WO2007065579A1 - Polycarbonat-formmassen - Google Patents
Polycarbonat-formmassen Download PDFInfo
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- WO2007065579A1 WO2007065579A1 PCT/EP2006/011337 EP2006011337W WO2007065579A1 WO 2007065579 A1 WO2007065579 A1 WO 2007065579A1 EP 2006011337 W EP2006011337 W EP 2006011337W WO 2007065579 A1 WO2007065579 A1 WO 2007065579A1
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
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- 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
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
Definitions
- the invention relates to thermoplastic compositions with improved processing stability containing polycarbonate and rubber-modified graft polymer and / or vinyl (co) polymer, a process for their preparation and their use for the production of moldings.
- Thermoplastic molding compositions made from polycarbonates and ABS polymers have been known for a long time.
- US Pat. No. 3,130,177 A describes readily processable molding compositions made from polycarbonates and graft polymers of monomer mixtures composed of acrylonitrile and an aromatic vinyl hydrocarbon on polybutadiene. These molding compounds are characterized by good toughness both at room temperature and at low temperatures, good melt fluidity and high heat resistance.
- a disadvantage of such molding compositions is that, in order to avoid harmful effects on the polycarbonate and the associated deterioration in the production, processing or aging associated with the application properties, they contain certain constituents, such as, for example, basic substances and certain inorganic metal compounds, in particular oxidic (transition ) Metal compounds must not contain any significant amounts, since such constituents usually catalytically decompose the polycarbonate at high temperatures, which typically occur during the manufacture and processing of the molding compounds, and after prolonged exposure to a warm, humid climate. Such polycarbonate degradation often manifests itself in damage to the properties of the molding compositions, in particular the mechanical parameters such as ductility and tensile / stretch properties. As a result, the selection of the possible starting materials for such compositions is very severely restricted.
- ABS polymers which are not intended to be mixed with polycarbonates right from the start, often contain, due to the manufacturing process, residual amounts of substances with a basic effect, which are used as polymerization aids, for example in emulsion polymerization or in the workup processes, as auxiliaries.
- ABS polymers are also specifically added additives with a basic effect (eg lubricants and mold release agents).
- additives with a basic effect eg lubricants and mold release agents.
- many commercially available polymer additives cannot be used in impact-modified PC compositions, or can only be used with considerable losses in the properties of the compositions, since they either have a basic effect or contain constituents / impurities which have a basic effect due to the preparation.
- additives can be mold release agents, antistatic agents, stabilizers, light stabilizers, flame retardants and dyes.
- oxidic metal compounds for example in the form of certain pigments, ten (eg titanium dioxide, iron oxide) and / or fillers and reinforcing materials (eg talc, kaolin, etc.) often lead to considerable undesirable losses in the processing stability of the compositions.
- PC / ABS compositions (polycarbonate / acrylonitrile / butadiene / styrene J) are known from US Pat. No. 4,299,929, which are characterized in that inorganic acids, organic acids or organic acid anhydrides are added.
- the resulting molding compositions are distinguished by improved thermal stability out.
- EP-A 0576950 PC / ABS compositions with a combination of high toughness and good surface quality and at the same time good heat resistance and ball pressure hardness are known, which are characterized in that a compound containing several carboxyl groups and having a molecular weight of 150 to 260 g / mol is included.
- the compositions disclosed in EP-A 0576950 preferably contain 50 to 100 parts by weight of ABS, 1 to 50 parts by weight of polycarbonate and 0.2 to 5 parts by weight of the compound containing several carboxyl groups.
- EP-A 0683200 discloses impact modified polycarboant compositions which contain a phosphorus-containing acid and a phosphite.
- the object on which the invention is based is to provide impact-modified polycarbonate compositions for the production of complex molded parts which are distinguished by improved processing stability and good hydrolysis resistance and a light raw tone.
- the acid according to component C is preferably selected so that it decomposes under the thermal conditions of the compounding with the release of volatile and / or neutral reactions (ie neither an acid nor a base remains in the polycarbonate composition as the decomposition product of component C) .
