt. polycarbonate mixt. - extrudable to high strength films resistant to unsaturated polyester solns. and stress corrosion
DE2755025 1977-12-09

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EP0845501A1 (en) * 1996-11-29 1998-06-03 Sumitomo Chemical Company, Limited Thermoplastic resin composition and molded article
US6127492A (en) * 1998-05-13 2000-10-03 Sumitomo Chemical Company, Limited Thermoplastic resin composition and heat-resistant tray for IC
EP0937749A3 (en) * 1998-02-20 2002-03-20 Sumitomo Chemical Company, Limited Aromatic polysulfone resin composition and article containing the same
CN113831535A (en) * 2021-09-29 2021-12-24 金发科技股份有限公司 Preparation method of polyarylethersulfone resin, polyarylethersulfone resin obtained by preparation method and application of polyarylethersulfone resin
CN115181409A (en) * 2022-08-19 2022-10-14 苏州奥美材料科技有限公司 Modified polycarbonate composite material and preparation method and application thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0845501A1 (en) * 1996-11-29 1998-06-03 Sumitomo Chemical Company, Limited Thermoplastic resin composition and molded article
EP0937749A3 (en) * 1998-02-20 2002-03-20 Sumitomo Chemical Company, Limited Aromatic polysulfone resin composition and article containing the same
US6127492A (en) * 1998-05-13 2000-10-03 Sumitomo Chemical Company, Limited Thermoplastic resin composition and heat-resistant tray for IC
CN113831535A (en) * 2021-09-29 2021-12-24 金发科技股份有限公司 Preparation method of polyarylethersulfone resin, polyarylethersulfone resin obtained by preparation method and application of polyarylethersulfone resin
CN113831535B (en) * 2021-09-29 2023-05-16 金发科技股份有限公司 Preparation method of polyarylethersulfone resin, obtained polyarylethersulfone resin and application
CN115181409A (en) * 2022-08-19 2022-10-14 苏州奥美材料科技有限公司 Modified polycarbonate composite material and preparation method and application thereof
CN115181409B (en) * 2022-08-19 2023-09-26 苏州奥美材料科技有限公司 A modified polycarbonate composite material and its preparation method and application

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DE2860233D1 (en) 1980-12-04
EP0000733B1 (en) 1980-08-20

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