WO2001034699A1 - Matieres moulables thermoplastiques presentant une couleur propre minime et une bonne moulabilite - Google Patents

Matieres moulables thermoplastiques presentant une couleur propre minime et une bonne moulabilite Download PDF

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WO2001034699A1
WO2001034699A1 PCT/EP2000/010773 EP0010773W WO0134699A1 WO 2001034699 A1 WO2001034699 A1 WO 2001034699A1 EP 0010773 W EP0010773 W EP 0010773W WO 0134699 A1 WO0134699 A1 WO 0134699A1
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block
weight
molding compositions
thermoplastic molding
styrene
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PCT/EP2000/010773
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German (de)
English (en)
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Norbert Güntherberg
Peter Ittemann
Axel Gottschalk
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Basf Aktiengesellschaft
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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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • Thermoplastic molding compounds with low intrinsic color and easy to process
  • the present invention relates to thermoplastic molding compositions containing improved processing properties
  • glass transition temperature T g of block B A is above 25 ° C and that of block B B / A is below 25 ° C and
  • phase volume ratio of block B A to block B B / A is chosen so that the proportion of the hard phase in the total block copolymer is 1 to 40 vol. % and the weight fraction of the diene in the entire block copolymer is less than 50% by weight,
  • (C) 0-300% by weight, based on (A) and (B) of at least one polymer selected from polycarbonates, styrene-maleic anhydride copolymers, imidized styrene-maleic anhydride copolymers, polymethyl methacrylates, polymethacrylimides, styrene -Phenyl-maleimide copolymers and styrene -acrylonitrile-phenylmaleimide copolymers.
  • polycarbonates styrene-maleic anhydride copolymers, imidized styrene-maleic anhydride copolymers, polymethyl methacrylates, polymethacrylimides, styrene -Phenyl-maleimide copolymers and styrene -acrylonitrile-phenylmaleimide copolymers.
  • the invention further relates to the use of these molding compositions for the production of moldings, foils, fibers and foams, and to shaped bodies, foils, fibers and foams made from these molding compositions. Finally, the invention relates to a method for producing the molding compositions.
  • thermoplastic copolymers based on vinyl aromatic polymers are known as SAN polymers
  • Blends of such SAN polymers with other thermoplastics in particular polycarbonates or imidized styrene-maleic anhydride copolymers, are also known.
  • additives are generally used to optimize these properties, but these often only improve one parameter and negatively influence another desired property. Additives to improve the flowability and the deep-drawing properties often lead to a loss of mechanical properties, while additives to improve the demoldability often impair the flowability.
  • SAN (styrene-acrylonitrile) polymers are transparent, they can be dyed particularly well in any color, either transparent or non-transparent (opaque), by adding colorants (for example dyes and / or pigments).
  • colorants for example dyes and / or pigments.
  • the slightly yellowish intrinsic color of the SAN polymer (yellow tinge) is annoying, since it falsifies the desired shade and makes it difficult to obtain the desired shade right away.
  • the yellow tinge is made by adding a soluble one Blue dye is compensated ("toned up") or higher amounts of colorant are used to obtain the desired shade. Both measures make the product more expensive because colorants are comparatively expensive.
  • DE Az. 198 58 141.6 discloses molding compositions of the ABS and ASA type which are impact-resistant due to the rubber-elastic graft polymer they contain.
  • the molding compositions described therein contain a block copolymer made from hard vinylaromatic blocks and soft vinylaromatic die blocks.
  • DE Az mentions rubber-free molding compositions. 198 58 141.6 not.
  • the task was to remedy the disadvantages described.
  • the object of the present invention was, in particular, to provide thermoplastic molding compositions based on vinylaromatic copolymers which have a balanced spectrum of properties.
  • the task was to provide molding compositions with good mechanical properties (high impact strength and flexural strength, good heat resistance), good processing properties (good flowability and demoldability) and at the same time a low intrinsic color (low yellow tinge).
  • the molding compositions according to the invention contain 80 to 99.995%, preferably 85 to 99.99% by weight, particularly preferably 90 to 99.9% by weight, based on the total weight of the molding composition, of a copolymer
  • R 1 , R 2 independently of one another H or -CC 8 alkyl
  • n 0, 1, 2 or 3
  • Such products can e.g. are produced by the process described in DE-A 10 01 001 and DE-A 10 03 436.
