Classifications

• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

• the invention relates to thermoplastic molding compositions containing impact-modified styrene / nitrile monomer copolymers, molded articles and films produced therefrom and to their use.
• Styrene-acrylonitrile copolymer (SAN) molding compounds are transparent and rigid and find many applications in the household and sanitary sector, in the packaging of cosmetic products as well as for electronic and office products.
• SAN copolymers are distinguished by high rigidity, dimensional stability and temperature resistance, and on the other hand by their high transparency and resistance to chemical reagents.
• a disadvantage is the unsatisfactory elongation at break of the SAN copolymers. In tensile elongation experiments, the break occurs even at low strains. Therefore, the mechanical properties of the SAN copolymers in terms of elongation at break and also the impact strength are in need of improvement.
• WO2008 / 063988 A2 discloses that diblock and triblock copolymers are efficient impact modifiers for biodegradable polymers, in particular polylactic acid.
• Polymethyl methacrylate, polybutyl acrylate-polymethyl methacrylate (PMMA-PBA-PMMA) - tri-block copolymers (Nano Strength ® (® registered trademark of Arkema) are used as compatibility agents for epoxy resins commercial use.
• WO 2007/140192 A2 describes acid-functionalized gradient triblock copolymers based on P (MMA) -bP (BA) -bP (MMA).
• the triblock copolymers modified in this way can be used in a variety of ways, including as impact modifiers for polymers. Application examples do not exist.
• WO 2013/030261 describes a process for the preparation of block copolymers by controlled free radical polymerization with the aid of Cu (O) -containing catalysts and initiators based on organic halides.
• Triblock copolymers of pMMA-b-pBA-b-pMMA are preferably prepared.
• Such triblock copolymers can be used inter alia as impact modifiers for styrene-acrylonitrile copolymers. There are no examples of such mixtures.
• An object of the invention is a thermoplastic molding composition containing or consisting of the components
• K1 1 70 to 85% by weight of at least one styrene or styrene derivative K1 1, K12: 30 to 15% by weight of at least one nitrile-containing ethylenically unsaturated monomer K12,
• K13 0 to 20% by weight of at least one further copolymerizable monomer K13, the sum of K1 1, K12 and K13 being 100% by weight;
• K2 40 to 10% by weight of at least one linear A-B-A triblock copolymer K2 from:
• a soft polymer block B consisting of at least one d- to C 2 alkyl acrylate B1;
• K3 0 to 10% by weight of auxiliaries and / or additives K3;
• K4 0 to 15 wt .-% of at least one copolymer K4 of styrene and another ethylenically unsaturated comonomer containing no nitrile group;
• thermoplastic molding compositions according to the invention from 65 to 90 wt .-% of the component K1, 35 to 10 wt .-% of the component K2, 0 to 10 wt .-% of the component K3 and 0 to 15 wt .-% of the component K4 ,
• thermoplastic molding compositions according to the invention particularly preferably consist of 70 to 90% by weight of component K1, 30 to 10% by weight of component K2, 0 to 10% by weight of component K3 and 0 to 15% by weight. the component K4.
• thermoplastic molding compositions consisting of the components K1 and K2 and optionally K3.
• Component K1 is used in amounts of from 60 to 90% by weight, preferably from 65 to 90% by weight, in particular from 70 to 90% by weight, very particularly preferably from 71 to 86% by weight.
• K1 is preferably a SAN copolymer having a molecular weight of 50,000 to 150,000 g / mol. These often have an AN content of 18 to 28 wt .-%.
• Suitable monomers K1 1 are styrene and styrene derivatives such as ⁇ -methylstyrene and ring-alkylated styrenes, such as p-methylstyrene and / or tert-butylstyrene. Preference is given to styrene, ⁇ -methylstyrene and / or p-methylstyrene, in particular styrene and / or ⁇ -methylstyrene, most preferably styrene is used.
• the monomers K12 used are preferably acrylonitrile and / or methacrylonitrile. Particularly preferred is acrylonitrile.
• the proportion of the monomer K1 1 in the copolymer K1 is generally from 70 to 85 wt .-%, particularly preferably 70 to 83 wt .-%, most preferably 73 to 83 wt .-%.
