JPS6160866B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises about 90% to 60% by weight linear polyaryl-sulfone and about 10% to 40% by weight linear polyaryl-sulfone.
and polyaryl-sulfone/polycarbonate mixtures having a weight average molecular weight of greater than 60,000. The proportion in the mixture is preferably about 85% to 70% by weight
wt% polyaryl-sulfone and about 15wt%~
30% by weight polycarbonate. Mixtures of polyaryl-ether-sulfones and polycarbonates have already been described (see DE 1719 244 and US Pat.
1719244, page 21). These mixtures are intended to eliminate, on the one hand, the undesirable embrittlement under load of polyaryl-ether-sulfones and, on the other hand, the susceptibility to stress cracking in the presence of solvents of polycarbonates ( (page 2 of the above-mentioned German publication specification). Mixtures of this type can be used for the production of cast films (Examples 8 and 9 of the above-mentioned German patent specification and Example 14 of the above-mentioned US patent specification).
and 16). Typically suitable polycarbonates for injection molding and extrusion are those whose w is, for example, about
35,000, and is described as polycarbonate in the above-mentioned document (Example 2 of the above-mentioned German publication). However, films made from this type of mixture exhibit a strong tendency to stress cracking. Instead of the W35000 polycarbonate component described in DE 1719244 and U.S. Pat. These products also exhibit a strong tendency to stress cracking and defective characteristic mechanical values. In contrast to this, the polyaryl according to the invention
The sulfone/polycarbonate mixture contains as the polycarbonate component a polycarbonate that cannot be extruded without reducing its molecular weight;
and the mixture is not suitable for producing cast film,
It was surprising to obtain an extruded film with a pattern of excellent properties. In principle, polyaryl-sulfones suitable according to the invention have an average molecular weight w (e.g., measured by light scattering) of about 15,000 to about 55,000;
All known linear aromatic polysulfones and polyethers, preferably about 20,000 to 40,000
It is a sulfone. Polyaryl-sulfones of this type are described, for example, in the following documents: the already mentioned DE 1719422 and US Pat. No. 3,365,517, which are hereby incorporated by reference. Preferred suitable polyaryl-sulfones can be obtained from bisphenols and dihalogenoaryl-sulfones and have structural units of the following formula (): Here, Ar ¹ corresponds to a biphenylene or oxybiphenylene group, n corresponds to 0 or 1, and Z corresponds to a p-phenylene group or m-phenylene group or a divalent group of the following formula (). Equivalent to: Here, R is a divalent _C1 - _C12 -alkylene or alkydene group, _C5 - _C12 -cycloalkydene or cycloalkydene group, _C7 - _C12 -aralkylene or aralkylidene or _C8 - _C12 -arylene -Bisalkylidene group or group -O-,-
It means S-, -SO-, -SO ₂ - and -CO-, or a single bond. Suitable polycarbonates 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, dihydroxydiphenyl, bis( hydroxyphenyl)-alkane,
Bis-(hydroxyphenyl)-cycloalkane, bis-(hydroxyphenyl) sulfide,
Bis-(hydroxyphenyl) ether, bis-
(hydroxyphenyl)ketone, bis-(hydroxyphenyl sulfoxide, bis-(hydroxyphenyl)-sulfone, α,α′-bis-(hydroxyphenyl)-diisopropylbenzene and their nuclear alkylation and nuclear halogenation Compounds.These and other suitable diphenols are
For example, U.S. Patents 3028365, 2999835, 3148172, 3271368, all incorporated herein by reference;
2991273, 3271367, 3280078, 3014891 and
2999846, German Publication Specification 1570703,
2063050, 2063052, 2211956 and 2211957, French patent specification 1561518, and monograph “H.
Schnell, Chemistry and Physics of
Polycarbonates, Interscience Publishers, New
York, 1964''. Aromatic polycarbonates can be prepared by known methods, for example by melt transesterification from bisphenols and diphenyl carbonates, as described in the aforementioned literature, and from bisphenols and diphenyl carbonates. and phosgene by a two-phase interfacial method. Aromatic polycarbonates are present in small amounts, preferably
Branching can be effected by adding from 0.05 to 2.0 mol % (relative to the diphenol used) of trifunctional or higher functional compounds, in particular compounds with 3 or more phenolic hydroxy groups. This type of polycarbonate is made of e.g.
German Publication Specification, incorporated herein by reference
1570533, 1595762, 2116974, 2113347 and
2500092, UK patent specification 1079821 and US patent specification 3544514. The average molecular weight of polycarbonates suitable according to the invention is greater than about 60,000, preferably about
65,000 to 120,000, especially about 75,000 to 95,000.