  • Such copolymers are also commercially available.
  • the weight-average molecular weight determined by light scattering is preferably in the range from 40,000 to 2,000,000, in particular from 40,000 to 1,000,000, particularly preferably from 80,000 to 250,000, which viscosity numbers are in the range from 40 to 200, in particular from 40 to 160 and particularly preferably 50 to 110 ml / g, corresponds (measured according to DIN 53726 in 0.5% by weight solution in dimethylformamide at 25 ° C).
  • Preferred monomers (ai) are styrene, ⁇ -methylstyrene and mixtures thereof.
  • Preferred monomers (a) are acrylonitrile, methacrylonitrile and mixtures thereof.
  • the polymer (A) can also be a mixture of different copolymers e.g. B. of styrene or ⁇ -methylstyrene and acrylonitrile, which differ for example in the content of acrylonitrile or in the average molecular weight.
  • the proportion of component (B) in the molding compositions is 0.005 to 20, preferably 0.01 to 15 and particularly preferably 0.1 to 10 wt .-%.
  • Component (B) is a rubber-elastic block copolymer
  • the glass transition temperature T g of block B A is above 25 ° C., preferably above 50 ° C., and that of block B B / A is below 25 ° C., preferably below 5 ° C., and
  • phase volume ratio of block B A to block B B / A is selected such that the proportion of the hard phase in the entire block copolymer is 1 to 40% by volume and the proportion by weight of the diene is less than 50% by weight, where
  • the relative proportion of 1,2-linkages of the polydiene, based on the sum of 1,2- and 1,4-cis / trans linkages, is below approximately 15%, preferably below 12%.
  • component B Detailed information on the structure and manufacture of component B is disclosed in DE-A 19 615 533, to which reference is made here.
  • Preferred vinylaromatic compounds are styrene and also ⁇ -methylstyrene, 1, 1-diphenylethylene and vinyltoluene and mixtures of these compounds.
  • Preferred dienes are butadiene and isoprene, also piperylene, 1-phenylbutadiene and mixtures of these compounds.
  • a particularly preferred monomer combination is butadiene and styrene. All of the weight and volume information below relates to this combination; if the technical equivalents of styrene and butadiene are used, the information may have to be converted accordingly.
  • the B B / A block is composed, for example, of 75-30% by weight of styrene and 25-70% by weight of butadiene.
  • a soft block particularly preferably has a butadiene content between 35 and 70% and a styrene content between 65 and 30%.
  • the weight fraction of the diene in the entire block copolymer is 15-65% by weight in the case of the styrene / butadiene monomer combination, and that of the vinylaromatic component accordingly
  • butadiene-styrene block copolymers with a monomer composition of 25-60% by weight of diene and are particularly preferred
  • a block copolymer B can e.g. through one of the general
  • Formulas 1 through 11 are shown: (1) (B A -B ( B / A) ) n;
  • B A stands for the vinylaromatic block and B (B / A ) for the soft phase, that is to say the block built up statistically from diene and vinylaromatic units
  • X the rest of an n-functional initiator
  • Y the rest of an m-functional coupling agent
  • m and n are natural numbers from 1 to 10.
  • Block copolymers of one of the general formulas B A -B (B / A ) - B A - X- [-B (B / A) -BA32 and Y- [-B (B / A) ⁇ B A ] 2 ( meaning From the cuts ⁇ as above) and a block copolymer whose soft phase is divided into blocks is particularly preferred
  • the blocks being constructed differently or their vinylaromatic / diene ratio in the individual blocks B ⁇ B / A ) changing such that a composition gradient B ( ⁇ / A) pl ⁇ B ( B / A ) P2 ⁇ : B ( B / A) p3 ... occurs, the glass transition temperature T g of each sub-block being below 25 ° C.
  • the p Monomers are formed, where p is an integer between 2 and 10.
  • the portionwise addition can serve, for example, to control the heat balance in the reaction mixture.
  • a block copolymer which has a plurality of blocks B ( B / A ) and / or B A , each with a different molecular weight per molecule, is also preferred.