- thermoplastic molding compositions comprising A) 10 to 90 parts by weight, preferably 40 to 80 parts by weight, in particular 55 to 75 parts by weight of aromatic polycarbonate and / or polyester carbonate, B) 10 to 90 parts by weight, preferably 20 to 60 parts by weight, in particular 25 to 45 parts by weight, of a rubber-modified graft polymer (B.1) or of a pre-compound made of rubber-modified graft polymer (B.1) with one (Co) polymer (B.2), or a mixture of a (co) polymer (B.2) with at least one polymer selected from the group of rubber-modified graft polymers (B.1) and the precompounds of rubber-modified graft polymer with a (Co ) Polymer (B.2) and
- component C 0.005 to 0.15 parts by weight, preferably 0.01 to 0.15 parts by weight, in particular 0.015 to 0.13 parts by weight, based on 100 parts by weight of the sum of components A and B. , at least one aliphatic and / or aromatic organic carboxylic acid, component C being mixed into the melt containing components A and B, or component B being premixed with component C in a first step and then the resultant in a second step Mixture of B and C with a melt containing component A is mixed.
- Aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the production of aromatic polycarbonates, see for example Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE -A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the production of aromatic polyester carbonates, e.g. DE-A 3 077 934) .
- aromatic polycarbonates takes place e.g. B. by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalogenides, preferably benzenedicarboxylic acid dihalides, after the phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents Triphenols or tetraphenols. It is also possible to use a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate.
- Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I) where a single bond, C to C 5 alkylene, C 2 to C 5 alkylidene, C to C cycloalkylidene, - O-, -SO-, -CO-, -S-, -SO 2 -, C fi to C ] 2 aryls to which further aromatic rings optionally containing heteroatoms can be condensed, or a radical of the formula (S) or (JS)
- C 1 to C ] 2 -alkyl preferably methyl, halogen, preferably chlorine and / or bromine x are each independently 0, 1 or 2, p 1 or 0, and
- R 5 and R 6 can be selected individually for each X 1 , independently of one another hydrogen or C to C alkyl, preferably hydrogen, methyl or ethyl, X 1 carbon and m is an integer from 4 to 7, preferably 4 or 5, with the Provided that at least one atom X 1 , R 5 and R 6 are alkyl at the same time.
- Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) C -C alkanes, bis (hydroxyphenyl) C 5 -C 6 cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.
- diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1 - Bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4- hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
- the diphenols can be used individually or as any mixtures.
- the diphenols are known from the literature or can be obtained by processes known from the literature.
- Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert.
- alkylphenols such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-
- thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured e.g. by GPC, ultracentrifuge or scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably 24,000 to 32,000 g / mol.
- thermoplastic, aromatic polycarbonates can be branched in a known manner, and preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three and more phenolic groups. Both homopolycarbonates and copolycarbonates are suitable.
- copolycarbonates according to the invention in accordance with component A 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, polydiorganosiloxa- ne with hydroxyaryloxy end groups can be used. These are known (US 3,419,634) and can be produced by processes known from the literature. The production of polydiorganosiloxane-containing polycarbonates is described in DE-A 3 334 782.
- preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis (3,5- dibromo-4-hydroxyphenyl) propane.
- Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4 1 -dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
- Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
- a carbonic acid halide preferably phosgene
- Suitable chain terminators for the production of aromatic polyester nor its Chlorkohlenklareester and the acid chlorides of aromatic monocarboxylic acids which may optionally be substituted by Ci to C22 alkyl groups or by halogen atoms, and aliphatic C 2 to C apart from the already mentioned monophenols 22 monocarboxylic acid chlorides Consideration.
- the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
- the aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids.
- the aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).
