Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen

Definitions

• a copolycarbonate is provided based on aromatic diphenol and an aromatic sulfonyl diphenol.
• an aromatic sulfonyl diphenol based on the total diphenol coatent, having a 4,4'-isomer purity of at least about 99 wt. % into the polymer, the heat deflection temperature cf the copolycarbonate is substantially improved.
• the copolycarbonate is reinforced with glass fibers to provide an advanced engineering composite having good physical properties, especially improyed heat deflection temperatures.
• This invention relates to polycarbonate polymers and more particularly to polycarbonate copolymers having improved heat deflection temperatures and good physical properties.
• thermoplastic polymers derived from reactions involving organic dihydroxy compounds and carbonic acid derivatives have found extensive commercial application because of their excellent mechanical and physical properties. These thermoplastic polymers are particularly suited for the manufacture of molded articles where impact strength, rigidity, toughness, thermal and dimensional stability as well as excellent electrical properties are required.
• the heat deflection temperature of the polycarbonate polymer defines the temperature at which a 0.25 mm deflection occurs when a specimen.127 mm in length, 13 mm in depth and 3 mm to 13 mm in width are subjected to a load applied at its center to give maximum fiber stresses of 66 psi (455 k Pa) or 264 psi (1820 k Pa).
• Typical polycarbonates known in the prior art exhibit heat deflection temperatures of from about 135 to 141°C at a 264 psi load.
• a copolycarbonate is provided with improved heat deflection temperature and good physical properties.
• a copolycarbonate having improved heat deflection temperatures along with good physical properties is provided which is comprised of the reaction product of an aromatic diphenol, an effective amount of an aromatic sulfonyl diphenol to improve the heat deflection temperature and a carbonic acid derivative such as phosgene or carbonyl bromide.
• copolycarbonate resin means the neat resin without additives
• copolycarbonate means the copolycarbonate resin with additives therein.
• the copolycarbonate resin of the invention may be prepared by conventional methods of preparation for polycarbonate resins and may have a weight average molecular weight of 10,000 to 200,000 and preferably have a melt flow rate of about 1 to 24 gm/10 min., most preferably about 2-6 gm/10 min., at 300°C according to ASTM D-1238,
• any suitable process, reactant, catalyst, solvent, reaction conditions and the like for the production of the copolycarbonate resins of the present invention which are customarily employed in polycarbonate resin synthesis may be used, such as disclosed in German Patent Nos. 962,274 and 1,046,311 and U.S. Patent N os. 2,964,794; 2,970,131; 2,991,273; 2,999,846; 3,028,365; 3,153,008; 3,187,065; 3,215,668; and 3,248,414, all incorporated herein by reference.
• the preferred process is the interfacial polycondensation process.
• copolycarbonate resins are obtained by reacting the aromatic dihydroxy compounds with an alkali metal hydroxide or alkaline earth metal oxide or hydroxide tc form the salt of the hydroxy compounds.
• the salt mixture is present in an aqueous solution or suspension and is reacted with phosgene, carbonyl bromide, or bischloroformic esters of the aromatic dihydroxy compounds.
• An.organic solvent is provided in the reaction admixture which is a solvent for the polymer but not for the aromatic dihydroxy salts.
• chlorinated and non-chlorinated aliphatic hydrocarbons are used as the organic solvent which dissolves the condensation product.
• Suitable solvents include cyclohexane, methylcyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene.
• reaction temperature should be about -20°C to + 150°C, preferably 0°C to about 100°C.
• the dissolved reaction components are polycondensed in an inert solvent in the presence of an equivalent amount of a tertiary amine base required for absorption of the generated HC1, such as e.g. N f N-dimethyl-aniline, N,N-dimethyl-cyclohexylamine or preferably pyridine and the like.
• a tertiary amine base required for absorption of the generated HC1, such as e.g. N f N-dimethyl-aniline, N,N-dimethyl-cyclohexylamine or preferably pyridine and the like.
• a diaryl carbonate can be transesterified with the aromatic dihydroxy compounds to form the polycarbonate resin.
