Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

• This invention relates to polycarbonate compositions having improved color stability and melt flow, said compositions comprising an admixture of an aromatic polycarbonate, pigment and a methyl hydrogen silicone fluid.
• MHSF methyl hydrogen silicone fluids
• Rhodia, Inc. under their trademark Rhodorsil hydrofugeant 68 fluid.
• MHSF can be employed in amounts of about 0.01-1.0 pph, preferably 0.02-0.20 pph, of said aromatic polycarbonate.
• MHSF is employed in amounts sufficient to provide about the same level of MHSF in the polycarbonate composition.
• the amount of MHSF employed to coat a pigment is about 0.05-10.0 pph, preferably 1.0-5.0 pph, of the pigment.
• aromatic polycarbonates that can be employed in the practice of this invention are homopolymers and copolymers and mixtures thereof that are prepared by reacting a dihydric phenol with a carbonate precursor.
• the dihydric phenols that can be employed are bisphenols such as bis (4-hydroxyphenyl)methane, 2,2-bis (4-hydroxyphenyl)propane (bisphenol-A) , 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3 ,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dibromophenyl)propane, etc.; dihydric phenol ethers such as bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, etc.; dihydroxydiphenyl ⁇ such as p,p'-dihydroxydiphenyl, 3 ,3'-dichloro-4,4-dihydroxydiphenyl, etc.; dihydroxyaryl sulfones such as bis(4-hydroxyphenyl) sulfone, bis (3,5
• dihydric phenols are also available to provide carbonate polymers such as are disclosed in U.S. Patents 2,999,835, 3,028,365 and 3,153,008.
• Also suitable for preparing the aromatic carbonate polymers are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis (3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, etc.
• the carbonate precursor can be either a carbonyl halide, a carbonate ester or a haloformate.
• the carbonyl halides which can be employed are carbonyl bromide, carbonyl chloride and mixtures thereof.
• Typical of the carbonate esters that can be employed are diphenyl carbonate, di-(halophenyl) carbonates such as di- (chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc., di-(alkylphenyl) carbonates such as di-(tolyl) carbonate, etc., di-(naphthyl) carbonate, di-(chloronaphthyl) carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof.
• haloformates suitable for use herein include bishaloformates of dihydric phenols (bischloroformates of hydroquinone, etc.) or glycols (bishaloformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). While other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred.
• the aromatic polycarbonates of this invention are prepared by employing a molecular weight regulator, an acid acceptor and a catalyst.
• the molecular weight regulators which can be employed include monohydric phenols such as phenol, chroman-I, paratertiarybutylphenol, parabromophenol, primary and secondary amines, etc.
• phenol is employed as the molecular weight regulator.
• a suitable acid acceptor can be either an organic or an inorganic acid acceptor.
• a suitable organic acid acceptor is a tertiary amine and includes such materials as pyridine, triethylamine, dimethylaniline, tributylamine, etc.
• the inorganic acid acceptor can be one which can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
• the catalysts which can be employed can be any of the suitable catalysts that aid the polymerization of bisphenol-A with phosgene.
• Suitable catalysts include tertiary amines such as triethylamine, tripropylamine, n,n-dimethylaniline, quaternary ammonium compounds such as tetraethylammonium bromide, cetyl triethylammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propylammonium bromide, tetramethylammonium chloride, tetramethylammonium hydroxide, tetra-n-butylammonium iodide, benzyltrimethylammonium chloride and quaternary pho ⁇ phonium compounds such as n-butyl-triphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
• quaternary ammonium compounds such as tetraethylammonium bromide, cetyl triethylammonium bro
• branched polycarbonates wherein a polyfunctional aromatic compound is reacted with the dihydric phenol and carbonate precursor to provide a thermoplastic randomly branched polycarbonate.
• polyfunctional aromatic compounds contain at least three functional groups which are carboxyl, carboxylic anhydride, haloformyl or mixtures thereof.
• these polyfunctional aromatic compounds include trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydride, and the like.
• the preferred polyfunctional aromatic compounds are trimellitic anhydride or trimellitic acid, or their haloformyl derivatives.
• blends of a linear polycarbonate and a branched polycarbonate are also included herein.
• aromatic polycarbonates of this invention can also be employed with the aromatic polycarbonates of this invention and include such materials as antistatic agents, mold release agents, ultraviolet light stabilizers, reinforcing fillers such as glass and other inert fillers, foaming agents and the like.
• Yellowness index was determined in accordance with ASTM Yellowness Index (YI) Test D-1925 on samples molded at 316oC, 343°C. and 360°C.