- trifunctional or multifunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarbonate acid tetrachloride or pyromellitic acid tetrachloride
- branching agents in quantities from 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or multifunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2- en, 4,6-dimethyl-2,4-6-tri- (4-hydroxyphenyl) heptane, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl ) -ethane
- Phenolic branching agents can be introduced with the diphenols, acid chloride branching agents can be introduced together with the acid dichlorides.
- the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
- the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the total of ester groups and carbonate groups. Both the ester and carbonate content of the aromatic polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
- the relative solution viscosity ( ⁇ re i) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride) Solution at 25 0 C).
- thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
- Component B.l comprises one or more graft polymers of
- the graft base B.1.2 generally has an average particle size (d 50 value) of 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.15 to 1 ⁇ m.
- Monomers B.1.1 are preferably mixtures of
- Preferred monomers B.1.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
- preferred monomers B.1.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
- Particularly preferred monomers are B.1.1.1 styrene and B.1.1.2 acrylonitrile.
- Graft bases B.1.2 suitable for the graft polymers B1 are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers and Silicone / acrylate composite rubbers.
- Preferred graft bases B.1.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to B.1.1.1 and B.1.1.2), with the proviso that that the glass transition temperature of component B.2 is below ⁇ 1O 0 C, preferably ⁇ 0 0 C, particularly preferably ⁇ -20 0 C. Pure polybutadiene rubber is particularly preferred.
- the gel fraction of the graft base B.1.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
- the graft copolymers B1 are produced by radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, particularly preferably by emulsion polymerization.
- ABS polymers which are produced by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285 are also particularly suitable graft rubbers.
- graft polymers B.l are also understood according to the invention to mean those products which are obtained by (co) polymerizing the graft monomers in the presence of the graft base and are also obtained in the working up.
- Suitable acrylate rubbers according to B.1.2 are preferably polymers made from acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.1.2, of other polymerizable, ethylenically unsaturated monomers.
- the preferred polymerizable acrylic acid esters include Ci to Cg alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen-Ci-C 8 alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
- Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
- Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as ethyl - glycol glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
- Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
- Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloyl hexahydro-s-triazine and triallyl benzenes.
- the amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base B.l .2. In the case of cyclic crosslinking monomers with at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.1.2.
- Preferred “other” polymerizable, ethylenically unsaturated monomers which can optionally be used in addition to the acrylic acid esters for the preparation of the graft base B.1.2 are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-dC 6 -alkyl ethers, methyl methacrylate, butadiene.
- Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
- Further suitable graft bases according to B.1.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
- the gel content of graft base B.1.2 is at 25 0 C in a suitable solvent loading is correct (M. Hoffmann, H. Kromer, R. Kuhn, polymer analysis I and ⁇ , Georg Thieme Verlag, Stuttgart 1977).
- the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
- Component B can also homo- and / or copolymers B.2 of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C; to C 8 ) alkyl esters, unsaturated carboxylic acids and Derivatives (such as anhydrides and imides) contain unsaturated carboxylic acids.
- vinyl aromatics such as, for example, styrene, ⁇ -methyl - styrene
- core-substituted vinyl aromatics such as p-methylstyrene, p-chlorostyrene
- acrylic acid (Ci-C 8 ) alkyl esters such as methyl methacrylate, n-buty
- vinyl cyanides such as unsaturated nitriles such as acrylonitrile and methacrylonitrile
- (meth) acrylic acid (Ci-C 8 ) Alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate
- unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids
- These (co) polymers B.2 are resinous, thermoplastic and rubber-free.
- the copolymer of styrene and acrylonitrile is particularly preferred.
- Such (co) polymers B.2 are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
- the (co) polymers preferably have average molecular weights M w (weight average, determined by GPC, light scattering or sedimentation) between 15,000 and 250,000.
- a pure graft polymer B1 or a mixture of several graft polymers according to B1, or a mixture of at least one graft polymer B1 with at least one (co) polymer B.2 can be used. If mixtures of several graft polymers or mixtures of at least one graft polymer with at least one (co) polymer are used, these can be used separately in the preparation of the compositions according to the invention or in the form of a precompound.