• aromatic diphenols useful in the practice of the invention include the following compounds: hydroquinone resorcinol, dihydroxydiphenyl, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-sulphides, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulphoxides and ⁇ - ⁇ -bis-(hydroxy-phenyl)-diisopropylbenzenes, as well as their nuclear-alkylated and nuclear-halogenated compounds.
• aromatic dihydroxy compounds are described, for example, in U.S. Patent Nos.
• Preferred bisphenols are those of the formula I in which
• bisphenols 4,4'-dihydroxydiphenyl, 2,2'-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexanexane, ⁇ , ⁇ -bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulphoxide, hydroxy-benzophenone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane,
• Examples of particularly preferred bisphenols are: 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4- 'hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydxoxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
• the most preferred bisphenol is 2,2,-bis-(4-hydroxyphenyl)-propane (bisphenol A).
• aromatic sulfonyl diphenols useful in the practice of the invention are those represented by the structural formula having a 4,4'-isomer purity of at least about 99.9 wt. % wherein
• the aromatic copolycarbonate resins can be branched due to the incorporation of small amounts, preferably of between about 0.05 and 2.0 mol % (relative to diphenols employed), of trifunctional or more than trifunctional com- poundsr especially compounds with three or more phenolic hydroxyl groups.
• Polycarbonate resins of this type are described, for example, in German Offenlegungsschriften (German Cosched Specifications) 1,570,533, 1,595,762, 2,116,974 and 2,113, 347, British Patent Specification 1,079,821 and U.S. Reissue Patent 27,682 (incorporated herein by reference).
• Some examples of compounds with three or more than three phenolic hydroxyl groups which can be used are phoro- glucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene-2, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,4,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenylmethane,2,2- bis-(4,4-bis-(4-hydroxyphenyl)-cyclohexyl)-propane, 2,4- bis-(4-hydroxyphenyl-isopropyl)-phenol,2,6-bis-(2-hydroxy-5'-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl) -2-(2,4-dihydroxyphenyl)-propane, hexa (4-(4-hydroxy
• the copolycarbonate may be reinforced with glass fibers, preferably present in from about 5 to 40% by weight, most preferably in from about 10 to 30% by weight, based on the weight of the total composition.
• Glass fibers which can be used in the present invention are, for example, fibers of low alkali, aluminum-borosilicate glass having a maximum alkali metal oxide content of about 0.2 % by weight (E-glass), of diameter between about 8-15 ⁇ and length between about 300 and 800 ⁇ (short glass fibers) or about 2000 to 12,000 ⁇ (chopped strands) as well as rovings.
• copolycarbonates of the present invention may also contain other conventional resin additives such as pigments, dyes, UV stabilizers, thermal stabilizers, mold release agents and fillers.
• any additives including glass fibers, may be blended with the copolycarbonate resin in known mixing devices such as kneaders, single-screw extruders, twin-screw extruders, mills and the like.
• the dopolycarbonate resins of the invention not only exhibit physical properties similar to standard bisphenol A-based polycarbonates, but also exhibit heat deflection temperatures which are about 5-8°C higher than those of standard bisphenol A-based polycarbonates. Although this improvement in heat deflection temperature may not at first glance appear to be significant, it is noted that this about 5-8°C increase is quite significant for it enlarges the high temperature applications in which aromatic polycarbonates are suitable. Based on past experience, this about 5-8°C increase is believed to equate to an about 10-20°C increase in continuous service temperature under normal part loading. It is noted that the 264 psi ASTM D-648/72 test loading is an extreme "torture test" condition and not one generally encountered in actual use.
• reinforcement of the copolycarbonate with glass fibers yields an advanced engineering composite which exhibits a similar improvement in heat deflection temperature and an improvement in adhesion properties of the copolycarbonate resin to the glass fibers as illustrated by the higher tensile strength, higher resistance to bending and somewhat lower ductility (drop dart). This particular combination of properties is desirable for applications such as power tool housings.
