EP0000732B1 - Mélanges de polyarylsulfones réticulées avec des polycarbonates et leur utilisation dans la préparation de feuilles extrudées - Google Patents

Mélanges de polyarylsulfones réticulées avec des polycarbonates et leur utilisation dans la préparation de feuilles extrudées Download PDF

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Publication number
EP0000732B1
EP0000732B1 EP78100509A EP78100509A EP0000732B1 EP 0000732 B1 EP0000732 B1 EP 0000732B1 EP 78100509 A EP78100509 A EP 78100509A EP 78100509 A EP78100509 A EP 78100509A EP 0000732 B1 EP0000732 B1 EP 0000732B1
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EP
European Patent Office
Prior art keywords
weight
bis
polycarbonate
hydroxyphenyl
polycarbonates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100509A
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German (de)
English (en)
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EP0000732A1 (fr
Inventor
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 DE19772735092 external-priority patent/DE2735092A1/de
Priority claimed from DE19772755026 external-priority patent/DE2755026A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000732A1 publication Critical patent/EP0000732A1/fr
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Classifications

    • 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 95% by weight to 30% by weight of branched polyarylsulfone and 5% by weight to 70% by weight of polycarbonate with an Mw (weight average molecular weight) of more than 60,000.
  • the mixing ratio is preferably between 90% by weight to 60% by weight of polyarylsulfone and between 10% by weight and 40% by weight of polycarbonate.
  • the mixing ratio is between 85% by weight to 70% by weight of polyarylsulfone and between 15% by weight and 30% 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 have 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 which cannot be extruded without molecular weight degradation.
  • Branched polyarylsulfones which are suitable according to the invention are, in particular, the branched polyaryl ether sulfones according to US Pat. No. 3,960,815 or DT-OS 2,305,413, whose Mw (weight average molecular weight, measured, for example, by means of light scattering) is between about 15,000 and about 55,000, preferably between about 20,000 and 40,000. According to this DT-OS 2 305 413, these polyaryl ether sulfones are produced.
  • the branched aromatic polyaryl ether sulfones thus have double-bonded structural elements of the formula wherein Ar 4 is a biphenylene or oxybisphenylene radical, n is 0 or 1, Z is a p-phenylene radical, m-phenylene radical or divalent radical of the following formula (11) corresponds, where R is a divalent C 1 -C 12 alkylene or. Alkylidene radical, C 3 ⁇ C 12 -Cydoalkylen- or. Cycloalkylidene radical, C 7 -C 12 aralkylene or. Aralkylidene residue or C 8 ⁇ C 12 arylene bisalkylidene residue or the group -0-, -S-, -SO-, ⁇ SO 2 - -CO- or a simple binding.
  • Hai and Ar in one of these formulas corresponds to chlorine or bromine or a mono- or multinuclear, divalent aromatic radical.
  • the aromatic polycarbonates can be prepared by known methods, e.g. by 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 the oil diphenols used), of three or more than three-functional compounds, in particular those with three or more than three phenolic hydroxyl groups.
  • Polycarbonates of this type are e.g. in German laid-open publications 1 570 533, 1 595762, 2116974, 2113347 and 2 500 092, British patent specification 1 079 821 and US patent specification 3 544514. 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 in the sense of the invention are in particular homopolycarbonates from bis - 2 - (4-hydroxyphenol) propane (bisphenol-A) and copolycarbonates 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).
  • Bis- (hydroxyaryl) -C 1 ⁇ C 8 -alkanes other than bisphenol A and bis- (hydroxyaryi) -C 5 ⁇ C 6 -cycloalkanes are suitable as other diphenols, in particular bis- (4-hydroxyphenyl) -C 1 -C 8 alkanes and bis (4-hydroxyphenol) -C 5 -C 6 cycloalkanes.
  • Examples of other diphenols are bis (4) hydroxyphenyl) methane (bisphenol F), 2,4-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxypheny) 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 - hydroxyphenyl) -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 mixtures according to the invention are rollers, kneading and screw machines.
  • Preferred apparatus are screw machines, in particular twin-screw machines.
  • the production of the extrusion films from the blends according to the invention can be carried out in a known manner e.g. are carried out on normal, catchy three-zone screws according to the state of the art, and the preforming into foils can take place both via wide-slot nozzles to form foils, and also via blown film heads to blown foils.
  • extrusion films according to the invention have a particularly advantageous property profile, which makes them suitable, for example, for use in the electrical sector.
  • 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.
  • the mixtures according to the invention may or filling st q ffe be added yet known in polycarbonate and poly 'sulfone chemical additives.
  • 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 all kinds, metal threads as well as fibers which remain stable in the melt of the polycarbonates and fibers which are not noticeably damaging to 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 all kinds, metal threads as well as fibers which remain stable in the melt of the polycarbonates and fibers which are not noticeably damaging to the polycarbonates.
  • a branched polyarylsulfone which by reacting 0.25 mol of 2,2 - bis - (4-hydroxyphenyl) propane, with 0.0025 mol of 2.6 - bis - (2'-hydroxy-5'-methylbenzyl ) - 4-methyl-phenol and 0.25375 mol of 4,4'-dichlorodiphenyl sulfone was produced (see US Pat. No. 3,960,815 Example 1), with a M w of 30,000 and 20% by weight of a polycarbonate based on bisphenol A with an M w of 95,000 are melted together in a 2-shaft screw, the cylinder temperatures being 340 ° C. The melt is pressed out as a strand. The strand is cooled and granulated.
  • the granules obtained are melted on a single-shaft screw with a removal zone, and the melt is pressed out through a slot die and drawn off to form films about 40 ⁇ m thick using a chill-roll system.
  • 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 methylene chloride being 17% by weight. After filtering and degassing, the solution was cast in a known manner on drum casting machines to about 40 ⁇ m thick foils. The film obtained was subsequently dried at 120 ° C. to remove the residual solvent content. The properties of the film are listed in the table below.
  • Example 1 From 80 wt .-% of a branched polysulfone acc. Example 1 and 20 wt .-% of a bisphenol A polycarbonate, whose M w is 30.00, a granulate according to Example 1 produced and processed on a single-shaft screw with a blow head to about 60 to 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 take-off speed of the film winder was set so that the desired film thickness of 60 ⁇ m was obtained at the selected screw speeds.
  • the property values of the film obtained are listed in the attached table.
  • reaction mixture obtained in this way is heated to a temperature of 140-150 ° C. for 6 hours, the water contained in the reaction mixture and the water formed during the formation of the phenolate being continuously distilled with the toluene as an azeotrope in the water collecting device and being separated off there while the toluene is again runs back into the reaction mixture.
  • the water collecting vessel When all water has been removed from the reaction system, the water collecting vessel is emptied, the toluene is distilled off and a solution of 72.882 g (0.25 + 0.00375 mol) of 4,4'-dichlorodiphenyl sulfone is added at a temperature of 120-140 ° C Add 100 ml of anhydrous dimethyl sulfoxide. The mixture is then gradually heated to a reaction temperature of 150 ° C. with stirring. The reaction mixture is left at this temperature for 6 hours, during which the sodium chloride formed during the condensation precipitates rapidly. After the reaction has ended, the cooled polymer solution is introduced into rapidly stirred water, the polyaryl ether sulfone obtained separating out in solid form.
  • the polysulfone obtained is dissolved in methylene chloride, filtered and poured into an excess of rapidly stirred methanol. The polysulfone separates in white flakes. It is filtered off and dried.