- Components B which contain constituents which degrade the polycarbonate under typical processing conditions are also particularly suitable for the compositions according to the invention.
- those components B are also suitable which contain substances having a basic effect due to the production. These can be, for example, residues of auxiliary substances which are used in emulsion polymerization or in the corresponding work-up processes, or specifically added polymer additives such as lubricants and mold release agents.
- the acids according to component C are preferably selected from at least one of the group of aliphatic dicarboxylic acids, aromatic dicarboxylic acids and hydroxy-functionalized dicarboxylic acids.
- component C are citric acid, oxalic acid, terephthalic acid or mixtures of the compounds mentioned.
- the acid according to component C is selected so that it decomposes thermally under the conditions of compounding with the release of volatile and / or neutral reacting compounds.
- the decomposition product of component C neither an acid nor a base remains in the polycarbonate composition.
- composition can contain further additives as component D.
- polyalkylene terephthalates are reaction products made from aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
- Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol-1 , 4 residues.
- the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, e.g. Residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanoic acid.
- the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols with 3 to 12
- Contain carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms e.g. Residues of propanediol-1,3, 2-ethylpropanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2,4,2- Methyl pentanediol-2,4,2,2,4-trimethylpentanediol-1,2,2
- the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or trihydric or tetra-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US Pat. No. 3,692,744.
- preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
- polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
- Mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.
- the polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
- the polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VEI, p. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973).
- the composition can also contain other conventional polymer additives such as flame retardants (for example organic phosphorus or halogen compounds, in particular bisphenol-A-based oligophosphate), antidripping agents (for example compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers), lubricants and mold release agents, for example pen - Taerythritol tetrastearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials (for example glass or carbon fibers, mica, kaolin, talc, CaCO 3 and glass flakes) as well as dyes and pigments (for example titanium dioxide or iron oxide).
- flame retardants for example organic phosphorus or halogen compounds, in particular bisphenol-A-based oligophosphate
- antidripping agents for example compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers
- lubricants and mold release agents for example pen - Taerythrito
- the composition can also contain those polymer additives which are known to catalytically decompose polycarbonates under processing conditions typical of such compositions.
- polymer additives which are known to catalytically decompose polycarbonates under processing conditions typical of such compositions.
- These include, in particular, oxidic compounds of metals, in particular metal oxides from subgroups 1 to 8 of the periodic table, such as titanium dioxide, iron oxide, kaolin and talc, which are generally used as fillers or reinforcing materials or as pigments.
- thermoplastic molding compositions may be prepared for example by mixing the particular constituents in a known manner and at temperatures of 200 0 C to 300 0 C, preferably at 230 to 28O 0 C in conventional units such as internal kneaders, extruders and Twin-shaft screws melt-compounded and melt-extruded.
- the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
- the compositions according to the invention are prepared by mixing components A to C and, if appropriate, further components D at temperatures in the range from 200 to 300 ° C., preferably 230 to 280 ° C. and a pressure of at most 500 mbar, preferably at most 200 mbar in a commercially available compounding unit, preferably in a twin-screw extruder.
- the conditions of the process according to the invention are thus chosen such that the acid according to component C reacts neutrally in this process with the formation Yielding and / or volatile compounds are decomposed and the volatile decomposition products are at least partially removed from the composition via the applied vacuum.
- the component B with the acid of component C and optionally further additives according to component D is initially at temperatures in the range of 180 to '260 0 C pre-mixed, and the mixture thus produced in a second compounding step at a temperature in the range 200 to 300 0 C, preferably 230 to 28O 0 C and a maximum pressure of 500 mbar, preferably at most 200 mbar in a commercially available compounding assembly with the component a and mixed, if necessary, further components D.
- the premix of components B and C and, if appropriate, further additives according to component D in the form of a polymer melt are passed into a melt stream of component A, which has a temperature of 220 to 300 ° C., and the polymer components are subsequently dispersed into one another.