• the proportion of the monomer K12 in the copolymer K1 is generally 30 to 15 wt .-%, particularly preferably 30 to 17 wt .-%, most preferably 27 to 17 wt .-%.
• the copolymer K1 may contain from 0 to 20% by weight, preferably from 0 to 10% by weight, of at least one further copolymerizable monomer K13, for example methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenylmaleimide, maleic anhydride , Acrylamide and / or vinyl methyl ether.
• at least one further copolymerizable monomer K13 for example methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenylmaleimide, maleic anhydride , Acrylamide and / or vinyl methyl ether.
• the copolymer K1 consists only of units of the monomers K1 1 and K12.
• Preferred copolymers K1 are copolymers of styrene and acrylonitrile and / or copolymers of ⁇ -methylstyrene and acrylonitrile.
• K1 is particularly preferably a copolymer of styrene and acrylonitrile.
• Preferred is a copolymer of 70 to 85 wt .-% of styrene and 30 to 15 wt .-%, acrylonitrile; particularly preferably from 70 to 83% by weight of styrene and 30 to 17% by weight of acrylonitrile, very particularly preferably from 73 to 83% by weight of styrene and 27 to 17% by weight of acrylonitrile.
• the number-average molecular weight (M n ) of the copolymer K1 is generally from 30,000 to 150,000 g / mol, preferably from 50,000 to 120,000 g / mol.
• the viscosity (Vz) of the copolymer K1 is (measured according to DIN 53726 at 25 ° C in a 0.5 wt .-% solution in DMF), for example, from 50 to 120 ml / g.
• the copolymer K1 can be prepared by a process such as, for example, in the Kunststoff-Handbuch, Vieweg-Daumiller, Volume V, (Polystyrene), Carl-Hanser-Verlag, Kunststoff 1969, pages 122 f., Lines 12 ff. Will be described.
• Component K2 acts as an impact modifier and is used in quantities of generally 40 to 10% by weight, preferably 35 to 10% by weight, particularly preferably 30 to 10% by weight, very particularly preferably 29 to 14% by weight. used.
• the triblock copolymer K2 is generally a linear hard-soft-hard (A-B-A) segment triblock copolymer of two hard polymer endblocks A and a soft polymer block B interposed between the blocks A.
• the molecular weights M n of the triblock copolymer K 2 are generally in the range from 15,000 to 300,000, preferably in the range from 50,000 to 150,000.
• the proportion of the polymer block B in the triblock copolymer K2 is generally 30 to 50 mol%; preferably 35 to 50 mol% of the proportion of the polymer blocks A in the triblock copolymer K2 is 50 to 70 mol%, preferably 50 to 65 mol%, wherein the proportions A and B add up to 100 mol%.
• the soft polymer block B consists of monomer units of one or more alkyl acrylates (B1) having a straight-chain or branched alkyl radical having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, particularly preferably 4 to 8 carbon atoms, in particular n-butyl acrylate and / or ethylhexyl acrylate. Particularly preferred is n-butyl acrylate.
• the hard polymer blocks A contain or consist of one or more C 1 to C 4 alkyl methacrylates (A1), preferably methyl methacrylate and / or ethyl methacrylate, more preferably methyl methacrylate.
• the abovementioned monomers (A1) can also be used in admixture with one or more monomers ( ⁇ 1 ').
• Suitable monomers ( ⁇ 1 ') are methacrylic ester derivatives, preferably epoxy-, hydroxyl- or carboxyl-functionalized alkyl methacrylates, particularly preferably epoxy-functionalized alkyl methacrylates ( ⁇ 1'), such as glycidyl methacrylate.
• glycidyl methacrylate is a common commercial product and commercially available, for example, from Aldrich.
• the proportion of the comonomer ( ⁇ 1 '), relative to the total monomer content (A1) + (A1'), can be from 2 to 10 mol%, preferably from 4 to 8 mol%.
• the molar ratio of the polymer blocks B: A is generally 1, 0: 2.5, preferably 1, 0: 1, 5, particularly preferably 1, 0: 1, 0.
• triblock copolymers K2 of the type methyl methacrylate / glycidyl methacrylate copolymer block-polybutyl acrylate block-methyl methacrylate glycidyl methacrylate copolymer (PMMA-co-PGMA-block-PBA-block-PMMA-co-PGMA).