  • the block polymers are preferably produced by anionic polymerization in a non-polar solvent, the initiation being carried out using organometallic compounds.
  • organometallic compounds Compounds of alkali metals, especially lithium, are preferred. Examples of initiators are methyl lithium, ethyl lithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyl lithium.
  • the organometallic compound is added as a solution in a chemically inert (inert) hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is generally in the range from 0.002 to 5 mol%, if it is based on the monomers. Aliphatic hydrocarbons such as cyclohexane or methylcyclohexane are preferably used as solvents.
  • the statistical blocks of the block copolymers which simultaneously contain vinylaromatic and diene are preferably prepared with the addition of a soluble potassium salt, in particular a potassium alcoholate.
  • potassium salt enters into a metal exchange with the lithium carbanion ion pair, potassium carbanions forming, which preferably attach styrene, while lithium cabanions preferably add butadiene.
  • potassium carbanions are much more reactive, a small fraction, namely 1/10 to 1/40, is enough to make the incorporation of styrene and butadiene equally likely on average, together with the predominant lithium carbanions.
  • potassium salts are potassium alcoholates, in particular tertiary alcoholates with at least 7 carbon atoms.
  • Typical corresponding alcohols are, for example, 3-ethyl-3-pentanol and 2, 3-dimethyl-3-pentanol.
  • Tetrahydrolinalool (3, 7-dimethyl-3-octanol) proved to be particularly suitable.
  • potassium alcoholates there are also other potassium salts which are inert towards metal alkyls. These include dialkyl potassium amides, alkylated diaryl potassium amides, alkyl thiolates and alkylated aryl thiolates.
  • the potassium salt is added to the reaction medium, the following should be said.
  • the solvent and the monomer for the first block are placed in the reaction vessel. It is not advisable to add the potassium salt at this point as it is at least partially hydrolyzed to KOH and alcohol by traces of protic impurities. The potassium ions are then irreversibly deactivated for the polymerization. Therefore, the lithium organyl should be added and mixed in first, then the potassium salt. If the first block is a homopolymer, it is advisable to add the potassium salt just before the statistical block is polymerized.
  • the potassium alcoholate can easily be prepared from the corresponding alcohol by stirring a cyclohexane solution in the presence of excess potassium-sodium alloy. After 24 hours at 25 ° C, the evolution of hydrogen and thus the reaction is complete. The reaction can also be shortened to a few hours by refluxing at 80 ° C.
  • An alternative implementation is to use alcohol with a small excess
  • a high-boiling inert solvent such as decalin or ethylbenzene
  • the proportion of 1, 2 linkages in relation to the sum of 1,2 and 1, 4 linkages of diene is achieved by adding the potassium compound in general. between 11 and 9%.
  • the proportion of 1,2- or 1,4-linkages of the diene units when using a Lewis base according to DE-A 44 20 952 e.g. a value of 15-40% for the 1,2- and 85-60% for the 1,4-linkages, in each case based on the total amount of diene units polymerized.
  • the polymerization temperature can be between 0 and 130 ° C.
  • the temperature range between 30 and 100 ° C. is preferred.
  • the volume fraction of the soft phase B B / A composed of diene and vinyl aromatic sequences is 60 to 99, preferably 70 to 90 and particularly preferably 80 to 90% by volume.
  • the from the Blocks B A formed from vinyl aromatic monomers form the hard phase, the volume fraction of which corresponds to 1 to 40, preferably 10 to 30 and particularly preferably 10 to 20% by volume.
  • the volume fraction of the two phases can be measured by means of contrasted electron microscopy or solid-state NMR spectroscopy.
  • the proportion of the vinyl aromatic blocks can be determined by osmium breakdown of the polydiene fraction by precipitation and weighing.
  • the future phase ratio of a polymer can also be calculated from the amounts of monomer used if it is allowed to polymerize completely each time.
  • the quotient of the volume fraction in percent of the soft phase formed from the B ( B / A ) blocks and the proportion of diene units in the soft phase for the styrene / butadiene combination is between 25 and 70% by weight.
  • the glass transition temperature (T g ) is influenced by the static incorporation of the vinylaromatic compounds into the soft block of the block copolymer and the use of potassium alcoholates during the polymerization.