- the invention therefore also relates to a process for the preparation of the compositions according to the invention.
- the molding compositions according to the invention can be used to produce moldings of any kind. These can be produced, for example, by injection molding, extrusion and blow molding. Another form of processing is the production of molded articles by deep drawing from previously produced plates or foils. Examples of such moldings are foils, profiles, housing parts of any kind, e.g. for household appliances such as juicers, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, especially for the automotive sector.
- household appliances such as juicers, coffee machines, mixers
- office machines such as monitors, flat screens, notebooks, printers, copiers
- Panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and
- the molding compositions according to the invention can also be used, for example, to produce the following shaped articles or molded parts: interior fittings for rail vehicles, ships, airplanes, buses and other motor vehicles, body parts for motor vehicles, housings for electrical transformers containing small transformers, housings for devices for information processing and transmission , Housing and cladding for medical devices, massage devices and housings therefor, toy vehicles for children, flat wall elements, housing for Safety devices, heat-insulated transport containers, molded parts for sanitary and bathroom equipment, cover grilles for ventilation openings and housings for garden tools.
- Component B-I is characterized by an A: B: S weight ratio of 17:26:57 and contains, due to the manufacturing process, Broenstedt-basic substances, such as from the. Powder pH of the cold-milled component B-I, measured in accordance with ISO 787/9, can be derived from 8.4.
- component B-2 Physical mixture of 85% by weight, based on component B-2, of an ABS polymer prepared by precompounding 50 parts by weight of an ABS graft polymer produced by the emulsion polymerization process and 50 parts by weight of a SAN copolymer, with 15 % By weight, based on component B-2, of a further SAN polymer.
- Component B-2 is characterized by an A: B: S weight ratio of 20:24:56.
- the powder pH of the ABS graft polymer used in component B-2 is 5.5, from which it can be concluded that the ABS graft polymer is essentially free of basic impurities caused by production.
- the SAN copolymers used in component B-2 do not contain any basic ingredients.
- Citric acid monohydrate (Merck KGaA, Darmstadt, Germany) component C-2
- Oxalic acid (Sigma-Aldrich Chemie GmbH, Steinheim, Germany)
- Irganox B900 (Ciba Specialty Chemicals Inc., Basel, Switzerland) component D-2 pentaerithritol tetrastearate component D-3
- TiO 2 Kronos 2233 (Kronos Titan GmbH, Leverkusen, Germany); Powder pH measured in accordance with ISO 787/9 in a mixture of 50% by weight water and 50% by weight 2-propanol is 5.8.
- All components A to D are mixed in a single compounding step in a twin-screw extruder (ZSK-25, Werner and Pfleiderer, Stuttgart, Germany) at a melt temperature of approximately 260 ° C. and a pressure of approximately 100 mbar.
- a twin-screw extruder ZSK-25, Werner and Pfleiderer, Stuttgart, Germany
- the mixing of the components B and C is performed in a first compounding step in a 3-1- kneader at about 220 0 C under atmospheric pressure.
- the precompound produced in this way is mixed with component A and component D in a second compounding step in a twin-screw extruder (ZSK-25, Werner and Pfleiderer, Stuttgart, Germany) at a melt temperature of approximately 260 ° C. and a pressure of approximately 100 mbar .
- test specimens are produced on an Arburg 270 E injection molding machine at 280 ° C. with a long residence time of 7.5 minutes.
- Method 1 Change in the melt flow (MVR " ) when the melt is stored at the processing temperature
- the MVR of the compounded composition is determined at 260 0 C with 5 kg load according to stamp ISOL 133rd Further, a (7,5 or 15 min min) likewise determined at 26O 0 C with 5 kg of load of the punch MVR at elevated temperature (280 0 C and 300 0 C) for a certain time stored sample of the compounded composition.
- the difference between these two MVR values before and after the thermal load serves as a measure of the degradation of the polycarbonate molecular weight and thus of the processing stability of the molding composition.