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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)
  • Polyesters Or Polycarbonates (AREA)

Claims (7)

1. Mélanges polycarbonate-polyarylsulfone consistant en 95 à 30 % en poids de polyarylsulfone ramifiée et 5 à 70 % en poids d'un polycarbonate présentant un poids moléculaire moyen Mw (moyenne en poids) supérieur à 60 000.
2. Mélanges selon la revendication 1, caractérisés en ce que le poids moléculaire Mw du composant polycarbonate se situe entre 65 000 et 120000.
3. Mélanges selon la revendication_1, caractérisés en ce que le poids moléculaire Mw du composant polycarbonate se situe entre 75 000 et 95 000.
4. Mélanges selon les revendications 1 à 3, caractérisés en ce qu'ils contiennent de 90 à 60 % en poids de polyarylsulfone ramifiée et de 10 à 40 % en poids de polycarbonate.
5. Mélanges selon les revendications 1 à 3, caractérisés en ce qu'ils continnent de 85 à 70 % en poids de polyarylsulfone et de 15 à 30 % en poids de polycarbonate.
6. Utilisation des mélanges selon les revendications 1 à 5 pour la préparation de feuilles extrudées.
7. Feulles extrudées obtenues à partir des mélanges des revendications 1 à 5.
EP78100509A 1977-08-04 1978-07-26 Mélanges de polyarylsulfones réticulées avec des polycarbonates et leur utilisation dans la préparation de feuilles extrudées Expired EP0000732B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19772735092 DE2735092A1 (de) 1977-08-04 1977-08-04 Abmischungen von verzweigtem polyarylsulfon-polycarbonat sowie ihre verwendung zur herstellung von extrusionsfolien
DE2735092 1977-08-04
DE19772755026 DE2755026A1 (de) 1977-12-09 1977-12-09 Abmischungen von verzweigtem polyarylsulfon-polycarbonat sowie ihre verwendung zur herstellung von extrusionsfolien
DE2755026 1977-12-09

Publications (2)

Publication Number Publication Date
EP0000732A1 EP0000732A1 (fr) 1979-02-21
EP0000732B1 true EP0000732B1 (fr) 1980-07-23