  • a glass transition temperature between -50 and + 25 ° C, preferably -50 to + 5 ° C is typical.
  • the glass transition temperature is on average 2 to 5 ° C. lower than that of the corresponding Lewis base-catalyzed products, because the latter have an increased proportion of 1,2-butadiene linkages.
  • 1,2-polybutadiene has a glass transition temperature that is 70-90 ° C higher than 1,4-polybutadiene.
  • the molecular weight of the block B A is generally between 1000 and 200,000, preferably between 3,000 and 80,000 [g / mol].
  • the B blocks can have different molar masses within one molecule.
  • the molecular weight of block B ( B / A ) is usually between 2,000 and 250,000 [g / mol], values between 5,000 and 150,000 [g / mol] are preferred.
  • a block B ( B / A ) can also, like a block B A, within a
  • the coupling center X is formed by the reaction of the living anion chain ends with an at least bifunctional coupling agent.
  • an at least bifunctional coupling agent examples of such compounds can be found in US 3,985,830, US 3,280,084, US 3,637,554 and US 4,091,053.
  • epoxidized glycerides such as epoxidized linseed oil or soybean oil are used; divinylbenzene is also suitable.
  • Dichlorodialkylsilanes, dialdehydes such as terephthalaldehyde and esters such as ethyl formate or ethyl benzoate are particularly suitable for dimerization.
  • Preferred polymer structures are B A -B ( B / A ) ⁇ CA; X ⁇ [ _ ( B / A) _ BA] 2 and Y- [-B ( B / A ) "B A ] 2 'where the statistical block B ( B / A) itself again in blocks B (BI / AI ) -B (B2 / A2) ⁇ B (B3 / A3) - • • • can be divided Before Trains t ⁇ is the random block of 2 to 15 random part-blocks, particularly preferably from 3 to 10 sub-blocks, the division of the random block B..
  • the block copolymers according to the invention have a spectrum of properties which is very similar to that of soft PVC, but can be produced completely free of migratable, low molecular weight plasticizers. They are stable against crosslinking under the usual processing conditions (180 to 220 ° C). The excellent stability of the polymers according to the invention against crosslinking can be clearly demonstrated by means of rheography.
  • the experimental setup corresponds to that of the MVR measurement. With a constant melt flow rate, the pressure rise is recorded as a function of time. The polymers according to the invention show no pressure rise even after 20 minutes at 250 ° C. and result in a smooth melt strand, while in a comparison sample produced according to DE-A 44 20 952 with tetrahydrofuran, the pressure triples and the pressure increases under the same conditions A barbed wire-like strand typical of networking
  • the polymerization is carried out in several stages and, for example, in the case of monofunctional initiation, the production of the hard block B A begins. Some of the monomers are placed in the reactor and the polymerization is started by adding the initiator. In order to achieve a defined chain structure that can be calculated from the monomer and initiator metering, it is advisable to carry out the process up to a high conversion (over 99%) before the second monomer is added. However, this is not absolutely necessary.
  • the sequence of the monomer addition depends on the selected block structure.
  • the vinylaromatic compound is either initially introduced or metered in directly. A cyclohexane solution of the potassium alcoholate is then added. Then diene and vinyl aromatic should be added at the same time if possible. The addition can take place in several portions.
  • the statistical structure and the composition of block B ( B / A ) are determined by the quantitative ratio of diene to vinylaromatic compound, the concentration of the potassium salt and the temperature. The diene takes up a proportion by weight of 25% to 70% relative to the total mass, including vinyl aromatic compound.
  • Block B A can then be polymerized by adding the vinylaromatic. Instead, the required polymer blocks can also be connected to one another by a coupling reaction. In the case of functional initiation, the B ( B / A ) block is built up first, followed by the B A block.
  • the thermoplastic molding compositions according to the invention can contain 0 to 300% by weight, based on the sum of (A) and (B), preferably 0 to 200% by weight of at least one polymer selected from polycarbonates, styrene-maleic anhydride copolymers - Ren, imidized styrene-maleic anhydride copolymers, poly methyl methacrylates, polymethacrylimides, styrene - phenyl aleinini - mid copolymers, styrene - acrylonitrile - phenyl maleimide copolymers and methyl methacrylate - phenyl maleimide copolymers.