• the preparation of the aforementioned triblock copolymers can be carried out by any technique of living or controlled polymerization. It has proved to be advantageous to carry out the polymerization as a two-stage one-pot synthesis, in which first with a bifunctional initiator of organic chlorides or bromides (such as 2,6 dibromo-diethylheptanedionate, 2.5 dibromadipic acid ethyl ester) the monomers B1 to produce the soft center block B polymerized and after reaching a conversion of 95 to 100%, the two hard outer blocks A by addition and polymerization of the monomers A1 and optionally A1 'are prepared.
• a bifunctional initiator of organic chlorides or bromides such as 2,6 dibromo-diethylheptanedionate, 2.5 dibromadipic acid ethyl ester
• CRP controlled radical polymerization
• SET-LRP polymerization process single electron transfer-living radical polymerization
• Suitable is the SET-LRP polymerization process described in WO 2008/019100 A2 using Cu (0), Cu 2 Te, CuSe, Cu 2 S and / or Cu 2 O catalysts.
• the catalyst used is Cu in the form of Cu (0), Cu (I), Cu (II) or mixtures thereof.
• Cu (0) is preferably used as a solid, in particular in the form of a wire, grid, mesh or powder.
• a halide salt is added before the addition of the monomers A1, preferably small amounts of a halide salt are added.
• the triblock copolymer obtainable in this way can be isolated and dried by customary methods.
• the novel thermoplastic molding compositions may optionally contain one or more copolymers K4.
• Copolymers K4 are copolymers of styrene (K4-1) and another ethylenically unsaturated comonomer which contains no nitrile group (K4-2).
• the copolymer K4 is a copolymer of styrene and methyl methacrylate.
• the copolymer K4 can be used in amounts of from 0 to 15% by weight, preferably from 5 to 10% by weight.
• thermoplastic molding compositions according to the invention consisting of the components K1 and K2 and, if present, K3.
• thermoplastic molding composition may optionally contain from 0 to 10% by weight of auxiliaries and / or additives.
• the thermoplastic molding compositions of the invention may contain from 0 to 5% by weight of fibrous or particulate fillers or mixtures thereof, in each case based on the total amount of components K1 to K4.
• fibrous or particulate fillers or mixtures thereof for example, glass fibers, which can be equipped with a size and an adhesion promoter, glass beads, mineral fibers or aluminum oxide fibers can be added as fillers or reinforcing materials.
• Examples of preferred fibrous or pulverulent fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass and glass beads, more preferably glass fibers.
• glass fibers When glass fibers are used, they can be provided with a size and an adhesion promoter for better compatibility with the blend components.
• the incorporation of the glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings). Furthermore, as excipients and / or additives (K3) are all such substances into consideration, which are usually used for processing or finishing of polymers used. Mention may be made, for example, of colorants, antistatic agents, antioxidants, stabilizers for improving the thermostability, stabilizers for increasing the light stability, stabilizers for increasing the hydrolysis resistance and the resistance to chemicals, agents against the heat decomposition and, in particular, lubricants which are suitable for the production of moldings or molded parts are appropriate.
• colorants for example, of colorants, antistatic agents, antioxidants, stabilizers for improving the thermostability, stabilizers for increasing the light stability, stabilizers for increasing the hydrolysis resistance and the resistance to chemicals, agents against the heat decomposition and, in particular, lubricants which are suitable for the production of moldings or molded parts are appropriate.
• Suitable colorants are e.g. all dyes which can be used for the transparent, semitransparent or non-transparent coloring of polymers, in particular those which are suitable for coloring styrene copolymers.
• flame retardants e.g. the halogen-containing or phosphorus-containing compounds known to those skilled in the art, magnesium hydroxide, as well as other conventional compounds, or mixtures thereof are used.
• Suitable antioxidants are e.g. sterically hindered mononuclear or polynuclear phenolic antioxidants, which may be substituted in various ways and may also be bridged via substituents. These include not only monomeric but also oligomeric compounds which can be composed of several phenolic basic bodies. Also suitable are hydroquinones and hydroquinone-analogous, substituted compounds, as well as antioxidants based on tocopherols and their derivatives. Also mixtures of different antioxidants can be used. In principle, all commercially available or suitable for styrene copolymers compounds can be used, e.g. Antioxidants from the Irganox series.
