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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

• the present invention relates to readily demoldable polycarbonate molding compositions with fatty acid esters based on 1,2-dihydroxypropane and C 1 to C 4 o-carboxylic acids as mold release agents, optionally in addition to other additives customary in polycarbonate.
• Thermoplastics in general and in particular describing polycarbonate are known.
• the most common substances used as mold release agents are the esters from long-chain aliphatic acids and alcohols. Examples include the use of esters from fatty acid alcohols or polyols such as e.g. Pentaerythritol with fatty acids, as described in DE 33 12 158, EP 100 918, EP 103 107, EP 561 629,
• fatty acid esters only show a significant release effect from amounts of more than 0.5% by weight.
• these concentrations often lead to turbidity and or to the formation of mold deposits.
• Siloxanes which are also used have sufficient temperature resistance, but are very poorly compatible with polycarbonate and, in the concentrations required for effectiveness, lead to undesirable cloudiness which compromises the applicability of severely restrict mainly in transparent settings of common material such as polycarbonate.
• the task was therefore to find mold release agents that equally minimize both mold release forces in order to enable all mold geometries to be removed from the mold without the formation of mold deposits.
• Another object is to reduce problems caused by the adhesion of molded polycarbonate moldings, as occurs, for example, when cups are pulled apart after storage.
• Another object is to reduce problems caused by the adhesion of molded polycarbonate moldings to metals, such as occurs when sliding on inclined metallic planes.
• Another task is to control the tying force, which e.g. is important for toys.
• care must be taken to ensure that the components are precisely matched, since insufficient tying force is also undesirable in some applications.
• the objects were achieved by using fatty acid esters based on 1, 2-dihydroxypropane and C] to C 4 o-carboxylic acids as mold release agents, which have sufficient solubility and stability in polycarbonate.
• the present invention relates to polycarbonate molding compositions with a content of 0.005 to 5.0% by weight, preferably 0.05 to 3.0% by weight, very particularly preferably 0.15 to 2.0% by weight, of fatty acid esters Basis of 1, 2-dihydroxy propane and C ⁇ to C 40 acids and esters of 1,2-dihydroxypropane with mixtures of different Ci to C 4 o-carboxylic acids where the alcohol can also be partially esterified and mixtures of partially esterified and fully esterified products and optionally using other additives customary in polycarbonate, such as, for example, thermal stabilizers, UV stabilizers, other mold release agents,
• Flame retardants, anti-dripping agents, fillers, glass fibers and blend partners such as ABS, ASA, SAN, EPDM or polyesters based on terephthalic acid and diols, which are characterized in that the molding compositions on a demoulding force measuring tool (friction coefficient measuring tool) for the static and sliding friction coefficients of friction preferably ⁇ 0.80, particularly preferably ⁇ 0.60 and very particularly preferably ⁇ 0.40, the Reference value of a mold release agent-free polycarbonate of the same viscosity measured on the friction coefficient tool has a value between 0.85 and 1.50.
• demoulding force measuring tool for the static and sliding friction coefficients of friction preferably ⁇ 0.80, particularly preferably ⁇ 0.60 and very particularly preferably ⁇ 0.40
• the Reference value of a mold release agent-free polycarbonate of the same viscosity measured on the friction coefficient tool has a value between 0.85 and 1.50.
• the molding compositions according to the invention can be contaminated with impurities which contain the individual constituents of the molding composition from their synthesis, processing, processing and storage, as well as contaminations which originate during the production or processing of the molding compositions according to the invention.
• the goal is to work with as clean products as possible.
• the molding compositions if they contain free OH groups, contain less than 10 ppm ions, particularly preferably less than 5 ppm. This is especially true for ions of the elements Na, K, Mg, Ca, Sn, Ti, Fe, Ni, Cr.
• the fatty acid esters to be used according to the invention if they are partially esterified and contain free OH groups, contain less than 10 ppm ions, particularly preferably less than 5 ppm. This is especially true for ions of the elements Na, K, Mg, Ca, Sn, Ti, Fe, Ni, Cr.