  • polycarbonates styrene-maleic anhydride copolymers - Ren, imidized styrene-maleic anhydride copolymers, poly methyl methacrylates, polymethacrylimides, styrene - phenyl alein
  • Suitable polycarbonates are, for example, those based on diphenols of the general formula II
  • Z is a single bond, a C ⁇ ⁇ to C 3 alkylene, a C 2 - to C 3 alkylidene, a C 3 - to C ⁇ cycloalkylidene, and -S- or -S0 2 - means.
  • Preferred diphenols of the formula II are, for example, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane,
  • the suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those with three or more than three phenolic OH- Groups.
  • the polycarbonates suitable as component (C) on the aromatic units can be substituted one to three times with halogen atoms, preferably with chlorine and / or bromine.
  • halogen-free compounds are particularly preferred.
  • the diphenols of the general formula II are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the interfacial process or with phosgene by a process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators , (Regarding polydiorganosiloxane-containing polycarbonates, see for example DE-A 33 34 782).
  • Suitable chain terminators are, for example, phenol, p-tert-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethyl-butyl) phenol, according to DE-A 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3, 5-di-tert-butylphenol, p-tert. -Octylphenol, p-dodecylphenol, 2- (3, 5-dimethyl-heptyl) -phenol and 4- (3, 5-dimethyl-heptyl) -phenol.
  • alkylphenols such as 4- (1,3-tetramethyl-butyl) phenol, according to DE-A 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the al
  • polycarbonates are those based on hydroquinone or resorcinol.
  • Suitable copolymers of styrene and maleic anhydride are e.g. prepared by radical copolymerization of styrene with MA, preferably in solution or in bulk.
  • the molar ratio MSA: styrene is preferably 1: 1 to 0.01: 1.
  • Suitable imidized styrene-MSA copolymers are obtained by subsequent reaction of the styrene-MSA copolymers with amines.
  • the functional group of the MSA units is first amidated in a two-stage reaction, after which the ring closure to the maleic imide takes place.
  • Suitable amines are e.g. Methylamine, ethylamine, cyclohexylamine and aniline.
  • the reaction with the amines can e.g. in solution (for example in a stirred tank reactor) or in the melt (e.g. continuously, in particular in an extruder, reactive extrusion).
  • Suitable polymethyl methacrylate is, for example, polymerization in bulk, emulsion, solution or suspension of methyl methacrylate (MMA) or MMA mixtures containing up to 20% by weight of comonomers.
  • Suitable comonomers are, for example, methyl, ethyl and butyl acrylate.
  • Polymerization is usually carried out by free radicals at preferred temperatures of 40 to 150 ° C., or anionically at low temperatures, or coordinatively using transition metal catalysts. Radically and coordinatively polymerized PMMA contains prefers products with certain steric configurations. Bulk products are usually manufactured in bulk, solution or suspension. The specialist can find more information, for example, H. Raudi-Puntigam, T. Völker: Chemistry, Physics and Technology of Plastics in Individual Presentations, Volume 9: Acrylic and Methacrylic Compounds, Springer-Verlag 1967.
  • Suitable polymethacrylimides are prepared analogously to the imidized styrene-MSA copolymers by reacting PMMA with amines, as described, for example, in DE-A 41575, EP-A 549922, EP-A 576877 and DE-AS 1165861 is.
  • Suitable styrene-phenyl maleimide copolymers, styrene-acrylonitrile-phenyl maleimide copolymers and methyl methacrylate-phenyl maleimide copolymers are e.g. prepared by radical solution polymerization of the corresponding monomers. Details are given, for example, in J. Macromol. Be. All, p. 267 (1977), U.S. Patent 4,451,617 and U.S. Patent 4,491,647.
  • thermoplastic molding compositions may also contain conventional additives and processing aids as component (D) in an amount of 0 to 30% by weight, based on the total weight of the molding compositions.
  • additives and processing aids are lubricants and mold release agents, colorants such as pigments and dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers and reinforcing agents and antistatic agents in the amounts customary for these agents.
  • the molding compositions according to the invention can be produced by mixing processes known per se, for example by melting in an extruder, Banbury mixer, kneader, roller mill or calender at temperatures of 150 to 300 ° C.