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EP78100509A Expired EP0000732B1 (fr) 1977-08-04 1978-07-26 Mélanges de polyarylsulfones réticulées avec des polycarbonates et leur utilisation dans la préparation de feuilles extrudées

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Country Link
US (1) US4152367A (fr)
EP (1) EP0000732B1 (fr)
JP (1) JPS6040473B2 (fr)
DE (1) DE2860069D1 (fr)
IT (1) IT1106864B (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2948673A1 (de) * 1979-12-04 1981-06-11 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von giessfolien aus polyarylsulfon-polycarbonat-abmischungen
EP0057214A4 (fr) * 1980-08-11 1982-12-20 Gen Electric Compositions de polycarbonate ignifuges.
US4477637A (en) * 1980-08-27 1984-10-16 Mobay Chemical Corporation Flame retardant alkylated polycarbonate compositions
US4358569A (en) * 1980-12-31 1982-11-09 General Electric Company Blends of copolyester-carbonate with polysulfone
WO1988000886A1 (fr) * 1986-08-07 1988-02-11 Amoco Corporation Article façonne forme a partir d'un melange d'un poly(aryle ether) et un polycarbonate
DE3836176A1 (de) * 1988-10-24 1990-05-03 Bayer Ag Polymermischungen
DE4208341A1 (de) * 1992-03-16 1993-09-23 Basf Ag Thermoplastische formmassen aus copolyarylenethern und polycarbonaten
US5633331A (en) * 1996-05-02 1997-05-27 The Dow Chemical Company Blends of polysulfone with diaryl fluorene carbonate polymer
US5910560A (en) * 1996-11-29 1999-06-08 Sumitomo Chemical Company, Ltd. Thermoplastic resin composition and molded article
US6776602B2 (en) * 1999-04-20 2004-08-17 Stratasys, Inc. Filament cassette and loading system
US7754807B2 (en) * 1999-04-20 2010-07-13 Stratasys, Inc. Soluble material and process for three-dimensional modeling
US7314591B2 (en) * 2001-05-11 2008-01-01 Stratasys, Inc. Method for three-dimensional modeling
US6722872B1 (en) * 1999-06-23 2004-04-20 Stratasys, Inc. High temperature modeling apparatus
DE10149871A1 (de) * 2001-10-10 2003-04-17 Basf Ag Thermoplastische Formmassen mit verbesserter Schmelzstabilität auf Basis von Polyarylenethersulfonen
US6869559B2 (en) * 2003-05-05 2005-03-22 Stratasys, Inc. Material and method for three-dimensional modeling
US7067608B2 (en) * 2003-11-25 2006-06-27 Xerox Corporation Process for preparing branched polyarylene ethers
US7396895B2 (en) * 2003-11-25 2008-07-08 Xerox Corporation Branched polyarylene ethers and processes for the preparation thereof
US7236166B2 (en) * 2005-01-18 2007-06-26 Stratasys, Inc. High-resolution rapid manufacturing
US7341214B2 (en) * 2005-06-30 2008-03-11 Stratasys, Inc. Cassette spool lock
US7384255B2 (en) * 2005-07-01 2008-06-10 Stratasys, Inc. Rapid prototyping system with controlled material feedstock
DE102007044146A1 (de) * 2007-09-12 2009-03-19 Bayer Materialscience Ag Thermoplast mit Metallkennzeichnungsplättchen
JP2011511322A (ja) * 2008-02-05 2011-04-07 バイエル・テクノロジー・サービシーズ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング セキュリティエレメント

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Publication number Priority date Publication date Assignee Title
US3365517A (en) * 1965-04-08 1968-01-23 Union Carbide Corp Mixtures of polycarbonates and polyarylene polyethers
DE1932067C3 (de) * 1969-06-25 1979-09-06 Bayer Ag, 5090 Leverkusen Polyaryläthersulfone und Verfahren zu ihrer Herstellung
US3652715A (en) * 1969-07-01 1972-03-28 Gen Electric Curable polycarbonate compositions
US3631222A (en) * 1970-01-02 1971-12-28 Minnesota Mining & Mfg Polyarylsulfone graft and block copolymers with chains of polyamide acid or polyimide
US3689464A (en) * 1970-12-18 1972-09-05 Gen Electric Imido-substituted polyamide compositions
JPS5027061B1 (fr) * 1971-03-08 1975-09-04
DE2305413C2 (de) * 1973-02-03 1982-05-13 Bayer Ag, 5090 Leverkusen Verzweigte aromatische Polyaryläthersulfone

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Publication number Publication date
IT1106864B (it) 1985-11-18
DE2860069D1 (en) 1980-11-13
JPS5428362A (en) 1979-03-02
JPS6040473B2 (ja) 1985-09-11
EP0000732A1 (fr) 1979-02-21
US4152367A (en) 1979-05-01
IT7850576A0 (it) 1978-08-02

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