• the adhesion of molded parts made of polycarbonate is preferably reduced by the content of 1.5% by weight to 2.5% by weight of mold release agent.
• the fatty acid esters according to the invention are commercially available.
• Thermoplastic, aromatic polycarbonates in the sense of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates can be linear or branched in a known manner.
• Some, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates suitable according to the invention can be replaced by aromatic dicarboxylic acid ester groups.
• aromatic dicarboxylic acid ester groups Such polycarbonates, the Both acidic residues of carbonic acid and acidic residues of aromatic dicarboxylic acids, incorporated into the molecular chain, are, to be precise, aromatic polyester carbonates. For the sake of simplicity, they should be summed up in the present application under the generic term of thermoplastic, aromatic polycarbonates.
• polycarbonates to be used according to the invention are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, with some of the carbonic acid derivatives being produced by aromatic dicarboxylic acids or to produce the polyester carbonates
• thermoplastic polycarbonates including the thermoplastic, aromatic polyester carbonates, have average molecular weights M w (determined by measuring the relative viscosity at 25 ° C. in CH 2 C1 2 and a concentration of 0.5 g per 100 ml of CH 2 C1 2 ) from 12,000 to 120,000, preferably from 15,000 to 80,000 and in particular from 22,000 to 60,000.
• Diphenols suitable for the preparation of the polycarbonates to be used according to the invention are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers , Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ( ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, and also their ring-alkylated and ring-halogenated compounds.
• Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -l-phenyl-propane, l, l-bis- (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -m / p diisopropylbenzene, 2,2-bis- (3-methyl-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) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (3,5-dimethyl-4 -hydroxyphenyl) -m / p
• diphenols are 4,4'-dihydroxydiphenyl, l, l-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3rd , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis (4-hydroxyphenyl) cyclohexane and l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
• Suitable chain terminators are both monophenols and monocarboxylic acids.
• Suitable monophenols are phenol, alkylphenols such as cresols, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol, halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, or mixtures thereof.
• Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halogenated benzoic acids.
• Preferred chain terminators are the phenols of the formula (I)
• R 6 is H or a branched or unbranched Ci -C 8 alkyl radical.
• the amount of chain terminator to be used is 0.5 mol% to 10 mol%, based on moles of diphenols used in each case.
• the chain terminators can be added before, during or after the phosgenation.
• Suitable branching agents are the trifunctional or trifunctional compounds known in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
• Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene 2,4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane , 1, 3,5-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-hydroxyphenyl-isopropyl) phenyl) orthoterephthalic acid
• the amount of branching agents which may be used is 0.05 mol% to 2.5 mol%, based in turn on moles of diphenols used in each case.
• the branching agents can either be introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or added dissolved in an organic solvent before the phosgenation.
• Aromatic dicarboxylic acids suitable for the production of the polyester carbonates are, for example, phthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'- Benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, trimethyl-3-phenyl indane-4,5'-dicarboxylic acid.
• aromatic dicarboxylic acids terephthalic acid and or isophthalic acid are particularly preferably used.
• dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dicarboxylic acid dimethyl esters.
• the carbonate groups are replaced by the aromatic dicarboxylic acid ester groups essentially stoichiometrically and also quantitatively, so that the molar
• the ratio of the reactants is also found in the finished polyester carbonate.
• the aromatic dicarboxylic acid ester groups can be incorporated either statistically or in blocks.
• Preferred methods of production of the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known melt transesterification process.
• phosgene is preferably used as the carbonic acid derivative, in the latter case preferably diphenyl carbonate.
• Catalysts, solvents, work-up, reaction conditions etc. for the production of polycarbonate are sufficiently described and known in both cases.
• the molding compositions according to the invention are prepared by adding the alkanes according to the invention into the melt during synthesis or, in the case of the phase interface process, a work-up or concentration step, but also in solution, by simultaneously dissolving the polycarbonates in a polycarbonate solvent or successively mixed with the alkanes according to the invention and optionally further additives and the polycarbonate solvent is then evaporated.