  • the components can also be mixed "cold" without melting and the powdery or granular mixture is only melted and homogenized during processing.
  • the present invention therefore furthermore relates to a process for producing the thermoplastic molding compositions according to the invention by mixing the components by mixing processes known per se.
  • Moldings of all kinds in particular foils and flat structures, can be produced from the molding compositions.
  • the films can be produced by extrusion, rolling, calendering and other processes known to the person skilled in the art.
  • the molding compositions according to the invention are formed by heating and / or friction alone or with the use of plasticizing or other additives to form a processable film or a sheet (plate).
  • the processing into three-dimensional shaped bodies of all kinds takes place, for example, by injection molding.
  • thermoplastic molding compositions according to the invention for the production of moldings, films, fibers and foams. Furthermore, the molded articles obtainable by using the thermoplastic molding compositions are films, fibers and foams.
  • thermoplastic molding compositions according to the invention have better flowability than, at the same time, improved mold release properties, deep-drawing strength and, in particular, a lower intrinsic color (less yellow tinge) and are largely free of evaporating and exuding components. They can be colored precisely and with small amounts of colorant.
  • They are suitable for the production of moldings, foils (especially sheets), fibers and foams, which can be further processed by thermoforming and deep drawing, and especially for the production of injection molded parts, especially for fast processing with short cycle times.
  • Component A was produced by the process of continuous solution polymerization, as described in the plastics handbook, ed. R. Vieweg and G. Daumiller, vol. V "Polystyrene", Carl-Hanser-Verlag, Kunststoff 1969, pages 122 to 124, is described.
  • AI component AI: A copolymer of styrene and acrylonitrile with 25 wt .-% acrylonitrile (AN) and a viscosity number of 60 ml / g, measured as a 0.5% solution in dimethylformamide according to DIN 53726 at 25 ° C.
  • component B a 50 liter stainless steel autoclave that could be heated and cooled simultaneously and was equipped with a crossbar stirrer was used by flushing with nitrogen, boiling with a solution of sec-butyllithium and 1,1-diphenylethylene in a molar ratio of 1: 1 prepared in cyclohexane and drying.
  • the temperature of the reaction mixture was controlled by heating or cooling the reactor jacket. After the end of the reaction (consumption of the monomers), titration was carried out until the mixture was colorless and the mixture was acidified with a 1.5-fold excess of formic acid. (Ciba-Geigy, Basel Irganox ® 3052) and 82 g of tris-nonylphenyl phosphite are added last 34 g of a commercially available stabilizer were. The solution was worked up on a degassing extruder (three domes, forward and backward degassing) at 200 ° C. The granules obtained in this way were used to produce the molding composition.
  • a degassing extruder three domes, forward and backward degassing
  • the average molar masses (in g / mol) of the polymer were determined by gel permeation chromatography (calibration against polystyrene).
  • M n means number average, M v viscosity average and M w weight average.
  • the glass transition temperatures T g were determined by DSC and were -55 ° C to -25 ° C for the soft phase and + 60 ° C to + 100 ° C for the hard phase.
  • the melt volume index MVI was determined at 200 ° C. and a load of 5 kg according to DIN 53 735 and was 8.5 ml / 10 min.
  • the molding compositions according to the invention and the comparison compositions were produced on a ZSK-30 extruder from Werner and Pfleiderer at 250 ° C. with 200 rpm and 10 kg / h throughput.
  • the product was cooled in a water bath, granulated and sprayed into test specimens on an injection molding machine (Arburg Allrounder).
  • Yellowness index YI The yellowness index is a measure of the intrinsic color of the
  • the yellowness index YI was determined by determining the color coordinates X, Y, Z according to DIN 5033 with standard light D 65 and 10 ° normal observer using the following definition equation:
  • Melt index MVR it was determined on the granulate according to DIN 53735/30 at 220 ° C melting temperature and 10 kg load.
  • a n the Charpy impact strength a n was determined on standard small bars according to ISO 179-2 / lell at 23 and at -30 ° C.
  • Vicat The heat resistance according to Vicat (method B) was determined on pressing plates according to ISO 306 / B with a load of 50 N and a heating rate of 50 K / h.
