EP0000732B1 - Blends of reticulated polyarylsulfones and polycarbonates and their application during the manufacture of extruded films - Google Patents
Blends of reticulated polyarylsulfones and polycarbonates and their application during the manufacture of extruded films Download PDFInfo
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- 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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- 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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Description
Gegenstand der vorliegenden Erfindung sind Polyarylsulfon-Polycarbonat-Abmischungen aus 95 Gew.-% bis 30 Gew.-% verzweigtem Polyarylsulfon und 5 Gew.-% bis 70 Gew.-% Polycarbonat mit einem Mw (Gewichtsmittelmolekulargewicht) größer 60 000.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.
Vorzugsweise liegt das Mischungsverhältnis zwischen 90 Gew.-% bis 60 Gew.-% an Polyarylsulfon und zwischen 10 Gew.-% und 40 Gew.-% an Polycarbonat.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.
Insbesondere liegt das Mischungsverhältnis zwischen 85 Gew.-% bis 70 Gew.-% an Polyarylsulfon und zwischen 15 Gew.-% und 30 Gew.-% an Polycarbonat.In particular, 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.
Mischungen aus linearen Polyaryläthersulfonen und Polycarbonaten sind bereits beschrieben (siehe DT-OS 1 719244 und US―PS 3365517); ebenfalls ihre Verwendung zur Herstellung von Folien (Seite 21 der DT-OS 1 719 244).Mixtures of linear polyaryl ether sulfones and polycarbonates have already been described (see DT-OS 1 719244 and US ― PS 3365517); likewise their use for the production of films (page 21 of DT-OS 1 719 244).
Durch diese Mischungen sollen einerseits die unerwünschte Belastungsversprödung der Polyaryläthersulfone und adererseits die Spannungsrißanfälligkeit der Polycarbonate gegenüber Lösungsmitteln behoben werden (Seite 2 der DT-OS).These mixtures are intended, on the one hand, to eliminate the undesirable embrittlement of the polyaryl ether sulfones and, on the other hand, to make the polycarbonates susceptible to stress cracking with 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 besitzen 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 literature 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 have a strong tendency to stress corrosion cracking.
Wird die in der DT-OS 1 719 244 bzw. US-PS 3 365 517 beschriebene Polycarbonatkomponente mit einem Mw von 35 000 durch ein hochmolekulares, ohne Molekulargewichtsabbau nicht extrudierbares Polycarbonat ersetzt und aus derartigen Mischungen Gießfolien hergestellt, zeigen diese Produkte ebenfalls eine starke Neigung zu Spannungsrißkorrosion sowie mangelhafte mechanische Eigenschaftswerte.If the polycarbonate component with an Mw of 35,000 described in DT-OS 1 719 244 or US Pat. No. 3,365,517 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 property values.
Demgegenüber war es überraschend, daß die erfindungsgemäßen Polyarylsulfon-Polycarbonat-Abmischungen Extrusionsfolien mit einem ausgezeichneten Eigenschaftsbild liefern, obwohl sie als Polycarbonatkomponente ein ohne Molekulargewichtsabbau nicht extrudierbares Polycarbonat enthalten.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 which cannot be extruded without molecular weight degradation.
Erfindungsgemäß geeignete verzweigte Polyarylsulfone sind insbesondere die verzweigten Polyaryläthersulfone gemäß US―PS 3 960 815 bzw. DT-OS 2 305 413, deren Mw (Gewichtsmittelmolekulargewicht, gemessen beispielsweise mittels Lichtstreuung) zwischen etwa 15000 und etwa 55000, vorzugsweise zwischen etwa 20000 und 40000 liegen. Gemäß dieser DT-OS 2 305 413 werden diese Polyaryläthersulfone hergestellt.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.
Die verzweigten aromatischen Polyaryläthersulfone haben somit zweibindige Strukturelemente der Formel
Die Definition der Symbole Hai und Ar in einer dieser Formeln entspricht Chlor oder Brom beziehungsweise einem ein- oder mehrkemigen, zweiwertigen aromatischen Rest.The definition of the symbols Hai and Ar in one of these formulas corresponds to chlorine or bromine or a mono- or multinuclear, divalent aromatic radical.