• the Streak Test YI included a visual examination of samples for surface degradation typically manifested by increased darkening or marbling; i.e., "streaking", of the surface color.
• the test samples for this test were obtain by beginning with a mold temperature of 349°C for each five shot run and increasing the mold temperature 11°C for each successive shot beginning with each third shot of each five shot run, the third shot molded at 371°C being subject to the YI test.
• Gottfert stability was determined by placing a test sample weighing about 15 grams in a rheometer, heating the sample to 149°C and maintaining this temperature for a period of 7 minutes following which the sample was pressed through a capillary at a constant speed of 0.28 cm/sec.
• the pressure needed to maintain this rate of flow is related to the melt viscosity (MV) of the test sample in the cylinder from which the melt stability (MS) is determined.
• a polycarbonate composition of a homopolymer of 2,2-bis (4-hydroxyphenyl)propane was prepared by reacting essentially equimolar amounts of bisphenol-A and phosgene in an organic medium with triethylamine, sodium hydroxide and phenol under standard conditions and was mixed with the stabilizers shown in Table I by tumbling the ingredients in a laboratory tumbler. This mixture was then fed to an extruder, which extruder was operated at about 500°F, and the extruded strands chopped into pellets. The pellets were then injected molded at 316°C and 360°C into test samples of about 7.6cm x 5.lcm x 0.3cm. thick.
• EXAMPLE 2 The aromatic polycarbonate of Example 1 was blended with commercially obtained phosphites, TiO 2 and MHSF and test samples obtained, following extrusion and molding, all as described in Example 1.
• PE phosphite-epoxide mixture
• DDP diphenyldecyl phosphite
• TNPP trinonylphenyl phosphite
• the data in Table I also indicates that the MHSF is a better color stabilizer than a phosphite (Sample N vs. Sample 0) , but a combination of both phosphite and MHSF improves both color and melt stability (Sample P) .
• EXAMPLE 3 The same procedure was followed as in Example 2 above using two different commercially obtained phosphites and two different commercially obtained methyl hydrogen silicone fluids (MHSF).
• the phosphites employed were diphenyl decyl phosphite (DDP) and bis-2,4-di-t-butyl-pentaerithrytol diphosphite (PEDP).
• DDP diphenyl decyl phosphite
• PEDP bis-2,4-di-t-butyl-pentaerithrytol diphosphite
• Example 3 The procedure of Example 3 was followed to obtain the same compositions as in Example 3 except that the extruded pellets were molded into test bars measuring 12.7 cm x 1.3 cm x 0.3 cm thick. These test bars (samples q-w corresponding to Q-W of Example 3) were then subjected to the S-tensile impact test after being heat aged in an oven at 140°C. The results obtained are set forth in Table III below.
• Example 5 The procedure of Example 2 was followed to prepare additional samples containing 2.0 pph TiO 2 to further compare the effects of employing MHSF and/or a phosphite in combination with TiO 2 .
• the YI, melt flow (MF) and Gottfert stability results obtained are shown in Table IV below wherein the phosphite employed was diphenyl decyl phosphite (DDP) :
• Example 2 The procedure of Example 2 was followed except that the aromatic polycarbonate was first mixed with 0.05 pph diphenyl decyl phosphite (DDP) and the TiO 2 was first coated with MHSF before being blended with the polycarbonate. Coating the TiO 2 was accomplished by charging a Patterson-Kelly twin shell blender with 5 Kg TiO 2 , turning on the blender, metering 100 g MHSF into the blender over a period of about 2 minutes, and continuing rotation of the blender for an additional time to provide a 2 pph MHSF coating. A 10 pph MHSF coating on the TiO 2 was similarly prepared, all parts being based on the TiO 2 .
• DDP diphenyl decyl phosphite
• the additional blending time to provide these MHSF coating levels was about 5 minutes and 10 minutes, respectively.
• the coated TiO 2 was then mixed with the polycarbonate to provide a TiO 2 concentration of 2 pph.
• the YI and melt flow were determined for the samples obtained and this data is set forth in TABLE V below.
• sample R' containing 2 pph MHSF-coated TiO 2 was roughly equivalent in melt flow and YI to sample Q' containing 0.1 pph added MHSF.
• sample Q' molded at 680°F splayed whereas sample R' molded at 680°F did not.
• Sample S' containing 10 pph MHSF-coated TiO 2 and a higher level (0.2 pph) of added MHSF, shows no improvement over sample R' .
• Example 6 The procedure of Example 6 was followed except that the TiO 2 was coated with lower levels of MHSF and was incorporated in the polycarbonate resin in lower concentrations. In addition to obtaining the melt flow results of the samples at 6 and 12 minutes, the samples were also subjected to the YI Streak Test at 700°F.

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• 1979
  • 1979-09-24 WO PCT/US1979/000771 patent/WO1980000708A1/en not_active Ceased
  • 1979-09-24 JP JP50164479A patent/JPS55500732A/ja active Pending
• 1980
  • 1980-04-22 EP EP19790901271 patent/EP0020460A4/de not_active Withdrawn

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