- Method 2 Toughness-brittle transition temperature in the impact test The determination of the impact strength a ⁇ is carried out according to ISO 180/1 A at various temperatures on test specimens measuring 80 mm x 10 mm x 4 mm, which at the comparatively high temperature of 280 0 C and with a comparatively long residence time of 7.5 min were hosed down.
- the a k -Zäh-brittle transition temperature is the temperature at which this impact experiment in about half of all experiments performed a viscous or brittle fracture is observed. It is a measure of the processing stability of the molding compound.
- Citric acid proves to be particularly advantageous in terms of improving processing stability (compare examples 1, 3 and 4). Furthermore, with regard to processing and hydrolysis stability, it proves advantageous to first premix components B and C in the melt (see Examples 1 and 2). Such a method proves to be an advantage in particular for colored materials in which the disadvantages of this method do not come into play with regard to the raw tone of the molding composition.
- Table 2 :
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06818836A EP1971641B1 (de) | 2005-12-09 | 2006-11-27 | Polycarbonat-formmassen |
BRPI0619564-4A BRPI0619564B1 (pt) | 2005-12-09 | 2006-11-27 | Massas de moldagem termoplásticas, seu uso e seus processos de preparação, e artigos moldados |
AT06818836T ATE547464T1 (de) | 2005-12-09 | 2006-11-27 | Polycarbonat-formmassen |
CA2632609A CA2632609C (en) | 2005-12-09 | 2006-11-27 | Polycarbonate molding compositions |
ES06818836T ES2380957T3 (es) | 2005-12-09 | 2006-11-27 | Masas de moldeo de policarbonato |
KR1020087013637A KR101409047B1 (ko) | 2005-12-09 | 2006-11-27 | 폴리카르보네이트 성형 조성물 |
CN2006800457928A CN101321821B (zh) | 2005-12-09 | 2006-11-27 | 聚碳酸酯模塑物料 |
JP2008543696A JP5344925B2 (ja) | 2005-12-09 | 2006-11-27 | ポリカーボネート成形組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005058847.6 | 2005-12-09 | ||
DE102005058847A DE102005058847A1 (de) | 2005-12-09 | 2005-12-09 | Polycarbonat-Formmassen |
Publications (1)
Publication Number | Publication Date |
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WO2007065579A1 true WO2007065579A1 (de) | 2007-06-14 |
Family
ID=37831607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/011337 WO2007065579A1 (de) | 2005-12-09 | 2006-11-27 | Polycarbonat-formmassen |
Country Status (13)
Country | Link |
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US (2) | US20070135544A1 (de) |
EP (1) | EP1971641B1 (de) |
JP (1) | JP5344925B2 (de) |
KR (1) | KR101409047B1 (de) |
CN (1) | CN101321821B (de) |
AT (1) | ATE547464T1 (de) |
BR (1) | BRPI0619564B1 (de) |
CA (1) | CA2632609C (de) |
DE (1) | DE102005058847A1 (de) |
ES (1) | ES2380957T3 (de) |
RU (1) | RU2439099C2 (de) |
TW (1) | TWI394795B (de) |
WO (1) | WO2007065579A1 (de) |
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JP2010537013A (ja) * | 2007-08-30 | 2010-12-02 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | 耐衝撃性改良充填ポリカーボネート組成物の製造方法 |
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- 2006-11-27 KR KR1020087013637A patent/KR101409047B1/ko active IP Right Grant
- 2006-11-27 CA CA2632609A patent/CA2632609C/en not_active Expired - Fee Related
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- 2006-12-05 US US11/633,972 patent/US20070135544A1/en not_active Abandoned