Erfindungsgemäß geeignete Polycarbonate sind die armoatischen Homopolycarbonate und aromatische Copolycarbonate, denen z.B. ein oder mehrere der folgenden Diphenole zugrunde liegen:
- Hydrochinon
- Resorcin
- Dihydroxydiphenyle
- Bis-(hydroxyphenyl)-alkane
- Bis-(hydroxyphenyl)-cycloalkane
- Bis-(hydroxyphenyl)-sulfide
- Bis-(hydroxyphenyl)-äther
- Bis-(hydroxyphenyl)-ketone
- Bis-(hydroxyphenyl)-sulfoxide
- Bis-(hydroxyphenyl)-sulfone
- a,a' - Bis - (hydroxyphenyl) - diisopropylbenzole
sowie deren kernalkylierte und kernhalogenierte Verbindungen. Diese und weitere geeignete Diphenole sind z.B. in der US-Patentschrift 3 028 365 und in der Monographie "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964" beschrieben.Polycarbonates suitable according to the invention are the armoatic 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) cycloalkanes
- Bis (hydroxyphenyl) sulfides
- Bis (hydroxyphenyl) ether
- Bis (hydroxyphenyl) ketones
- Bis (hydroxyphenyl) sulfoxides
- Bis (hydroxyphenyl) sulfones
- a, a '- bis - (hydroxyphenyl) diisopropylbenzenes
and their nuclear alkylated and nuclear halogenated compounds. These and other suitable diphenols are described, for example, in US Pat. No. 3,028,365 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience 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 obengenannten Literatur beschrieben ist.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.
Die aromatischen Polycarbonate können durch den Einbau geringer Mengen, vorzugsweise von Mengen zwischen 0.05 und 2.0 Mol- % (bezogen auf eingesetzte Öiphenole), an drei-oder mehr als dreifunktionellen Verbindungen, insbesondere solchen mit drei oder mehr als drei phenolischen Hydroxygruppen verzweigt sein.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.
Polycarbonate dieser Art sind z.B. in den deutschen Offenlegungsschriften 1 570 533, 1 595762, 2116974, 2113347 und 2 500 092, der britischen Patentschrift 1 079 821 und der US-Patentschrift 3 544514 beschrieben. beschrieben.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.
Die Gewichtsmittelmolekulargewichte der erfindungsgemäß geeigneten Polycarbonate sollen über 60000, vorzugsweise 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 insbesondere Homopolycarbonate aus Bis - 2 - (4-hydroxyphenol)-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 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).
Als andere Diphenole sind andere Bis-(hy- droxyaryl)-C1―C8-alkane als Bisphenol A sowie Bis-(hydroxyaryi)-C5―C6-cycloalkane geeignet, insbesondere Bis-(4-hydroxyphenyl)-Cl-C8- alkane und Bis-(4-hydroxyphenol)-C5-C6- cycloalkane.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.
Als andere Diphenole sind beispielsweise Bis-(4)hydroxyphenyl)-methan (Bisphenol F), 2,4-Bis-(4-hydroxyphenyl)-butan, 1,1-Bis-(4-hydroxypheny)-cyclohexan, 2,2-Bis-(3-methyl-4-hydroxyphenyl)-propan, Bis-(3,5-dimethyl-4-hydroxyphenyl)-methan, 2,2 - Bis - (3,5 - dimethyl - 4 - hydroxyphenyl)-propan 2,4 - Bis - (3,5-dimethyl - 4 - hydroxyphenyl)-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-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.
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-Abmishungen können nach folgenden vier Verfahren hergestellt werden:
- 1. Durch gemiensames Aufschmelzen des Polycarbonats und des Polyarylsulfons unter gleichzeitiger oder nachfolgender inniger Vermischung der Schmelze und anschließender Extrusions 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 Polyarlysulfons, Ausdampfen des Lösungsmittels unter Aufschmelzen des Polycarbonats, Homogenisierung der Schmelze und anschließende Extrusion in einer geeigneten Apparatur.
- 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 Abmischungen sind Walzen, Knetund Schneckenmaschinen zu verstehen. Bevorzugte Apparaturen sind Schneckenmachinen, insbesondere Zweiwellenschneckenmaschinen.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.
Die Herstellung der Extrusionsfolien aus den erfindungsgemäßen Abmischungen kann in bekannter Weise z.B. auf normalen, dem Stand der Technik gemäßen eingängigen Dreizonenschnecken erfolgen, wobei die Vorformung zu Folien sowohl über Breitschlitzdüsen zu Fachfolien, als auch über Folienblasköpfen zu Blasfolien erfolgen kann.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.
Die erfindungsgemäßen Extrusionsfolien haben ein besonders vorteilhaftes Eigenschaftsbild, was sie beispielsweise für die Verwendung auf dem Elektrosektor geeignet macht.The extrusion films according to the invention have a particularly advantageous property profile, which makes them suitable, for example, for use in the electrical sector.
Unter 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 Poly-' sulfon-Chemie bekannten Additive bzw. Füll- stqffe zugesetzt werden.The mixtures according to the invention may or filling st q ffe be added yet known in polycarbonate and poly 'sulfone chemical additives.
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 Glasfasern der verschiedensten Art, Metallfäden sowie währen 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 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.