• co-stabilizers can be used, in particular phosphorus or sulfur-containing co-stabilizers.
• P- or S-containing co-stabilizers are known to the person skilled in the art.
• suitable light stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones.
• Suitable matting agents are both inorganic substances such as talc, glass spheres or metal carbonates (such as MgCC> 3, CaCC> 3), as well as polymer particles - in particular spherical particles with diameters d 50 over 1 mm - based on, for example, methyl methacrylate, styrene compounds , Acrylonitrile or mixtures thereof. Furthermore, it is also possible to use polymers which comprise copolymerized acidic and / or basic monomers.
• Suitable anti-drip agent are, for example, polytetrafluoroethylene (Teflon) polymers and ultra-high molecular weight polystyrene (molecular weight M w over 2,000,000).
• Suitable antistatics include, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines, polyethylene glycol esters, copolymers of ethylene oxide glycol and propylene oxide glycol (especially diblock or triblock copolymers of ethylene oxide and propylene oxide blocks) and glycerol mono- and distearates , as well as their mixtures.
• Suitable stabilizers are, for example, sterically hindered phenols, but also vitamin E or analogously constructed compounds, as well as butylated condensation products of p-cresol and dicyclopentadiene.
• Hindered amine light stabilizers benzophenones, resorcinols, salicylates, benzotriazoles are also suitable.
• Other suitable compounds are, for example, thiocarboxylic acid esters.
• Mono- settable are also C 6 -C 2 o alkyl esters of thiopropionic acid, especially the stearyl and lauryl esters. It is also possible to use dilauryl thiodipropionate (dilauryl thiodipropionate), thio dipropionic acid diaryl ester (distearyl thiodipropionate) or mixtures thereof.
• HALS absorbers such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebazate
• UV absorbers such as 2H-benzotriazol-2-yl- (4-methylphenol).
• HALS absorbers such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebazate
• UV absorbers such as 2H-benzotriazol-2-yl- (4-methylphenol).
• Such additives are usually used in amounts of 0.01 to 2 wt .-% (based on the total mixture).
• Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters, amide waxes (bisstearylamide), polyolefin waxes or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms.
• Ethylene-bis-stearamide eg Irgawax, manufacturer Ciba, Switzerland
• the amounts of these additives are in the range of 0.05 to 5 wt .-%.
• Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives. The usual amounts, if used, are from 0.001 to 3 wt .-% based on the amount of components K1 to K4.
• pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are usable.
• Processing aids and stabilizers such as UV stabilizers, heat stabilizers (eg butylated reaction products of p-cresol and dicyclopentadiene, Wingstay L, manufacturer: Omnova, or thiouripropionic acid dilauryl ester, Irganox PS 800, manufacturer: BASF), lubricants and antistatics (eg ethylene oxide -Propylene oxide copolymers such as Pluronic (manufacturer: BASF), if used, are usually used in amounts of 0.01 to 5 wt .-%, based on the total amount of components K1 to K4.
• the individual additives are generally used in the usual quantities.
• the preparation of the novel molding materials from the components K1 and K2 (and optionally K4 and K3) can be carried out by customary known methods.
• the mixing of the components preferably takes place by melt mixing, for example coextrusion, kneading or rolling of the components. This is carried out at temperatures in the range of 160 to 400 ° C, preferably from 180 to 280 ° C.
• thermoplastic molding compositions have a significantly improved elongation at break and impact resistance compared to pure SAN copolymers.
• thermoplastic molding composition according to the invention has good transparency and UV stability.
• thermoplastic molding composition Another object of the invention are molded articles and films made from the thermoplastic molding composition according to the invention.
• the processing can be carried out by means of the known methods of thermoplastic processing, in particular the production by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
• the invention likewise relates to the use of these films and molded articles for exterior applications, for example in the automotive sector, and for the production of packaging material or for the production of devices of medical technology or medical diagnostics as well as in the toy and household sector.