  • ⁇ f B the bending strength was determined on test specimens 80 x 10 x 4 mm according to ISO 178 at 23 ° C and 50% relative humidity (RH).
  • the impact strength at room temperature and in the cold is better than in the case of molding compositions which do not contain B (not according to the invention) (a n values are higher for molding compositions according to the invention).

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Abstract

Matières moulables thermoplastiques qui contiennent (A) 80 à 99,995 % en poids, par rapport au poids total de la matière moulable, d'un copolymère constitué (a1) de 50 à 99 % en poids, par rapport au poids de la substance (A), d'au moins un monomère vinylaromatique, et (a2) de 1 à 50 % en poids, par rapport au poids total de la substance (A), d'au moins un comonomère polaire, copolymérisable, (B) 0,005 à 20 % en poids, par rapport au poids des substances (A), (B), et éventuellement (C), d'un copolymère séquencé caoutchouteux constitué d'au moins une unité incorporée par polymérisation d'un bloc BA contenant des monomères vinylaromatiques et formant une phase dure et d'au moins une unité incorporée par polymérisation d'un bloc BB/A élastomère contenant des monomères vinylaromatiques ainsi qu'un diène et formant une phase molle, la température Tg de transition vitreuse du bloc BA étant supérieure à 25 °C et celle du bloc BB/A étant inférieure à 25 °C, (C) 0-300 % en poids, par rapport aux substances (A) et (B), d'au moins un autre polymère, et (D) 0 à 30 % en poids, par rapport au poids total des matières moulables, d'adjuvants et auxiliaires de moulabilité habituels.
PCT/EP2000/010773 1999-11-09 2000-10-31 Matieres moulables thermoplastiques presentant une couleur propre minime et une bonne moulabilite WO2001034699A1 (fr)

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DE19953955.3 1999-11-09
DE1999153955 DE19953955A1 (de) 1999-11-09 1999-11-09 Thermoplastische Formmassen mit geringer Eigenfarbe und guter Verarbeitbarkeit

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WO2019201782A1 (fr) * 2018-04-16 2019-10-24 Ineos Styrolution Group Gmbh Compositions de copolymère styrène-acrylonitrile à fluidité ultra élevée

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DE102008001695A1 (de) 2008-05-09 2009-11-12 Evonik Röhm Gmbh Poly(meth)acrylimide mit verbesserten optischen und Farbeigenschaften, insbesondere bei thermischer Belastung
KR101727351B1 (ko) * 2009-10-29 2017-04-14 스티롤루션 유럽 게엠베하 감소된 오염물 입자 함량을 갖는 무수물-함유 비닐방향족-비닐 시아니드 공중합체의 제조 방법

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EP0270515A2 (fr) * 1986-12-04 1988-06-08 Fina Research S.A. Procédé pour fabriquer des copolymères blocs transparents
WO1998012256A1 (fr) * 1996-09-19 1998-03-26 Basf Aktiengesellschaft Matieres moulables thermoplastiques
DE19710442A1 (de) * 1997-03-13 1998-09-17 Basf Ag Expandierbare Styrolpolymerisate
WO2000036010A1 (fr) * 1998-12-16 2000-06-22 Basf Aktiengesellschaft Matieres moulables thermoplastiques

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EP0270515A2 (fr) * 1986-12-04 1988-06-08 Fina Research S.A. Procédé pour fabriquer des copolymères blocs transparents
WO1998012256A1 (fr) * 1996-09-19 1998-03-26 Basf Aktiengesellschaft Matieres moulables thermoplastiques
DE19710442A1 (de) * 1997-03-13 1998-09-17 Basf Ag Expandierbare Styrolpolymerisate
WO2000036010A1 (fr) * 1998-12-16 2000-06-22 Basf Aktiengesellschaft Matieres moulables thermoplastiques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019201782A1 (fr) * 2018-04-16 2019-10-24 Ineos Styrolution Group Gmbh Compositions de copolymère styrène-acrylonitrile à fluidité ultra élevée
US11352488B2 (en) 2018-04-16 2022-06-07 Ineos Styrolution Group Gmbh Ultra-high flow styrene acrylonitrile copolymer compositions

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