80 Gew.-% eines verzweigten Polyarylsulfons, das durch Umsetzen von 0,25 Mol 2,2 - Bis - (4-hydroxyphenyl)-propan, mit 0,0025 Mol 2.6 - Bis - (2'-hydroxy-5'-methylbenzyl) - 4 - methyl-phenol und 0,25375 Mol 4,4'-Dichlordiphenylsulfon hergestellt wurde (s. US―PS 3,960,815 Beispeil 1), mit einem
Das erhaltene Granulat wird auf einer Einwellenschnecke mit Entagsungszone aufgeschmolzen, und die Schmelze über eine Breitschlitzdüse ausgedrückt und über eine Chill-Roll-Anlage zu ca. 40 µm dicken Folien abgezogen. Die erhaltenen Eigenschaftswerte sind in nachfolgender Tabelle aufgeführt.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 μm thick using a chill-roll system. The property values obtained are listed in the table below.
Herstellung von Folien gem. Beispiel 1, jedoch unter Verwendung von 70 Gew.-% eines verzweigten Polyarylsulfons gem. Beispiel 1 und 30 Gew.-% eines Bisphenol-A-Polycarbonates, dessen Mw 75.000 beträgt. Die Eigenschaftswerte der erhaltenen Folie sind in nachfolgender Tabelle aufgeführt.Production of foils acc. Example 1, but using 70 wt .-% of a branched polyarylsulfone acc. Example 1 and 30% by weight of a bisphenol A polycarbonate, the M w of which is 75,000. The property values of the film obtained are listed in the table below.
Die Polymeren gem. Beispiel 1 wurden gemeinsam in Methylenchlorid gelöst, wobei die Konzentration der Polymermischung in Methylenchlorid 17 Gew.-% beträgt. Die Lösung wurde nach Filtrieren und Entgasen in bekannter Weise auf Trommelgießmaschinen zu ca. 40,um dicken Folien vergossen. Zur Entfernung des Restgehaltes an Lösungsmitteln wurde die erhaltene Folie bei 120°C nachgetrocknet. 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 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 μm 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.
Aus 80 Gew.-% eines verzweigten Polysulfons gem. Beispiel 1 und 20 Gew.-% eines Bisphenol-A-Polycarbonats, dessen Mw 30.00 beträgt, wird ein Granulat gem. Beispiel 1 hergestellt und auf einer Einwellenschnecke mit Blaskopf zu ca. 60,um dicken Folien verarbeitet.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.
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.
57,075 g (0,25 Mol) 2,2 - Bis - (4-hydroxyphenyl)-Propan und 0,871 g (0.0025 Mol) 2.6 - Bis - (2'-hydroxy-5'-methylbenzyl) - 4 - methyl-phenol werden in ein Metallgefäß eingewogen und in 500 ml Dimethlysulfoxid gelöst. Das Gefäß wird mit einem Gaseinleiterungsrohr, einem Rührwerk, einem Thermometer, einem Rückflußkühler und einer mit Toluol gefüllten Wasserauffangvorrichtung versehen. Dann wird ein langsamer Stickstoffstrom durch die Apparatur geleitet, um eine Inertgasatmosphäre zu erzeugen. Es werden 20,03 g (0,5 + 0,0075 Mol) Natriumhydroxid in fester Form oder als konzentrierte wässrige Lösung hinzugefügt un nach dem Lösen des Natriumhydroxids 150 ml Toluol eingetropft. Das so erhaltene Reaktionsgemisch wird 6 Stunden auf eine Temperatur von 140 - 150°C erhitzt, wobei das im Reaktionsgemisch enthaltene und das bei der Phenolatbildung entstehende Wasser kontinuierlich mit dem Toluol als Azeotrop in die Wasserauffangvorrichtung destilliert wird und sich dort abscheidet, während das Toluol wieder in das Reaktionsgemisch zurückläuft. Ist alles Wasser aus dem reaktionssystem entfernt, leert man das Wasserauffanggefäß, destilliert das Toluol ab und gibt bei einer Temperatur von 120 - 140°C eine Lösung von 72,882 g (0,25 + 0,00375 Mol) 4,4'-Dichlordiphenylsulfon in 100 ml wasserfreiem Dimethylsulfoxid hinzu. Dann erhitzt man unter Rühren allmählich auf eine Reaktionstemperatur von 150°C. Bei dieser Temperatur beläßt man die Reaktionsmischung 6 Stunden, wobei sich das bei der Kondensation entstehende Natriumchlorid schnell abscheidet. Nach Beendigung der Reaktion wird die abgekühlte Polymerlösung in schnell gerührtes Wasser eingetragen, wobei sich das erhaltene Polyaryläthersulfon in fester Form abscheidet. Es wird abgenutscht, sorgfältig gewaschen und unter Vakuum getrocknet. Zur Reinigung wird das erhaltene Polysulfon in Methylenchlorid gelöst, filtriert und in einen Übershuß schnell gerührten Methanols gegossen. Dabei scheidet sich das Polysulfon in weißen Flocken ab. Es wird abgenutscht und getrocknet.57.075 g (0.25 mol) of 2,2 - bis - (4-hydroxyphenyl) propane and 0.871 g (0.0025 mol) of 2.6 - bis - (2'-hydroxy-5'-methylbenzyl) -4-methylphenol weighed into a metal vessel and dissolved in 500 ml of dimethyl sulfoxide. The vessel is equipped with a gas inlet tube, an agitator, a thermometer, a reflux condenser and a water collecting device filled with toluene. A slow stream of nitrogen is then passed through the apparatus to create an inert gas atmosphere. 20.03 g (0.5 + 0.0075 mol) of sodium hydroxide in solid form or as a concentrated aqueous solution are added and 150 ml of toluene are added dropwise after the sodium hydroxide has been dissolved. The 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. 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. It is filtered off, washed thoroughly and dried under vacuum. For purification, 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.