(Determined from intrinsic viscosity measured in CH ₂ Cl ₂ solution). Aromatic polycarbonates in the sense of the invention are in particular homopolycarbonates of bis-2-(4-hydroxyphenyl)-propane (bisphenol A) and at least about 30 mol %, preferably at least about 60 mol %, in particular at least It is a copolycarbonate of about 80 mol % of bisphenol A and up to about 70 mol %, preferably up to about 40 mol %, especially up to about 20 mol % of other diphenols. (The mole percentages in each case relate to the total molar amount of cocondensed diphenols). Other diphenols that are suitable are bis-(hydroxyaryl)-C ₁ to
C ₈ -alkanes, and bis-(hydroxyaryl)-C ₅ -C ₆ -cycloalkanes, especially bis-
(4-hydroxyphenyl)-C ₁ -C ₈ -alkanes and bis-(4-hydroxyphenyl)-C ₅
~C ₆ - cycloalkane. Examples of other diphenols that are suitable 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-
hydroxyphenyl)-2-methylbutane and 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane. A preferred copolycarbonate according to the invention contains bisphenol A and 1,1-bis-(4-hydroxyphenyl)-cyclohexane (bisphenol Z). The polyaryl-sulfone/polycarbonate mixture according to the invention can be produced in four ways: 1. Melting the polycarbonate and polyaryl-sulfone together, simultaneously or subsequently mixing the melt homogeneously, and subsequently adding a suitable The homogenized melt is extruded in the device. 2. Melt the polyaryl-sulfone in a suitable device, meter the polycarbonate into the polyaryl-sulfone melt, homogenize the melt and subsequently extrude the mixture in a suitable device. 3. Mix the polycarbonate solution and the polyaryl-sulfone solution, evaporate the solvent, melt the mixture, and simultaneously extrude the melt. 4. Mix the polycarbonate solution into the polyaryl-sulfone melt, evaporate the solvent, melt the polycarbonate, homogenize the melt and subsequently extrude it in a suitable device. Preferred mixing methods are 2 to 4, and mixing method 4 is particularly preferred. Mills, kneaders and screw extruders are to be understood as suitable equipment for the preparation of the polycarbonate mixtures according to the invention. Preferred equipment is a screw extruder, especially a twin screw extruder. Films extruded from the mixtures according to the invention are produced by known methods, for example by conventional
It can be manufactured using a zoned single-thread screw, and shaping into the film can be accomplished using a sheet die to provide the subject film or a film blow head to provide the blown film. Films extruded according to the invention have a pattern of particularly advantageous properties and are therefore suitable for use, for example, in the electrical field. Films extruded according to the invention exhibit, inter alia, high mechanical strength, high resistance to stress cracking under the influence of heat and in the presence of organic liquids, and high deflection temperatures and stability against long-term exposure to heat. have They are particularly notable for their resistance to unsaturated polyester resin solutions. Additives and fillers known in polycarbonate chemistry and polysulfone chemistry,
It can also be added to the mixture according to the invention. In this connection, the following may be mentioned, for example: dyes, pigments, mold release agents, moisture resistance agents, heat resistance agents, UV stabilizers, lubricants, fillers, such as glass powders, quartz products, graphite, Molybdenum sulfide, metal powders, powders of high-melting plastics, such as polytetrafluoroethylene powders, natural fibers, cotton, sisal, asbestos, as well as glasses of the most diverse nature, filaments and fibers of metals, in the melt of these polycarbonates. is stable during residence and does not appreciably damage the polycarbonate. EXAMPLES Example 1 Prepared from 80% by weight, preferably 4-4'-dichlorodiphenyl-sulfone and bis-2-(4-hydroxyphenyl)-propane, where w is
20000 linear polyaryl-sulfone, 20
Based on wt% bisphenol, w is 95000
The polycarbonate is melted together in a twin-screw extruder, and the barrel temperature is 340°C. Extrude the melt as a strand. Cool this strand,
Granulate. The obtained particles are melted in a single-screw extruder with a degassing zone, and the melt is extruded through a sheet die and taken through a cooling roll unit to a size of about 40 μm.
The film should have a thickness of . The obtained characteristic values are listed in the table below. Example 2 A film is prepared according to Example 1, but using 70% by weight of polyaryl-sulfone according to Example 1 and 30% by weight of bisphenol A polycarbonate, w75000. The characteristic values of the obtained film are listed in the table below. Example 3 (comparative example) The polymer according to Example 1 is always dissolved in methylene chloride, the concentration of the polymer mixture in methylene chloride is 17% by weight. After filtration and degassing, the solution is cast in a known manner on a drum casting machine into films approximately 40 μm thick. The obtained film
Post-drying at 120° C. removes solvent residues.
The characteristic values of this film are listed in the table below. Example 4 (comparative example) Particles were prepared according to example 1 from 80% by weight of polysulfone according to example 1 and 20% by weight of bisphenol A polycarbonate, w30000,
Approximately 60μ using a single screw extruder with a blow head
It was processed into a film with a thickness of m. Barrel temperature is 280°C in the intake zone and in the continuation zone.
It was 310℃. The die temperature was also adjusted to 310°C. The die gap was 0.8mm. The tube was inflated at a ratio of 1:4. Adjust the take-up speed of the film to reach the desired film thickness of 60%.
μm was obtained at the selected screw speed. The characteristic values of the obtained film are listed in the table below. 【table】

Claims (1)

Claims: 1. A polyaryl-sulfone/polycarbonate mixture consisting of 90% to 60% by weight of linear polyaryl-sulfone and 10% to 40% by weight of polycarbonate having a weight average molecular weight greater than 60,000. 2 The w of the polycarbonate component is 65,000~
120,000. 3 The w of the polycarbonate component is 75,000 to 95,000
The mixture according to claim 2, which is 4 Claims 1, 2 or 3 containing 85% to 70% by weight of linear polyaryl-sulfone and 15% to 30% by weight of polycarbonate
Mixtures as described in Section. 5. The polycarbonate is a homocarbonate of bisphenol A or a copolycarbonate of at least 30 mol % of bisphenol A and up to 70 mol % of other diphenols, with respect to the total molar amount of cocondensed diphenols. A mixture according to range 1. 6. A mixture according to claim 5, wherein the copolycarbonate comprises at least 80 mol% bisphenol A and up to 20 mol% other diphenols. 7 The other diphenol is 1,1-bis-(4-
6. The mixture according to claim 5, which is hydroxyphenyl)-cyclohexane.