• the invention is further illustrated by the following examples and the claims:
• the viscosity is measured according to DIN 53726 at 25 ° C in a 0.5 wt .-% solution in DMF. d) modulus of elasticity (MPa)
• the modulus of elasticity is determined according to ISO 527-2: 1993. e) yield stress (MPa)
• the yield stress is determined according to DIN ISO 527 at 23 ° C. f) Charpy notched impact strength [kJ / mm 2 ]:
• the notched impact strength is determined on test specimens (80 ⁇ 10 ⁇ 4 mm, produced by injection molding at a melt temperature of 240 ° C. and a mold temperature of 70 ° C.), at 23 ° C. in accordance with ISO 179-1A. g) flowability (MVR [ml / 10 min]):
• the flowability is determined on a polymer melt at 220 ° C and 10 kg load according to ISO 1 133. h) Vicat softening temperature A 50 (° C)
• the Vicat softening temperature is determined according to DIN ISO 306. i) elongation at break (%)
• the elongation at break is determined according to DIN ISO 527 at 23 ° C. j) transmission (%)
• the transmission is measured according to DIN 53236. k) haze
• the Haze is determined according to ASTM D1003 on 2mm thick rods.
• the reactor was equipped with a blade stirrer around which a 0.5 m long copper wire was wound.
• the apparatus was charged successively with 447.0 g of butyl acrylate (BA), 300 ml of methyl ethyl ketone (MEK), 100 ml of methanol (MeOH), 2.51 g of 2,6-dibromo diethylheptanedionate (DBDEHD) as initiator and 0.161 g of tris [ 2- (dimethylamino) ethyl] amine (Me 6 -TREN) as ligand.
• BA butyl acrylate
• MEK methyl ethyl ketone
• MeOH methanol
• DBDEHD 2,6-dibromo diethylheptanedionate
• Me 6 -TREN 2,6-dibromo diethylheptanedionate
• the polymerization of the second block could be carried out by feeding 558 g of methyl methacrylate (MMA) and 0.815 g of NaCl. To reduce the viscosity of the reaction solution was added another 100 ml of DMSO. The increase of the external temperature to 80 ° C ensured the complete monomer conversion, which was determined by solids content and 1 H-NMR spectroscopy. The product was recovered by precipitation in methanol and drying in a vacuum oven.
• MMA methyl methacrylate
• NaCl NaCl
• the stirring magnet of the reaction apparatus was wrapped with a 12.5 cm long copper wire before successively 17.8 g of butyl acrylate (BA), 20 ml of DMSO, 0.10 g of 2,6-Dibromdiethylheptandionat (DBDEHD) as initiator and
• the triblock copolymers K2-1 and K2-2 were also prepared according to the above instructions for K2-3 and K2-4, respectively.
• thermoplastic molding compositions according to the invention
• thermoplastic molding compositions according to the invention, the respective components (SAN copolymer + triblock copolymer) were intimately mixed in an extruder (ZSK 30 twin-screw extruder from Werner & Pfleiderer) at a temperature of 220 ° C and corresponding moldings by injection molding at a mold temperature of 90 ° C generated.
• ZSK 30 twin-screw extruder from Werner & Pfleidererer
• the various triblock copolymers could be mixed homogeneously into all three SAN polymer matrices. Shares of the respective triblock copolymer of up to 20 wt .-%, based on the total amount of components K1 and K2, resulting in a transparent, clear composite material (Table 4 and Figure 1).
• thermoplastic molding compositions according to the invention in comparison to SAN copolymers
• Figure 1 shows photographs of composite materials of the SAN copolymer K1 -1 and the triblock copolymer K2-1.
• the proportion of triblock copolymer K2-1 is 0, 5, 10 and 20 wt .-%, based on the total amount of components K1 and K2.
• thermoplastic molding compositions according to the invention The investigation of the mechanical properties of the thermoplastic molding compositions according to the invention in comparison to the SAN copolymers used alone is shown in Tables 5 and 6.
• the SAN copolymers K1 -2 and K1 -1 show no elongation at break.
• Table 6 shows that very good elongation values of 15 and 12% before fracture for the novel thermoplastic molding compositions of SAN copolymers K1 -2 and K1 -1 and the triblock copolymer K2-2 were obtained. At the same time, the modulus of elasticity was reduced only slightly to an acceptable level.

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• 2014
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