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2735092 | 1977-08-04 | ||
| DE19772735092 DE2735092A1 (en) | 1977-08-04 | 1977-08-04 | Branched poly:aryl:sulphone and high mol. wt. polycarbonate mixt. - extrudable to high strength films resistant to unsaturated polyester solns. and stress corrosion |
| DE2755026 | 1977-12-09 | ||
| DE19772755026 DE2755026A1 (en) | 1977-12-09 | 1977-12-09 | Branched poly:aryl:sulphone and high mol. wt. polycarbonate mixt. - extrudable to high strength films resistant to unsaturated polyester solns. and stress corrosion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000732A1 EP0000732A1 (en) | 1979-02-21 |
| EP0000732B1 true EP0000732B1 (en) | 1980-07-23 |
Family
ID=25772463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100509A Expired EP0000732B1 (en) | 1977-08-04 | 1978-07-26 | Blends of reticulated polyarylsulfones and polycarbonates and their application during the manufacture of extruded films |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4152367A (en) |
| EP (1) | EP0000732B1 (en) |
| JP (1) | JPS6040473B2 (en) |
| DE (1) | DE2860069D1 (en) |
| IT (1) | IT1106864B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2948673A1 (en) * | 1979-12-04 | 1981-06-11 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING CASTING FILMS FROM POLYARYLSULPHONE-POLYCARBONATE MIXTURES |
| JPS57501185A (en) * | 1980-08-11 | 1982-07-08 | ||
| 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 (en) * | 1986-08-07 | 1988-02-11 | Amoco Corporation | A shaped article formed from a blend of a poly(aryl ether) and a polycarbonate |
| DE3836176A1 (en) * | 1988-10-24 | 1990-05-03 | Bayer Ag | POLYMER BLENDS |
| DE4208341A1 (en) * | 1992-03-16 | 1993-09-23 | Basf Ag | Thermoplastic moulding materials with high impact properties - contain co-polyarylene-ether] with at least 2 different repeat units and polycarbonate |
| 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 (en) * | 2001-10-10 | 2003-04-17 | Basf Ag | Molding composition containing polyarylether sulfone and an impact modifying rubber useful in production of shaped parts, films, fibers or foams, household articles, electronic parts, medical equipment, and automobile parts |
| 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 (en) * | 2007-09-12 | 2009-03-19 | Bayer Materialscience Ag | Thermoplastic with metal identification plate |
| KR20100127748A (en) * | 2008-02-05 | 2010-12-06 | 바이엘 테크놀로지 서비시즈 게엠베하 | Security element |
Family Cites Families (7)
| 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 (en) * | 1969-06-25 | 1979-09-06 | Bayer Ag, 5090 Leverkusen | Polyaryl ether sulfones and processes for their preparation |
| 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 (en) * | 1971-03-08 | 1975-09-04 | ||
| DE2305413C2 (en) * | 1973-02-03 | 1982-05-13 | Bayer Ag, 5090 Leverkusen | Branched aromatic polyaryl ether sulfones |
-
1978
- 1978-07-25 US US05/927,808 patent/US4152367A/en not_active Expired - Lifetime
- 1978-07-26 DE DE7878100509T patent/DE2860069D1/en not_active Expired
- 1978-07-26 EP EP78100509A patent/EP0000732B1/en not_active Expired
- 1978-08-02 JP JP53093720A patent/JPS6040473B2/en not_active Expired
- 1978-08-02 IT IT50576/78A patent/IT1106864B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6040473B2 (en) | 1985-09-11 |
| EP0000732A1 (en) | 1979-02-21 |
| JPS5428362A (en) | 1979-03-02 |
| IT1106864B (en) | 1985-11-18 |
| DE2860069D1 (en) | 1980-11-13 |
| IT7850576A0 (en) | 1978-08-02 |
| US4152367A (en) | 1979-05-01 |
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