• the present invention thus also relates to a process for the preparation of the polycarbonate molding compositions according to the invention, which is characterized in that polycarbonates are mixed with the esters according to the invention either simultaneously or successively, either in bulk or in solution, and then the mixtures either at temperatures between 260 ° C and 450 ° C ° C, preferably
• the polycarbonate molding compositions according to the invention can still be the usual
• Additives such as glass fibers, fillers, pigments, UV stabilizers, thermal stabilizers, antioxidants, flame retardants, impact modifiers and optionally other mold release agents, are present in the amounts customary for thermoplastic polycarbonates.
• Suitable glass fibers are all commercially available glass fiber types and types, i.e. cut glass types long glass fibers (chopped strands) and short glass (milled fibers), provided that they are compatible with polycarbonate by suitable sizes.
• the glass fibers used to manufacture the molding compounds are made from E-glass.
• e-glass is an aluminum-boron-silicate glass with an alkali oxide content of less than 1% by weight. Glass fibers with a diameter of 8 to 20 ⁇ m and a length of 3 to 6 mm (chopped strands) are usually used. Short glass (milled fibers) can also be used, as can suitable glass balls.
• Flame retardants such as find use in polycarbonate and can also be used in the molding compositions according to the invention are alkali metal salts of organic and inorganic acids, in particular sulfonic acids such as, for example
• the polycarbonate molding compositions according to the invention can be processed to moldings on the customary processing machines by known methods under the processing parameters customary for polycarbonate.
• Injection molding is preferred.
• the invention therefore also relates to parts made from the molding compositions according to the invention, such as molded parts and semi-finished products.
• the molded parts are used, for example, in the electrical, electronics, lighting, computer, construction, vehicle and or aircraft sectors and in the packaging, food or toy industries
• the molding compositions are suitable for injection molding and extrusion articles, such as, for example, films, cups, plates, twin-wall sheets, lights, housings for electrical appliances, computers or motor vehicle equipment such as panes, dashboard parts, lenses, coverings and the like or toy articles.
• the demolding properties of the polycarbonate molding compositions according to the invention and the comparative examples of the prior art were measured on a demolding force measuring tool (friction coefficient measuring tool).
• the friction coefficients for static and sliding friction are determined, which represent a measure of the demolding forces for adhesion and sliding of the mold out of the injection molding tool.
• a plate-shaped molded part with a melt temperature of 300 ° C and a mold temperature of 90 ° C is injected.
• a process data acquisition system measures the breakaway torque of the plate and the pressing force of the tool stamp on the plate. The coefficients are determined from the measurement parameters.
• the amounts in the examples relate to the weight of the total mixture.
• the coefficients of friction were measured using a specially made measuring tool.
• the same plate-shaped molded part was always injected at a melt temperature of 300 ° C at a mold temperature of 90 ° C. After cooling for 20 seconds, the molded part is rotated through an angle of 90 ° in the closed mold.
• a process data acquisition system measures the breakaway torque of the plate and the pressing force of the tool stamp on the plate. The coefficients are determined from the measurement parameters.
• Examples 1 and 2 and comparative examples 1 to 3 are listed in Table 1.
• a mold-free polycarbonate and a product containing PETS pentaerythritol tetrastearate were given as a comparison.
• the molding compositions according to the invention are distinguished by significantly smaller coefficients of friction and are already more effective in smaller quantities than the standard demoulder PETS used.
• the molding compositions according to the invention were subjected to a sliding test molded part on molded part.
• the molding compositions according to the invention also show low haze and better transmission (examples 3 and 4) at higher mold release contents than comparative example 4 (see table 2).

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• Chemical Kinetics & Catalysis (AREA)
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• Organic Chemistry (AREA)
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• 2000
  • 2000-05-23 MX MXPA01012389A patent/MXPA01012389A/es not_active Application Discontinuation
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  • 2000-05-23 KR KR1020017015409A patent/KR20020005766A/ko not_active Application Discontinuation
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  • 2000-05-23 EP EP00936785A patent/EP1189982A1/de not_active Withdrawn
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  • 2000-05-23 JP JP2001500701A patent/JP2003501506A/ja active Pending
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