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JP2010537013A (ja) * | 2007-08-30 | 2010-12-02 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | 耐衝撃性改良充填ポリカーボネート組成物の製造方法 |
KR20100125344A (ko) * | 2008-03-22 | 2010-11-30 | 바이엘 머티리얼사이언스 아게 | 본래 색조, 가수분해 안정성 및 용융 안정성의 우수한 조합을 갖는 내충격성 개질된 폴리카보네이트 조성물 |
KR101599084B1 (ko) | 2008-03-22 | 2016-03-14 | 바이엘 머티리얼사이언스 아게 | 본래 색조, 가수분해 안정성 및 용융 안정성의 우수한 조합을 갖는 내충격성 개질된 폴리카보네이트 조성물 |
CN102015891B (zh) * | 2008-04-24 | 2015-04-29 | 拜尔材料科学股份公司 | 高耐水解和浅本色的冲击改性聚碳酸酯组合物 |
US7943686B2 (en) | 2008-12-04 | 2011-05-17 | Bayer Material Science Ag | Impact-modified polycarbonate compositions which have an emulsion graft polymer precipitated under basic conditions and comprise acidic phosphorus compounds |
DE102008060536A1 (de) | 2008-12-04 | 2010-06-10 | Bayer Materialscience Ag | Saure Phosphorverbindungen enthaltende schlagzähmodifizierte Polycarbonat-Zusammensetzungen mit basisch gefälltem Emulsionspfropfpolymersiat |
WO2013060687A1 (de) | 2011-10-26 | 2013-05-02 | Bayer Intellectual Property Gmbh | Stabilisierte polycarbonatzusammensetzungen mit abmischungen aus kieselsäure und einer anorganischen säure |
US9056977B2 (en) | 2011-10-26 | 2015-06-16 | Bayer Intellectual Property Gmbh | Stabilised polycarbonate compositions with blends of silica and an inorganic acid |
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US9637632B2 (en) | 2011-10-26 | 2017-05-02 | Covestro Deutschland Ag | Method for the production and stabilization of impact-modified polycarbonate compositions using diluted solutions of acidic compounds |
US10696841B2 (en) | 2015-05-27 | 2020-06-30 | Kingfa Sci. & Tech. Co., Ltd. | Polycarbonate composition and preparation method thereof |
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WO2017068045A1 (de) | 2015-10-23 | 2017-04-27 | Covestro Deutschland Ag | Verfahren zur herstellung von polycarbonat-formmassen mit verbesserter thermischer verarbeitungsstabilität |
US10844182B2 (en) | 2015-10-23 | 2020-11-24 | Covestro Deutschland Ag | Method for producing polycarbonate molding compositions with improved thermal processing stability |
US11993061B2 (en) | 2016-07-04 | 2024-05-28 | Covestro Deutschland Ag | Multilayer composite material containing special polycarbonate compositions as a matrix material |
WO2019121463A1 (de) | 2017-12-19 | 2019-06-27 | Covestro Deutschland Ag | Thermoplastische zusammensetzungen mit guter stabilität |
Also Published As
Publication number | Publication date |
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RU2008127447A (ru) | 2010-01-20 |
US20070135544A1 (en) | 2007-06-14 |
CN101321821B (zh) | 2013-02-06 |
EP1971641B1 (de) | 2012-02-29 |
EP1971641A1 (de) | 2008-09-24 |
TWI394795B (zh) | 2013-05-01 |
CA2632609A1 (en) | 2007-06-14 |
JP5344925B2 (ja) | 2013-11-20 |
DE102005058847A1 (de) | 2007-06-14 |
BRPI0619564B1 (pt) | 2018-01-16 |
KR20080073324A (ko) | 2008-08-08 |
CN101321821A (zh) | 2008-12-10 |
BRPI0619564A2 (pt) | 2011-10-04 |
ES2380957T3 (es) | 2012-05-21 |
KR101409047B1 (ko) | 2014-06-18 |
TW200740920A (en) | 2007-11-01 |
US20130253114A1 (en) | 2013-09-26 |
ATE547464T1 (de) | 2012-03-15 |
CA2632609C (en) | 2013-10-15 |
RU2439099C2 (ru) | 2012-01-10 |
JP2009518474A (ja) | 2009-05-07 |
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