• glass fiber-reinforced copolycarbonates of the invention With respect to the glass fiber-reinforced copolycarbonates of the invention, it is noted that the heat deflection temperature and the tensile strength improvements, while apparently modest, are in actuality quite significant when taken in combination with the other properties, especially ductility. All glass fiber-reinforced thermoplastics, with the exception of polycarbonate, are brittle. Composites based on a polycarbonate matrix are ductile, but are excluded from use in certain applications because of relatively minor deficiencies in tensile strength, stiffness (as measured by E-modulus) and continuous use temperature (as measured by heat deflection temperature).
• the glass-fiber-reinforced composites of the instant invention based on aromatic diphenol/aromatic sulfonyl diphenol copolymers, correct the above-described deficiencies while retaining substantial ductility and all the other useful properties of conventional polycarbonate composites including moldability, excellent surface appearance, low moisture absorption, good dimensional stability, good electrical properties and the like. Since all previous attempts to raise the heat deflection temper rature have resulted in a significant loss of ductility and/or some other important property, the present results herein reported are suprising and unexpected.
• a copolycarbonate resin was prepared by reacting a mixture of the disodium salts of 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) and 4,4'-sulfonyl diphenol (greater than 99.9% isomer purity) with phosgene in accordance with the interfacial polycondensation synthesis hereinbefore discussed. 5 wt. % of 4,4'-sulfonyl diphenol and 95 wt. % of bisphenol A, based on the weight of the diphenols, were used. The copolycarbonate resin was mixed with an amount of a phosphate-based stabilizer necessary to produce a concentration of about 0.01 wt.% in the final product.
• the mixture was then extruded in a 2" single screw Welding Engineers' Extruder.
• the extruder strands were then pelletized, and 1/8" thick standard samples were molded for evaluation of physical properties. The properties measured are reported in Table I. Additionally, the molded copolycarbonate samples were found to be highly transparent.
• Example 1 was repeated except 10 wt. % of 4,4'-sulfonyl diphenol and 90 wt. % of bisphenol A, based on the total weight of diphenols, were used. 1/8" thick molded samples were again prepared for evaluation of physical properties. The properties are reported in Table I. Again, the molded polycarbonate samples were found to be highly transparent.
• Example 1 was repeated except that.the polycarbonate produced was based on 100 wt. % bisphenol A. The physical properties measured are reported on Table I.
• Example 4 was repeated except that the reinforced copolycarbonate contained 17.8 % by weight of 3/16" glass fibers.
• the test results are reported in Table II.
• Example 4 was repeated except that the copolycarbonate resin used having a melt flow rate of 2.6 gms/10 min. (ASTM D-1238), was blended with 50 gms. of a phosphite-based stabilizer and was reinforced with 10 wt. % of 3/16" glass fibers. The test results are reported in Table II.
• Example 6 was repeated except that the copolycarbonate was reinforced with 18.4 wt. % of 3/16" glass fibers.
• the test results are reported in Table II.
• Example 4 was repeated except that the copolycarbonate resin contained 10 wt. % of 4,4'-sulfonyl diphenol and had a melt flow rate of 2.9 gms/10 min. (ASTM D-1238), was blended with 50 gms. of a phosphite-based stabilizer and was reinforced with 9.6 wt. % of 3/16" glass fibers. The test results are reported in Table II.
• Example 8 was repeated except that the copolycarbonate was reinforced with 19.8 wt. % of 3/16" glass fibers.
• the test results are reported in Table II.
• Example 4 was repeated except that no 4,4'-sulfonyl diphenol was used, the polycarbonate resin had a melt flow rate of 3.4 gms/10 min. (ASTM D-1238) and the polycarbonate was reinforced with 9.6 wt % of 3/16" glass fibers. The test minuss are reported in Table II.
• Example 10 was repeated except that the polycarbonate was reinforced with 20 wt % of 3/16" glass fibers. The test results are reported in Table II.
• Example 11 was repeated except that the polycarbonate had a melt flow rate of 12-14 gms/10 min. (ASTM D-1238). The test results are reported in Table II.

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• 1978
  • 1978-07-20 EP EP78100447A patent/EP0000547A1/de not_active Withdrawn
  • 1978-07-31 JP JP9269078A patent/JPS5426896A/ja active Pending

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